CN109161702B - Method for selectively extracting non-cerium rare earth in mixed rare earth concentrate - Google Patents
Method for selectively extracting non-cerium rare earth in mixed rare earth concentrate Download PDFInfo
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- CN109161702B CN109161702B CN201811024529.1A CN201811024529A CN109161702B CN 109161702 B CN109161702 B CN 109161702B CN 201811024529 A CN201811024529 A CN 201811024529A CN 109161702 B CN109161702 B CN 109161702B
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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- C22B1/02—Roasting processes
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- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
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Abstract
The invention discloses a method for selectively extracting non-cerium rare earth from mixed rare earth concentrate, which comprises the following steps: carrying out air oxidation roasting on the mixed rare earth concentrate containing the bastnaesite and the monazite for 1-3 hours at the temperature of 400-650 ℃ to generate thermal oxidation roasted ore; oxidizing trivalent cerium in the fluorine-carbon-cerium rare earth in the mixed rare earth concentrate into tetravalent cerium; uniformly mixing the thermal oxidation roasted ore and concentrated sulfuric acid, roasting at the low temperature of 800 ℃ for 0.5-2 hours at 150 ℃, and dissolving the thermal oxidation roasted ore by using the concentrated sulfuric acid to form cerium phosphate and trivalent rare earth sulfate; the formed cerium phosphate and trivalent rare earth sulfate are subjected to water leaching and size mixing and solid-liquid separation to obtain a cerium-less rare earth sulfate solution and a cerium phosphate enrichment. The invention fully combines the technical advantages of oxidizing and roasting the bastnaesite to form high-valence cerium and decomposing the monazite with sulfuric acid to form phosphoric acid, and realizes the fixation of cerium and phosphorus resources and the selective development of non-cerium rare earth by utilizing the high-stability cerium phosphate.
Description
Technical Field
The invention relates to a hydrometallurgy technology, in particular to a method for selectively extracting non-cerium rare earth from mixed rare earth concentrate.
Background
The Baiyunebo ore is the largest rare earth ore in China. The rare earth mineral mainly comprises bastnaesite and monazite, and is a mineral which is accepted in the world and is difficult to select and smelt. In the existing production process, concentrated sulfuric acid high-temperature roasting decomposition process and concentrated alkali liquor decomposition process are mainly adopted for treatment. In recent years, the 'three wastes' treatment and the comprehensive utilization of resources such as fluorine, phosphorus and the like in the rare earth concentrate smelting industry become research hotspots, and the formed mineral disposal method is almost the integration and improvement of the traditional smelting process, and although the method has various characteristics, the method is established on the technical guide of extracting all 15 rare earth elements.
The rare earth elements in the Baiyunebo rare earth mineral are mainly light rare earth elements such as lanthanum, cerium, praseodymium, neodymium and the like, wherein the lanthanum accounts for about 25 percent, the cerium accounts for about 50 percent, the praseodymium and the neodymium account for 23 percent, and the rest medium and heavy rare earth elements account for 2 percent. In back-end application, the praseodymium and neodymium are used in a large amount, the market gap is also large, and lanthanum is basically balanced, so that a cerium product is excessive and is overstocked in a large amount. In the mineral smelting process, the elements are combined, extracted and developed, and the extraction cost of each ton of single rare earth oxide reaches 3-3.5 ten thousand yuan. And the market price of the cerium oxide product is kept between 0.8 and 1.2 ten thousand yuan for a long time, which causes serious enterprise loss. The excess capacity formed for extracting high-value resources (praseodymium neodymium) cannot be radically cured for a long time.
The bayan obo rare earth concentrate contains valuable resources such as fluorine, phosphorus and the like besides rare earth resources. In the existing smelting process, phosphorus resources in minerals are not utilized. For example, in the concentrated sulfuric acid high-temperature roasting process, phosphorus and added iron powder form a compound which enters radioactive waste residue and cannot be reused; in the alkali decomposition process, phosphorus resources in the form of sodium phosphate and sodium hydroxide, sodium fluoride, sodium carbonate, even sodium sulfate and the like form mixed alkali wastewater, and the mixed alkali wastewater is difficult to recycle.
Disclosure of Invention
The invention aims to provide a method for selectively extracting non-cerium rare earth from mixed rare earth concentrate, which has the innovation points that: (1) and oxidizing cerium in the fluorine-carbon cerium rare earth in the mixed rare earth concentrate to tetravalent cerium by air oxidizing roasting. (2) The concentrated sulfuric acid is used for fast dissolving, oxidizing and roasting to form rare earth compounds, and ceric sulfate and trivalent rare earth sulfate are formed. (3) The cerous sulfate formed by dissolving the phosphoric acid decomposed from monazite and sulfuric acid and air moisture are dissolved by using low-temperature roasting of sulfuric acid to form stable cerous phosphate, and sulfuric acid is generated to release oxygen. Under the action of sulfuric acid, the rest trivalent rare earth is fully dissolved and decomposed, and then a cerium-less rare earth sulfate solution and a high cerium phosphate concentrate are obtained by water extraction, so that the selective extraction and balanced development of non-cerium rare earth are realized, and cerium and phosphorus resources are protected. The main reaction equation is:
(1) air oxidizing roasting
2REF3·RE2(CO3)3＝RE2O3+3REOF+REF3+6CO2↑
2CeF3·Ce2(CO3)3+3/2O2＝3CeO2+3CeOF2+6CO2↑
(2) Roasting at low temperature with sulfuric acid
RE2O3+3H2SO4＝RE2(SO4)3+3H2O
CeO2+2H2SO4＝Ce(SO4)2+2H2O
3REOF+REF3+6H2SO4＝2RE2(SO4)3+6HF↑+3H2O
CeOF2+2H2SO4＝Ce(SO4)2+2HF↑+H2O
2REPO4+3H2SO4＝RE2(SO4)3+2H3PO4
4Ce(SO4)2+4H3PO4+2H2O＝4CePO4+4H2SO4+O2↑
The technical scheme is as follows:
the mixed rare earth concentrate of the bastnaesite and the monazite is subjected to air oxidation roasting for 1 to 3 hours at the temperature of 400-650 ℃. The oxidized roasted ore and concentrated sulfuric acid with the mass percentage content of more than 85 percent are uniformly mixed according to the weight ratio of 1:0.6-1.2, and are roasted for 0.5-2 hours at the temperature of 150-. And (3) carrying out water leaching and size mixing on the formed roasted sulfuric acid ore and water according to the weight ratio of 1: 4-1: 7, and carrying out solid-liquid separation to obtain a cerium-less rare earth sulfate solution and a cerium phosphate concentrate.
The invention fully combines the technical advantages of oxidizing and roasting the bastnaesite to form high-valence cerium and decomposing the monazite with sulfuric acid to form phosphoric acid, and utilizes the high-stability cerium phosphate to realize the fixation of cerium and phosphorus resources and the high-selectivity development of non-cerium rare earth.
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FIG. 1 is a flow chart of a method for selectively extracting non-cerium rare earth from a mixed rare earth concentrate according to the present invention.
Detailed Description
The following description sufficiently illustrates specific embodiments of the invention to enable those skilled in the art to practice and reproduce it.
Fig. 1 is a flow chart of the method for selectively extracting non-cerium rare earth from mixed rare earth concentrate according to the present invention. The method comprises the following specific steps:
step 1: carrying out air oxidation roasting on the mixed rare earth concentrate containing the bastnaesite and the monazite at the temperature of 400-650 ℃ for 1-3 hours to generate an oxidation roasted ore; oxidizing trivalent cerium in the fluorine-carbon-cerium rare earth in the mixed rare earth concentrate into tetravalent cerium;
step 2: the thermal oxidation roasted ore and concentrated sulfuric acid with the mass percentage content of more than 85 percent are mixed according to the weight ratio of 1:0.6 to 1.2, roasting at the temperature of 150 ℃ and 800 ℃ for 0.5 to 2 hours, and dissolving, oxidizing and roasting by using concentrated sulfuric acid to form stable cerium phosphate and trivalent rare earth sulfate (sulfuric acid roasted ore);
and step 3: the weight ratio of the formed cerium phosphate and trivalent rare earth sulfate to water is 1: 4-1: 7 water leaching and size mixing, and solid-liquid separation to obtain a cerium-less rare earth sulfate solution and a cerium phosphate enrichment.
The rare earth sulfate solution with less cerium and the enrichment of the cerium phosphate are obtained by water extraction, thereby realizing the selective extraction and balanced development of non-cerium rare earth and protecting cerium and phosphorus resources.
Example 1
100g of bastnaesite and monazite mixed rare earth concentrate (REO: 64.0%, P)2O5: 6.8%) was air-oxidizing roasted at 550 c for 1 hour to form 85g of oxidizing roasted ore. The roasted ore is uniformly mixed with 68g of concentrated sulfuric acid with the mass percentage of 98 percent, and then roasted for 2 hours at the temperature of 150 ℃. The weight ratio of the formed sulfuric acid roasted ore to water is 1: 5, leaching roasted sulfuric acid ore with water, pulping, and performing solid-liquid separation to obtain 590ml of cerium-less rare earth sulfate solution and cerium phosphate enrichment, wherein the cerium-less rare earth sulfate solution is ThO20.2g/L of CeO2The dissolution rate is 48.0 percent, P2O5The dissolution rate was 9.4%.
Example 2
100g of bastnaesite and monazite mixed rare earth concentrate (REO: 52.0%, P)2O5: 8.9%) was air-oxidizing calcined at 400 deg.c for 3 hours. 82.7g of the oxidized roasted ore formed was uniformly mixed with 74.4g of concentrated sulfuric acid having a mass percentage of 92%, and then roasted at 600 ℃ for 1 hour. The formed sulfuric acid roasted ore and water are subjected to water leaching and size mixing and solid-liquid separation according to the weight ratio of 1:6 to obtain 730ml of cerium-less rare earth sulfate solution and cerium phosphate enrichment, wherein the cerium-less rare earth sulfate solution ThO2＜0.01g/L，CeO2The dissolution rate is 20.0 percent, P2O5The dissolution rate was 3.2%.
Example 3
100g of bastnaesite and monazite mixed rare earth concentrate (REO: 63.5%, P)2O58.8%) was air-oxidizing roasted at 650 ℃ for 1 hour to form 86.5g of an oxidized roasted ore. The oxidized roasted ore is uniformly mixed with 103.8g of concentrated sulfuric acid with the mass percentage of 85 percent, and then roasted for 1.5 hours at the temperature of 300 ℃. The formed sulfuric acid roasted ore and water are mixed by water according to the weight ratio of 1:7Slurry and solid-liquid separation to obtain 880ml cerium-less rare earth sulfate solution and cerium phosphate concentrate, cerium-less rare earth sulfate solution ThO20.18g/l of CeO2The dissolution rate is 37.8 percent, P2O5The dissolution rate was 6.8%.
Example 4
1000g of bastnaesite and monazite mixed rare earth concentrate (REO: 61.9%, P)2O5: 10.7%) was air-oxidatively roasted at 500 c for 2 hours to form 837g of oxidatively roasted ore. Mixing the oxidized roasted ore with 753g of concentrated sulfuric acid with the mass percentage content of more than 92 percent uniformly, and roasting for 0.5 hour at 800 ℃. The formed sulfuric acid roasted ore and water are subjected to water leaching and size mixing and solid-liquid separation according to the weight ratio of 1:4 to obtain 5000ml of cerium-less rare earth sulfate solution and cerium phosphate enrichment, and the cerium-less rare earth sulfate water leaching solution ThO2＜0.01g/L，CeO2The dissolution rate is 20.6 percent, P2O5The dissolution rate was 4.6%.
It should be understood that the above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of changes or substitutions within the technical scope of the present invention, and the present invention should be covered thereby. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (3)
1. A method for selectively extracting non-cerium rare earth from mixed rare earth concentrate comprises the following steps:
carrying out air oxidation roasting on the mixed rare earth concentrate containing the bastnaesite and the monazite at the temperature of 400-650 ℃ for 1-3 hours to generate an oxidation roasted ore; oxidizing trivalent cerium in the fluorine-carbon-cerium rare earth in the mixed rare earth concentrate into tetravalent cerium;
uniformly mixing the oxidized roasted ore and concentrated sulfuric acid, roasting at the low temperature of 150-800 ℃ for 0.5-2 hours to form sulfuric acid roasted ore, and dissolving the oxidized roasted ore by utilizing the concentrated sulfuric acid to form cerium phosphate and trivalent rare earth sulfate;
and carrying out water leaching and size mixing on the formed sulfuric acid roasted ore and water, and carrying out solid-liquid separation to obtain a cerium-less rare earth sulfate solution and a cerium phosphate enrichment.
2. The method for selectively extracting non-cerium rare earth in the mixed rare earth concentrate as claimed in claim 1, wherein the oxidized roasted ore and concentrated sulfuric acid with a mass percentage of more than 85% are mixed according to a weight ratio of 1:0.6 to 1.2 are mixed evenly.
3. The method for selectively extracting non-cerium rare earth elements from a misch metal concentrate as claimed in claim 1, wherein the weight ratio of the roasted sulfuric acid ore to water is 1: 4-1: 7, soaking and pulping in water.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102031363A (en) * | 2011-01-06 | 2011-04-27 | 中冶东方工程技术有限公司 | Multi-stage roasting method for rare earth ore concentrate and equipment thereof |
| CN102051477A (en) * | 2010-12-15 | 2011-05-11 | 内蒙古科技大学 | Method for chemically separating bastnaesite and urdite from mixed rare earth concentrate |
| CN103045851A (en) * | 2013-01-17 | 2013-04-17 | 中国科学院长春应用化学研究所 | Technique for decomposing Baotou rare-earth ores |
| CN104862502A (en) * | 2014-02-20 | 2015-08-26 | 中国科学院过程工程研究所 | Cleaning smelting technology of bastnaesite and monazite mixed rare earth ore concentrate |
| CN105132682A (en) * | 2015-09-10 | 2015-12-09 | 中国科学院长春应用化学研究所 | Method for extracting and separating cerium, fluorine and phosphorus from sulfuric acid leaching solution of Baotou rare earth mine |
| CN106756128A (en) * | 2016-12-10 | 2017-05-31 | 包头稀土研究院 | A kind of method that low acid consumption mixed rare earth concentrates concentrated sulfuric acid is decomposed |
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- 2018-09-04 CN CN201811024529.1A patent/CN109161702B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051477A (en) * | 2010-12-15 | 2011-05-11 | 内蒙古科技大学 | Method for chemically separating bastnaesite and urdite from mixed rare earth concentrate |
| CN102031363A (en) * | 2011-01-06 | 2011-04-27 | 中冶东方工程技术有限公司 | Multi-stage roasting method for rare earth ore concentrate and equipment thereof |
| CN103045851A (en) * | 2013-01-17 | 2013-04-17 | 中国科学院长春应用化学研究所 | Technique for decomposing Baotou rare-earth ores |
| CN104862502A (en) * | 2014-02-20 | 2015-08-26 | 中国科学院过程工程研究所 | Cleaning smelting technology of bastnaesite and monazite mixed rare earth ore concentrate |
| CN105132682A (en) * | 2015-09-10 | 2015-12-09 | 中国科学院长春应用化学研究所 | Method for extracting and separating cerium, fluorine and phosphorus from sulfuric acid leaching solution of Baotou rare earth mine |
| CN106756128A (en) * | 2016-12-10 | 2017-05-31 | 包头稀土研究院 | A kind of method that low acid consumption mixed rare earth concentrates concentrated sulfuric acid is decomposed |
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