CN101451200A - Rare-earth enrichment recovery method from phosphorite - Google Patents
Rare-earth enrichment recovery method from phosphorite Download PDFInfo
- Publication number
- CN101451200A CN101451200A CNA2007101783776A CN200710178377A CN101451200A CN 101451200 A CN101451200 A CN 101451200A CN A2007101783776 A CNA2007101783776 A CN A2007101783776A CN 200710178377 A CN200710178377 A CN 200710178377A CN 101451200 A CN101451200 A CN 101451200A
- Authority
- CN
- China
- Prior art keywords
- phosphorus ore
- rare
- phosphoric acid
- rare earth
- 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.)
- Granted
Links
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 invention discloses a method for enriching and recovering rare earth from phosphorite, which drives a large quantity of rare earth elements to be enriched into a phosphate system and be separated and recovered by inhibiting loss of the rare earth in phosphogypsum through optimizing the technological conditions and adding a calcium sulphate crystal seed and/or an active additive on the premise of not changing the wet-method phosphate process. Compared with the prior art, the method controls proper technological conditions and particularly adds the calcium sulphate crystal seed and/or the active additive, can improve the crystalline morphology of the phosphogypsum, reduce the eutectic effect and the adsorption effect of phosphate rare earth and calcium sulphate, reduce enrichment of the phosphate rare earth and the calcium sulphate to the phosphogypsum, make the enrichment ratio of the rare earth in phosphate reach more than 80 percent, and be favorable for recovering the rare earth from the phosphate. Moreover, the method can meet the requirements of wet-method phosphate production, has simple technique and high content of rare earth in the phosphate, and can adopt proper technology to recover rare earth from the phosphate and realize effective combination of rare earth recovery technology and phosphorization technology.
Description
Technical field
The present invention relates to a kind of from phosphorus ore the method for rare-earth enrichment recovery, particularly decompose and contain the rare earth phosphorus ore and produce in the process phosphoric acid method of rare-earth enrichment recovery from phosphorus ore with sulfuric acid.
Background technology
The rare earth element of occurring in nature also has a sizable part and phosphatic rock and the symbiosis of phosphorite ore deposit except in tax the exists various rare-earth mineral.World's phosphorus ore total reserves is about 1,000 hundred million tons, is 0.05% estimation by the rare earth average content, and association rare earth total reserves can be 5,000 ten thousand tons in world's phosphorus ore.The rare earth that reclaims in the phosphorus ore is originated as a kind of potential rare earth, and is significant.
At present, according to the kind of used acid in the Wet-process Phosphoric Acid Production, the main method that reclaims rare earth in the world from phosphorus ore has: (1) nitrate method; (2) salt acid system; (3) sulfuric acid process.In general, the comprehensive rare earth that reclaims has the high characteristics of yield in the nitrophosphate fertilizer method technology, and to the pure phosphoric acid that contains rare earth, the rare earth yield can reach more than 85% from phosphorus ore, and from the phosphorus ore to the rareearth enriching material, total recovery can reach about 70%.In addition, this method is little to the phosphorous chemical industry process influence, and chemical raw material consumes low, so on-road efficiency is good.But nitrophosphate fertilizer preparation technology mainly is applicable to high-quality phosphate rock resource, and along with phosphate rock resource constantly is exploited, the world is just turning to low-quality phosphorus ore to the utilization of phosphorus at present.World's phosphorous chemical industry facts have proved that this method treatment process has no longer had economic advantages on low-quality phosphorus ore is handled.
Generate phosphoric acid and water-insoluble crystal of calcium sulfate with the sulfuric acid decomposing phosphate rock, this is the present main method of Wet-process Phosphoric Acid Production in the world.In leaching process, phosphorus ore middle-weight rare earths element enters phosphoric acid solution and influenced by leaching condition with the ratio that the generation precipitation enters phosphogypsum, therefore relates to and reclaims rare earth and two kinds of technologies of recovery rare earth from phosphogypsum from phosphoric acid.Various countries have mainly carried out the research of handling recovery rare earth the depleted phosphogypsum of back from the phosphorus ore sulfuric acid wet process at present.Russia has announced that in disclosed patent RU2225892C1 in 2002 a kind of sulfuric acid of employing 20-25% leaches the technology that reclaims the phosphogypsum middle-weight rare earths, adopt heating concentrated vitriol leach liquor again and add the crystal seed mode, impel crystallization to separate out rareearth enriching material, transfer nitric acid or rare earth chloride to nitrocalcite or calcium chloride processing again, filtrate the returning behind the filtration rare earth crystal is used for phosphogypsum and leaches.The technology that magnesium oxide or magnesiumcarbonate neutralization precipitation sulfuric acid middle-weight rare earths are adopted in the patent RU2158317 proposition that Russia announced in 2000, Russia proposes directly to handle the technology that the dissolving rareearth enriching material adopts oxalic acid precipitation again with nitric acid or hydrochloric acid in the patent RU2148019 that announced in 2000.Poland researchist has reported that also the employing dilute sulphuric acid leaches phosphogypsum, and leach liquor obtains to contain rare earth 10-18% enriched substance through evaporation concentration, adopts hydrofluoric acid precipitation or NPPA solvent extration to prepare Purity of Rare Earth greater than 40% enriched substance again.The J.S.Preston in South Africa proposes to adopt the rare nitric acid that adds nitrocalcite to leach rare earth from half water phosphogypsum slurry, leaching yield can reach 85%, adopt dibutyl butyl phosphonium salt Shellsol2325 from leach liquor, to extract again and reclaim rare earth, prepare 1600 kilogram 89-94% mishmetal altogether.Extract rare earth from phosphogypsum, though feasible technically, flow process is very complicated, and bigger difficulty is arranged economically.
At recovery trace rare-earth from sulfuric acid wet process phosphoric acid research is arranged also in the world, carry in the uranium process, take into account the recovery of rare earth but mainly concentrate on extraction.Under normal Wet-process Phosphoric Acid Production condition, the enrichment of phosphoric acid middle-weight rare earths only is 20%～30%.France Rhone-Poulenc Chimie de Base has invented a kind of from the process of phosphorus ore Wet-process phosphoric acid (WPPA), reclaim the method (US4636369) of metals such as uranium, yttrium, thorium and rare earth, this invention is pointed out, when phosphorus ore adopts sulfuric acid to decompose, uranium in the phosphorus ore dissolves fully and enters solution, and metals such as rare earth, yttrium and thorium only have minimal amounts of dissolved to enter solution in the acidolysis process.In order to realize the unified metals such as uranium and rare earth that reclaim from phosphoric acid solution, when the sulfuric acid decomposing phosphate rock, in ore pulp, introduce aluminum ion, iron ion, silicon ion or its hybrid ionic, can increase the solubleness of rare earth in solution, the highest enrichment of this rare earth only is 56% at present, and, directly influence the subsequent technique of phosphoric acid by wet process in production process of phosphoric acid because the silicon plasma of introducing is a detrimental impurity.
In a word, reclaiming the problem that exists in the trace rare-earth technology from phosphorus ore is: extract rare earth from phosphogypsum, though feasible technically, flow process is very complicated, and bigger difficulty is arranged economically; Reclaim rare earth from phosphoric acid, phosphoric acid middle-weight rare earths enrichment is lower, and research level does not meet technology and requirement economically only up to about 60% at present.
Summary of the invention
The objective of the invention is at low characteristics and the deficiencies in the prior art of China's phosphorus ore middle-weight rare earths content, abandon the method for expensive recovery rare earth from sour wet processing phosphorus ore waste-phosphogypsum, providing a kind of is to decompose with sulfuric acid to contain the method that the rare earth phosphorus ore is produced rare-earth enrichment recovery in the process phosphoric acid.Adopting active additive to suppress rare earth runs off in phosphogypsum, impel most of rare earth element to be enriched in the phosphoric acid system, guaranteed under the prerequisite that does not change the sulfuric acid wet process flow process, realized the low-cost comprehensive purpose that reclaims rare earth, realized that rare earth reclaims effective combination of technology and phosphorous chemical industry technology.
Purpose of the present invention is realized by following technical scheme:
A kind of from phosphorus ore the method for rare-earth enrichment recovery, this method is: handle at sulfuric acid wet process and contain in the process that the rare earth phosphorus ore prepares phosphoric acid, improve the enrichment of rare earth in phosphoric acid by adding calcium sulfate crystal seed and/or active additive, make most of rare-earth enrichment process Separation and Recovery in phosphoric acid.Concrete steps are as follows: add entry or phosphoric acid and stir the reaction of sizing mixing in certain temperature range in phosphorus ore, add calcium sulfate crystal seed and/or additive, add the vitriol oil then, stirring reaction 0.1～50 hour, ageing 0.01～50 hour, filtration obtains phosphoric acid and phosphogypsum, the enrichment of rare earth in phosphoric acid can reach more than 80%, even more than 90%, more even reach more than 95%, phosphogypsum water or weak acid scrubbing, the filtrate that obtains can be returned and size mixing.
The quality liquid-solid ratio that adds in phosphorus ore among this preparation method behind entry or the phosphoric acid is 1:1～10:1, preferred 3:1～6:1, and the phosphoric acid concentration that adds in phosphorus ore is 0.01wt%～40wt%P
2O
5, preferred 20wt%～25wt%.Add in phosphorus ore that the stirring reaction time is 0.5～8 hour behind entry or the phosphoric acid, preferred 1.5～3 hours.
Adding the calcium sulfate crystal seed is 0.1%～30% of phosphorus ore quality, preferred 10%～20%.Additive is organic additive and/or inorganic additives, wherein organic additive is sodium laurylsulfonate, Sodium dodecylbenzene sulfonate anion active additive, cetyl trimethylammonium bromide cation activity additive, at least a in polyacrylamide, polyoxyethylene glycol, the polyvinyl alcohol nonionic additives, optimization polypropylene acid amides, polyoxyethylene glycol, polyvinyl alcohol nonionic additives, inorganic additives are sodium polyphosphate, (NH
4)
2SO
4, Na
2SO
4, NaCl, NH
4Cl, NH
4NO
3, NaNO
3In at least a, preferred (NH
4)
2SO
4Additive, additive amount are the 0.0001wt%～8wt% of phosphorus ore, preferred 0.1wt%～3wt%.
The stirring reaction temperature is 20 ℃～85 ℃, preferred 50～75 ℃.The used sulfuric acid of decomposing phosphate rock is that concentration is 90%～98%H
2SO
4, add the metering of vitriolic chemical quality than being 0.85～1.30, preferred 1.05～1.10.Washing is 0.0001～3molL with dilute sulphuric acid concentration
-1, preferred 0.2～1molL
-1
In principle, to being applicable to phosphorus ore of the present invention without limits, as long as it contains rare earth element.But,, will influence the economy of method of the present invention if the content of rare earth element is too low.Usually, be applicable to that phosphorus ore middle-weight rare earths content of the present invention should be 0.01wt ‰ at least, to the upper limit of ree content without limits, content of rare earth REO after the enrichment in the phosphoric acid is 0.01-5g/L, adopt one or both method separation and Extraction in extraction process, chromes, ion exchange method precipitation, the crystallization process, obtain the mishmetal enriched substance.。
In the sulfuric acid wet process phosphorite process and nitrophosphate fertilizer method when handling phosphorus ore, rare earth mainly exists with the rare-earth phosphorate form, the solubility product constant of rare-earth phosphorate is less, easily eutectic and the adsorption because of calcium sulfate enters in the phosphogypsum in the sulfuric acid wet process process, thereby cause rare earth enrichment in phosphogypsum, therefore by the control suitable process conditions, particularly by adding tensio-active agent, can improve the crystal habit of phosphogypsum, reduce eutectic and adsorption, minimizing is beneficial to and reclaims rare earth from phosphoric acid to the phosphogypsum enrichment.
Enrichment=the be enriched to total amount of rare earth in the rare earth/phosphorus ore in the phosphoric acid.
Effect of the present invention and advantage are:
At the low characteristics of China's phosphorus ore middle-weight rare earths content, abandon the method for expensive recovery rare earth from sour wet processing phosphorus ore waste-phosphogypsum, proposing to adopt the promoting agent additive to suppress rare earth first runs off in phosphogypsum, impel most of rare earth element to be enriched in thinking in the phosphoric acid system, guaranteed under the prerequisite that does not change the sulfuric acid wet process flow process, realized the low-cost comprehensive purpose that reclaims rare earth.Traditional sulfuric acid wet process is handled in the phosphorite process, rare earth element in phosphogypsum the enrichment ratio more than 70%, when reducing the enrichment ratio of rare earth in phosphogypsum, take into account the stability of phosphorous chemical industry production process technology condition, reduce the influence that the rare earth removal process is handled phosphorus ore, realize that rare earth reclaims effective combination of technology and phosphorous chemical industry technology.Compared with prior art, the present invention is by the control suitable process conditions, particularly by adding calcium sulfate crystal seed and/or active additive, can improve the crystal habit of phosphogypsum, reduce the eutectic and the adsorption of rare earth, reduce it, help from phosphoric acid, reclaiming rare earth to the phosphogypsum enrichment.The present invention can satisfy the requirement of Wet-process Phosphoric Acid Production, and technology is simple, and phosphoric acid middle-weight rare earths content height adopts extraction process or precipitated crystal method separation and Extraction, obtains the mishmetal enriched substance, realizes that rare earth reclaims effective combination of technology and phosphorous chemical industry technology.
Concrete embodiment
Below in conjunction with embodiment the present invention further is described:
Embodiment 1:
Under 85 ℃, get the phosphorus ore 100g that contains rare earth 5.51wt ‰, be that 4:1 adds 5%P by liquid-solid ratio
2O
5Phosphoric acid, stirring reaction 1.5 hours, add calcium sulfate crystal seed 10g (for phosphorus ore quality 10%) and 0.1g (consumption be phosphorus ore 0.1%) Macrogol 4000 additive, slowly add stoichiometric ratio then and be 0.85 sulfuric acid, stirring reaction 40 hours, ageing 0.1 hour is filtered and is obtained phosphoric acid solution and phosphogypsum, and water washs phosphogypsum.Content of rare earth REO after the enrichment in the phosphoric acid is 1.10g/L, and the amount that rare earth enters in the phosphoric acid accounts for 80.1% of phosphorus ore middle-weight rare earths total amount.Adopt extraction process or precipitated crystal method separation and Extraction, obtain the mishmetal enriched substance.
Embodiment 2:
Under 70 ℃, get the phosphorus ore 100g that contains rare earth 1.28wt ‰, be that 4:1 adds 21%P by liquid-solid ratio
2O
5Phosphoric acid, stirring reaction 1.5 hours adds calcium sulfate crystal seed 5g and 0.3g Macrogol 4000 additive, slowly add stoichiometric ratio then and be 1.05 sulfuric acid, stirring reaction 0.5 hour, ageing 35 hours, filtration obtains phosphoric acid solution and phosphogypsum, and water washs phosphogypsum.Content of rare earth REO after the enrichment in the phosphoric acid is 0.25g/L, and the amount that rare earth enters in the phosphoric acid accounts for 80.19% of phosphorus ore middle-weight rare earths total amount.Adopt extraction process or precipitated crystal method separation and Extraction, obtain the mishmetal enriched substance.
Embodiment 3:
Under 70 ℃, get the phosphorus ore 100g that contains rare earth 0.53wt ‰, be that 4:1 adds 25%P by liquid-solid ratio
2O
5Phosphoric acid, stirring reaction 3 hours adds calcium sulfate crystal seed 10g and 0.2g polyacrylamide additive, slowly add stoichiometric ratio then and be 1.05 sulfuric acid, stirring reaction 2.5 hours stirs ageing 1 hour, filtration obtains phosphoric acid solution and phosphogypsum, uses 0.5molL
-1Sulfuric acid washs phosphogypsum.Content of rare earth REO after the enrichment in the phosphoric acid is 0.11g/L, and the amount that rare earth enters in the phosphoric acid accounts for 83.02% of phosphorus ore middle-weight rare earths total amount.Adopt extraction process or precipitated crystal method separation and Extraction, obtain the mishmetal enriched substance.
Embodiment 4:
Under 70 ℃, get and contain rare earth 5.51wt ‰ phosphorus ore 100g, be that 3:1 adds 21%P by liquid-solid ratio
2O
5Phosphoric acid, stirring reaction 3 hours adds calcium sulfate crystal seed 15g and 0.3g polyvinyl alcohol additive, slowly adds stoichiometric ratio then and be 1.05 sulfuric acid, stirring reaction 4.5 hours, ageing 5 hours is filtered and is obtained phosphoric acid solution and phosphogypsum, uses 1molL
-1Sulfuric acid washs phosphogypsum.Content of rare earth REO after the enrichment in the phosphoric acid is 1.57g/L, and the amount that rare earth enters in the phosphoric acid accounts for 85.65% of phosphorus ore middle-weight rare earths total amount.Adopt extraction process or precipitated crystal method separation and Extraction, obtain the mishmetal enriched substance.
Embodiment 5:
Under 70 ℃, get and contain rare earth 5.5wt ‰ phosphorus ore 100g, be that 3:1 adds 21%P by liquid-solid ratio
2O
5Phosphoric acid, stirring reaction 3 hours adds calcium sulfate crystal seed 15g and 0.3g Sodium dodecylbenzene sulfonate additive, slowly add stoichiometric ratio then and be 1.05 sulfuric acid, stirring reaction 4.5 hours, ageing 5 hours, filtration obtains phosphoric acid solution and phosphogypsum, uses 1molL
-1Sulfuric acid washs phosphogypsum.Content of rare earth REO after the enrichment in the phosphoric acid is 1.51g/L, and the amount that rare earth enters in the phosphoric acid accounts for 82.3% of phosphorus ore middle-weight rare earths total amount.Adopt extraction process or precipitated crystal method separation and Extraction, obtain the mishmetal enriched substance.
Embodiment 6:
Under 60 ℃, get and contain rare earth 1.28wt ‰ phosphorus ore 100g, be that 6:1 adds 21%P by liquid-solid ratio
2O
5Phosphoric acid, stirring reaction 5 hours adds calcium sulfate crystal seed 15g and 0.3g cetyl trimethylammonium bromide additive, slowly add stoichiometric ratio then and be 1.1 sulfuric acid, stirring reaction 15 hours, ageing 20 hours, filtration obtains phosphoric acid solution and phosphogypsum, uses 0.5molL
-1Sulfuric acid washs phosphogypsum.Content of rare earth REO after the enrichment in the phosphoric acid is 0.18g/L, and the amount that rare earth enters in the phosphoric acid accounts for 84.62% of phosphorus ore middle-weight rare earths total amount.Adopt extraction process or precipitated crystal method separation and Extraction, obtain the mishmetal enriched substance.
Embodiment 7:
Under 50 ℃, get and contain rare earth 1.28wt ‰ phosphorus ore 100g, be that 6:1 adds 21%P by liquid-solid ratio
2O
5Phosphoric acid, stirring reaction 5 hours adds calcium sulfate crystal seed 15g and 1.0g (NH
4)
2SO
4Additive slowly adds stoichiometric ratio and is 1.1 sulfuric acid then, stirring reaction 15 hours, and ageing 20 hours is filtered and is obtained phosphoric acid solution and phosphogypsum, uses 0.5molL
-1Sulfuric acid washs phosphogypsum.Content of rare earth REO after the enrichment in the phosphoric acid is 0.19g/L, and the amount that rare earth enters in the phosphoric acid accounts for 91.34% of phosphorus ore middle-weight rare earths total amount.Adopt extraction process or precipitated crystal method separation and Extraction, obtain the mishmetal enriched substance.
Embodiment 8:
Under 50 ℃, get and contain rare earth 1.28wt ‰ phosphorus ore 100g, be that 6:1 adds 21%P by liquid-solid ratio
2O
5Phosphoric acid, stirring reaction 5 hours adds calcium sulfate crystal seed 15g and 0.3g Macrogol 4000 additive, slowly adds stoichiometric ratio then and be 1.1 sulfuric acid, stirring reaction 15 hours, ageing 20 hours is filtered and is obtained phosphoric acid solution and phosphogypsum, uses 0.5molL
-1Sulfuric acid washs phosphogypsum.Content of rare earth REO after the enrichment in the phosphoric acid is 0.20g/L, and the amount that rare earth enters in the phosphoric acid accounts for 92.57% of phosphorus ore middle-weight rare earths total amount.Adopt extraction process or precipitated crystal method separation and Extraction, obtain the mishmetal enriched substance.
Embodiment 9:
Under 60 ℃, get the phosphorus ore 100g that contains rare earth 0.53wt%, be that 6:1 adds 21%P by liquid-solid ratio
2O
5Phosphoric acid, stirring reaction 3 hours adds calcium sulfate crystal seed 20g and 0.5g ammonium sulfate, 0.25g Macrogol 4000 additive, slowly add stoichiometric ratio then and be 1.05 sulfuric acid, stirring reaction 10 hours, ageing 20 hours, filtration obtains phosphoric acid solution and phosphogypsum, uses 2molL
-1Sulfuric acid washs phosphogypsum.Content of rare earth REO after the enrichment in the phosphoric acid is 0.85g/L, and the amount that rare earth enters in the phosphoric acid accounts for 95.65% of phosphorus ore middle-weight rare earths total amount.Adopt extraction process or precipitated crystal method separation and Extraction, obtain the mishmetal enriched substance.
Claims (12)
1. the method for a rare-earth enrichment recovery from phosphorus ore, it is characterized in that: handle at sulfuric acid wet process and contain in the process that the rare earth phosphorus ore prepares phosphoric acid, improve the enrichment of rare earth in phosphoric acid by adding calcium sulfate crystal seed and/or active additive, make most of rare-earth enrichment process Separation and Recovery in phosphoric acid.
2. according to claim 1 a kind of from phosphorus ore the method for rare-earth enrichment recovery, it is characterized in that: its concrete steps are: add entry and/or phosphoric acid and stir the reaction of sizing mixing in certain temperature range in phosphorus ore, add calcium sulfate crystal seed and/or active additive, add the vitriol oil then, stirring reaction 0.1～50 hour, ageing 0.01～50 hour, filtration obtains phosphoric acid and phosphogypsum, the enrichment of rare earth in phosphoric acid reaches more than 80%, phosphogypsum water or weak acid scrubbing, the filtrate that obtains can be returned and size mixing.
3. according to claim 2 a kind of from phosphorus ore the method for rare-earth enrichment recovery, it is characterized in that: in 20～85 ℃ of temperature ranges, in phosphorus ore, add entry and/or phosphoric acid stirring reaction, add calcium sulfate crystal seed and/or active additive, add the vitriol oil then, stirring reaction 0.5～20 hour, ageing 2～20 hours is filtered and is obtained phosphoric acid and phosphogypsum, and the enrichment of rare earth in phosphoric acid reaches more than 90%.
4. according to claim 2 a kind of from phosphorus ore the method for rare-earth enrichment recovery, it is characterized in that: in 50～75 ℃ of temperature ranges, in phosphorus ore, add dilute phosphoric acid and/or dilute sulphuric acid stirring reaction, add calcium sulfate crystal seed and/or active additive, add the vitriol oil then, stirring reaction 1～10 hour, ageing 5～20 hours is filtered and is obtained phosphoric acid and phosphogypsum, and the enrichment of rare earth in phosphoric acid reaches more than 95%.
5. according to claim 2 a kind of from phosphorus ore the method for rare-earth enrichment recovery, it is characterized in that: the quality liquid-solid ratio that adds in the phosphorus ore behind entry or the phosphoric acid is 1:1～10:1, preferred 3:1～6:1, the phosphoric acid concentration that adds in phosphorus ore is 0.01wt%～40wt%P
2O
5, preferred 20wt%～25wt%.
According to claim 2 or 3 or 5 described a kind of from phosphorus ore the method for rare-earth enrichment recovery, it is characterized in that: add in phosphorus ore that the stirring reaction time is 0.5～8 hour behind entry or the phosphoric acid, preferred 1.5～3 hours.
According to claim 1 or 2 or 6 described a kind of from phosphorus ore the method for rare-earth enrichment recovery, it is characterized in that: adding the calcium sulfate crystal seed is 0.1%～30% of phosphorus ore quality, preferred 10%～20%.
According to claim 1 or 2 or 6 described a kind of from phosphorus ore the method for rare-earth enrichment recovery, it is characterized in that: additive is organic additive and/or inorganic additives, wherein organic additive is sodium laurylsulfonate, Sodium dodecylbenzene sulfonate anion active additive, cetyl trimethylammonium bromide cation activity additive, at least a in polyacrylamide, polyoxyethylene glycol, the polyvinyl alcohol nonionic additives, optimization polypropylene acid amides, polyoxyethylene glycol, polyvinyl alcohol nonionic additives, inorganic additives are sodium polyphosphate, (NH
4)
2SO
4, Na
2SO
4, NaCl, NH
4Cl, NH
4NO
3, NaNO
3In at least a, preferred (NH
4)
2SO
4Additive, additive amount are the 0.0001wt%～8wt% of phosphorus ore, preferred 0.1wt%～3wt%.
According to claim 2 or 7 or 8 described a kind of from phosphorus ore the method for rare-earth enrichment recovery, it is characterized in that: the used sulfuric acid concentration of decomposing phosphate rock is 90wt%～98wt%H
2SO
4, add the metering of vitriolic chemical quality than being 0.85～1.30, preferred 1.00～1.10.
10. according to claim 2 a kind of from phosphorus ore the method for rare-earth enrichment recovery, it is characterized in that: it is 0.0001～3molL that dilute sulphuric acid, its concentration are used in washing
-1, preferred 0.2～1molL
-1
11. according to claim 1 a kind of from phosphorus ore the method for rare-earth enrichment recovery, it is characterized in that: phosphorus ore middle-weight rare earths content REO is 0.1wt ‰～5wt%, and the content of rare earth REO after the enrichment in the phosphoric acid is 0.01-5g/L.
12. according to claim 1 a kind of from phosphorus ore the method for rare-earth enrichment recovery, it is characterized in that: the phosphoric acid that will be enriched with rare earth adopts one or both method separation and Extraction in extraction process, chromes, ion exchange method precipitation, the crystallization process, obtains the mishmetal enriched substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101783776A CN101451200B (en) | 2007-11-29 | 2007-11-29 | Rare-earth enrichment recovery method from phosphorite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101783776A CN101451200B (en) | 2007-11-29 | 2007-11-29 | Rare-earth enrichment recovery method from phosphorite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101451200A true CN101451200A (en) | 2009-06-10 |
| CN101451200B CN101451200B (en) | 2011-04-20 |
Family
ID=40733688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101783776A Active CN101451200B (en) | 2007-11-29 | 2007-11-29 | Rare-earth enrichment recovery method from phosphorite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101451200B (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101979335A (en) * | 2010-12-02 | 2011-02-23 | 刘小南 | Process for recycling trace rare earth produced by treatment of waste residues and waste water of rare earth mine |
| CN102220488A (en) * | 2011-05-31 | 2011-10-19 | 北京矿冶研究总院 | Method for separating rare earth from phosphate ore |
| CN102442653A (en) * | 2010-09-30 | 2012-05-09 | 贵州大学 | Method for enriching P2O5 and rare-earth elements in low/middle-grade phosphorite |
| CN102639729A (en) * | 2010-09-14 | 2012-08-15 | 双子贸易开放式股份公司 | Method for extracting rare earth elements from phosphogypsum |
| CN103184356A (en) * | 2011-12-28 | 2013-07-03 | 北京有色金属研究总院 | Treatment method for rare earth phosphate rock and enrichment method for rare earth |
| CN103864037A (en) * | 2014-03-21 | 2014-06-18 | 昆明理工大学 | Method for removing magnesium from phosphorite and recycling rare earth element in phosphorite through industrial smoke |
| CN104724746A (en) * | 2015-02-15 | 2015-06-24 | 台夕市 | Method for recycling ardealite |
| CN104774125A (en) * | 2015-03-20 | 2015-07-15 | 台夕市 | Method for producing nitrogen-enriched sulfate fertilizer from phosphogypsum and recycling rare earth |
| CN104860288A (en) * | 2015-05-07 | 2015-08-26 | 深圳市芭田生态工程股份有限公司 | Method for preparing phosphoric acid by using wet method |
| CN105154689A (en) * | 2015-08-11 | 2015-12-16 | 贵州大学 | Method for separation and enrichment of rare earth in phosphorite |
| CN105525092A (en) * | 2014-09-30 | 2016-04-27 | 北京矿冶研究总院 | Method for removing phosphorus and calcium from rare earth-containing phosphorite by preferential leaching to enrich rare earth |
| CN106391293A (en) * | 2016-08-30 | 2017-02-15 | 北京矿冶研究总院 | Method for separating and enriching rare earth in phosphorite through mineral separation |
| CN107162843A (en) * | 2017-04-25 | 2017-09-15 | 长江师范学院 | The method that hot pickled mustard tube special fertilizer is produced with phosphate ore flotation tailings |
| CN109847716A (en) * | 2018-12-10 | 2019-06-07 | 哈尔滨工程大学 | It is a kind of using natural minerals be base extraction of uranium from seawater adsorbent and preparation method thereof |
| CN110408802A (en) * | 2019-09-04 | 2019-11-05 | 贵州理工学院 | A method of the leaching recovering rare earth of ardealite containing rare earth |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2535702B1 (en) * | 1982-11-10 | 1986-09-12 | Rhone Poulenc Chim Base | PROCESS FOR GLOBAL RECOVERY OF URANIUM, YTTRIUM, THORIUM AND RARE EARTH CONTAINED IN A PHOSPHATE ORE DURING THE PREPARATION OF PHOSPHORIC ACID BY WET |
| CN1257290C (en) * | 2002-12-10 | 2006-05-24 | 中国科学院长春应用化学研究所 | Method of extracting rare earth from apatite |
| CN100439239C (en) * | 2006-10-12 | 2008-12-03 | 贵州宏福实业开发有限总公司 | Method of reducing rare earth content in phosphoric acid |
-
2007
- 2007-11-29 CN CN2007101783776A patent/CN101451200B/en active Active
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102639729A (en) * | 2010-09-14 | 2012-08-15 | 双子贸易开放式股份公司 | Method for extracting rare earth elements from phosphogypsum |
| CN102442653A (en) * | 2010-09-30 | 2012-05-09 | 贵州大学 | Method for enriching P2O5 and rare-earth elements in low/middle-grade phosphorite |
| CN101979335A (en) * | 2010-12-02 | 2011-02-23 | 刘小南 | Process for recycling trace rare earth produced by treatment of waste residues and waste water of rare earth mine |
| CN102220488A (en) * | 2011-05-31 | 2011-10-19 | 北京矿冶研究总院 | Method for separating rare earth from phosphate ore |
| CN102220488B (en) * | 2011-05-31 | 2012-10-17 | 北京矿冶研究总院 | Method for separating rare earth from phosphate ore |
| WO2012163200A1 (en) * | 2011-05-31 | 2012-12-06 | 北京矿冶研究总院 | Method for separating rare earth from phosphorus ore |
| CN103184356A (en) * | 2011-12-28 | 2013-07-03 | 北京有色金属研究总院 | Treatment method for rare earth phosphate rock and enrichment method for rare earth |
| CN103184356B (en) * | 2011-12-28 | 2014-12-17 | 有研稀土新材料股份有限公司 | Treatment method for rare earth phosphate rock and enrichment method for rare earth |
| CN103864037A (en) * | 2014-03-21 | 2014-06-18 | 昆明理工大学 | Method for removing magnesium from phosphorite and recycling rare earth element in phosphorite through industrial smoke |
| CN103864037B (en) * | 2014-03-21 | 2016-08-17 | 昆明理工大学 | Industrial smoke is utilized to carry out phosphorus ore de-magging and the method reclaiming phosphorus ore rare earth elements |
| CN105525092A (en) * | 2014-09-30 | 2016-04-27 | 北京矿冶研究总院 | Method for removing phosphorus and calcium from rare earth-containing phosphorite by preferential leaching to enrich rare earth |
| CN105525092B (en) * | 2014-09-30 | 2017-10-27 | 北京矿冶研究总院 | Method for removing phosphorus and calcium from rare earth-containing phosphorite by preferential leaching to enrich rare earth |
| CN104724746B (en) * | 2015-02-15 | 2017-01-11 | 潍坊学院 | Method for recycling ardealite |
| CN104724746A (en) * | 2015-02-15 | 2015-06-24 | 台夕市 | Method for recycling ardealite |
| CN104774125A (en) * | 2015-03-20 | 2015-07-15 | 台夕市 | Method for producing nitrogen-enriched sulfate fertilizer from phosphogypsum and recycling rare earth |
| CN104860288A (en) * | 2015-05-07 | 2015-08-26 | 深圳市芭田生态工程股份有限公司 | Method for preparing phosphoric acid by using wet method |
| CN105154689A (en) * | 2015-08-11 | 2015-12-16 | 贵州大学 | Method for separation and enrichment of rare earth in phosphorite |
| CN106391293A (en) * | 2016-08-30 | 2017-02-15 | 北京矿冶研究总院 | Method for separating and enriching rare earth in phosphorite through mineral separation |
| CN107162843A (en) * | 2017-04-25 | 2017-09-15 | 长江师范学院 | The method that hot pickled mustard tube special fertilizer is produced with phosphate ore flotation tailings |
| CN109847716A (en) * | 2018-12-10 | 2019-06-07 | 哈尔滨工程大学 | It is a kind of using natural minerals be base extraction of uranium from seawater adsorbent and preparation method thereof |
| CN109847716B (en) * | 2018-12-10 | 2021-12-24 | 哈尔滨工程大学 | Natural mineral-based uranium extraction adsorbent from seawater and preparation method thereof |
| CN110408802A (en) * | 2019-09-04 | 2019-11-05 | 贵州理工学院 | A method of the leaching recovering rare earth of ardealite containing rare earth |
| CN110408802B (en) * | 2019-09-04 | 2022-01-25 | 贵州理工学院 | Method for leaching phosphogypsum containing rare earth and recovering rare earth |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101451200B (en) | 2011-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101451200B (en) | Rare-earth enrichment recovery method from phosphorite | |
| CN106830012B (en) | Method for producing high-quality sodium fluoride by using fluorine-containing wastewater as raw material | |
| AU2008286599B2 (en) | A metallurgical process for iron-rich monazite rare earth ore or concentrate | |
| CN102220488B (en) | Method for separating rare earth from phosphate ore | |
| CN102718200B (en) | Method for preparing industrial-grade phosphoric acid by decomposing mid-low-grade phosphorite with nitric acid | |
| CN103073061B (en) | Method for extracting tungsten and molybdenum in high molybdenum scheelite | |
| AU2016200606B2 (en) | A method for recovering phosphorus and rare earth from rare earth containing phosphorite | |
| CN110885090A (en) | Method for preparing battery-grade lithium carbonate by using lepidolite as raw material through one-step method | |
| CN102312089B (en) | Method for recovering rare earth from rare earth-containing phosphorite | |
| CN102828025B (en) | Method for extracting V2O5 from stone coal navajoite | |
| CN104745823B (en) | Method for recycling lithium from waste lithium ion battery | |
| CN102876889B (en) | Method for extracting rare earth from rare-earth-contained apatite ores | |
| CN108707748B (en) | Method for purifying stone coal pickle liquor and recovering aluminum, potassium and iron | |
| CN105238929B (en) | A kind of recovery of waste and old Nd-Fe-B permanent magnet material middle rare earth and utilization | |
| CN104099483A (en) | Preparation method of highly pure vanadium pentoxide | |
| CN101440430A (en) | Method for recycling rare earth from phosphogypsum leaching solution by fluoride precipitation method | |
| CN103274470B (en) | Method for preparing electronic-grade manganese sulfate by utilizing tungsten ore alkaline leaching slag | |
| CN103014379A (en) | Process for extracting vanadium from stone coal vanadium mine | |
| CN105366654A (en) | Wet process phosphoric acid purification technology of nonphosphate precipitation | |
| CN103787396A (en) | Method for preparing high-purity potassium alum and aluminum sulfate from alunite ore | |
| CN102992291A (en) | Method for preparing feed grade calcium hydrophosphate by phosphorite decomposition by hydrochloric acid | |
| CN104803417A (en) | Ammonium paratungstate and preparation method thereof | |
| CN115976324A (en) | Method for extracting aluminum-gallium-lithium system from coal gangue | |
| CN105441674A (en) | Method for comprehensive recovery of phosphor and rare earth from monazite-containing phosphate rock | |
| CN111850296B (en) | Method for recovering and preparing high-purity strontium compound from rare earth ore |
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 | ||
| 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. |