CN107983529B - Method for extracting rare earth from deep sea sediment - Google Patents
Method for extracting rare earth from deep sea sediment Download PDFInfo
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- CN107983529B CN107983529B CN201711202665.0A CN201711202665A CN107983529B CN 107983529 B CN107983529 B CN 107983529B CN 201711202665 A CN201711202665 A CN 201711202665A CN 107983529 B CN107983529 B CN 107983529B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B7/00—Combinations of wet processes or apparatus with other processes or apparatus, e.g. for dressing ores or garbage
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
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Abstract
The invention discloses a method for extracting rare earth from deep sea sediments, which comprises the following steps: (1) carrying out desliming pretreatment on the deep-sea sediment; (2) carrying out ore grinding and flotation separation on the product after desliming pretreatment to obtain flotation rough concentrate; (3) leaching the flotation rough concentrate to obtain a leaching solution enriched with heavy rare earth and leaching residue containing light rare earth; (4) and (4) carrying out flotation separation on the leached residues after scrubbing to obtain rare earth concentrate. The method has the advantages of mild selecting and smelting conditions, low energy consumption, high efficiency, reduction of the discharge amount of waste liquid and waste residue, environmental friendliness and cyclic regeneration and utilization of the dilute acid used in the leaching operation.
Description
Technical Field
The invention belongs to the technical field of rare earth, and particularly relates to a method for extracting rare earth from deep sea sediments.
Background
Rare earth is non-renewable important natural resource, the content of the rare earth in the earth crust is not rare, and the abundance of the rare earth in the earth crust is 200 multiplied by 10-6The abundance of the elements is higher than that of gold, platinum, tungsten, molybdenum, cobalt, lead, zinc and the like. About 250 rare earth minerals have now been found, of which only 10 are valuable for mining, such as bastnaesite, monazite and the like.
The rare earth elements are applied to the traditional industrial fields of metallurgy, machinery, petroleum and the like in the economic society, for example, the rare earth oxide CeO is blown into molten steel2The powder can improve the strength and toughness of the steel; the conductivity can be obviously improved by adding a proper amount of La into the aluminum conductor; la and Sm can accelerate the catalytic cracking of petroleum and improve the yield of gasoline; after the rare earth is applied to crops, the yield can be improved, and the disaster resistance can be enhanced. The rare earth functional material is also used in aerospace and national defenseThe technology is widely applied to the prior art.
With the increasing desire for rare earths in various countries, terrestrial rare earth resources have not met human needs. Currently, the globally exploitable rare earth ore is mainly concentrated in several countries such as China, America, Russia, Australia and the like. However, countries such as the united states and australia have stopped domestic rare earth mining and purchased from china for future use, and japan also stores available rare earth resources purchased from china for 20 years on the seabed. The rare earth industry in China occupies the first 4 resources in the world, namely the reserve, the yield, the sales and the usage. For example, the rare earth reserves of 2009 in China are 360 multiplied by 104t, 36% of the world, and the yield is 12X 104t, 97% of the world. At present, China bears over 90% of the world market supply by 23% of rare earth resources. In 2012, the export amount of rare earth in China reaches 9267t, and the main export countries are Japan, France and America.
However, after long-term ultra-strength mining, the reserve of rare earth and the guarantee period of the rare earth are continuously reduced, so that the development of marine rare earth is increasingly emphasized. In 2011, about 880 × 10 of the island in the middle of the pacific ocean including hawaii was discovered in gargtai hao japan4km2About 240X 10 near Taxiti island in the sea and southeast4km2Sea sediment contains high-concentration rare earth, and the recoverable yield of the sediment is about 1000 times that of land sediment. The rare earth contained in the submarine sediments brings prospect to people, so that people pay attention to the understanding of the submarine sediments, and the distribution of the rare earth is of great importance.
Deep sea sediments have the following characteristics: 1. the total content of rare earth is high, and the content of medium and heavy rare earth elements is high; 2. contains very low concentrations of the radioactive elements thorium and uranium.
The occurrence state and leaching research of rare earth in the deep sea clay in the middle of the pacific (No. 4 of volume 33 of Chinese rare earth journal 2015.8) shows the occurrence state of rare earth elements in the deep sea clay in the middle of the pacific, and simultaneously researches a process for leaching the rare earth by using a sulfuric acid solution, and examines the influence of factors such as sulfuric acid concentration, leaching time, liquid-solid ratio, leaching temperature and the like on the Y leaching rate in the deep sea clay.
From the pacific oceanThe study on the extraction and recovery of yttrium from deep sea clay leachate (china rare earth academy 2016.2 volume 34, phase 1) teaches a process for extracting rare earth from sediments by leaching with dilute acid: direct extraction and recovery of Y from high-concentration HCl leachate by using novel extractant P5353+And investigating the influence of the acidity of the feed liquid, the concentration of the extracting agent, the extraction time and the phase ratio on the extraction and the influence of HCl and sulfuric acid stripping agents on the stripping.
By the methods disclosed in the above documents, the deep-sea sediments are not pre-enriched or treated, the rare earth elements are directly extracted by adopting a hydrometallurgical leaching process, a large amount of waste acid liquid and waste residues are generated in the leaching process, the method is not environment-friendly, the problem of environmental protection treatment is brought when the rare earth is extracted from the deep-sea sediments, and the production cost, particularly the pollution treatment cost, is greatly increased.
Disclosure of Invention
The invention aims to provide a method for extracting rare earth from deep-sea sediments, which realizes the extraction of rare earth elements with high efficiency and low consumption and reduces the discharge amount of waste liquid and waste residues.
The invention realizes the purpose through the following technical scheme:
a method for extracting rare earth from deep sea sediment comprises the following steps:
(1) carrying out desliming pretreatment on the deep-sea sediment;
(2) carrying out ore grinding and flotation separation on the product subjected to desliming pretreatment in the step (1) to obtain flotation rough concentrate;
(3) leaching the flotation rough concentrate obtained in the step (2) to obtain a leaching solution enriched with heavy rare earth and leaching residue containing light rare earth;
(4) and (4) scrubbing the leaching residue obtained in the step (3) and then performing flotation separation to obtain rare earth concentrate.
Further, in the step (1), a desliming pretreatment is performed through a cyclone.
Further, in the step (2) and the step (4), the inhibitor adopted in the flotation separation operation is modified water glass, and the collector is WR-80; the modified water glass is prepared by compounding water glass with the modulus of 2.6 and sodium hexametaphosphate according to the mass ratio of 999:1Preparing; WR-80 is sodium oleate and C7-9The mixture of the sodium hydroximate and the tween is compounded by the three materials according to the mass ratio of 90:9: 1.
Further, in the step (3), the flotation rough concentrate is leached after being mixed and stirred with dilute acid.
Further, in the step (3), the leaching solution is used for extracting heavy rare earth raw materials and preparing apatite products.
The invention has the beneficial effects that:
the deep-sea sediment is subjected to desliming pretreatment, so that the floating grade is improved, the floating amount is greatly reduced, most of fine mud influencing flotation is removed, and grinding-flotation separation is performed, so that the high enrichment ratio of flotation rough concentrate is realized, the feeding of subsequent leaching operation is greatly reduced, the leaching efficiency is improved, and the discharge of waste liquid and leaching residue is reduced. Therefore, the method has the advantages of mild selecting and smelting conditions, low energy consumption, high efficiency, reduction of the discharge amount of waste liquid and waste residue, environmental friendliness and cyclic regeneration and utilization of the dilute acid used in the leaching operation.
Drawings
FIG. 1 is a process flow diagram of the present invention for extracting rare earth from deep sea sediments.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described with reference to the accompanying drawings and specific embodiments.
Example 1
(1) Aiming at 765ppm of deep sea sediment TREO in certain field of Pacific ocean, desliming pretreatment is carried out through a cyclone, the TREO content in the product reaches 1080ppm, and the operation recovery rate is 65%;
(2) grinding the product subjected to the desliming pretreatment in the step (1), then carrying out size mixing until the concentration is 35%, adding modified water glass as an inhibitor, using WR-80 as a collecting agent, and carrying out rough and fine flotation operation at normal temperature, wherein the consumption of the rough-flotation modified water glass is 2500 g/t & ore feeding, the consumption of the collecting agent is 1500 g/t & ore feeding, the consumption of the scavenging operation modified water glass is 500 g/t & ore feeding, the consumption of the collecting agent is 500 g/t & ore feeding, the fine flotation is blank fine flotation, and the flotation rough concentrate with the REO grade of 1.03% and the operation recovery rate of 70% is obtained through flotation separation;
(3) mixing and stirring dilute acid and the flotation rough concentrate obtained in the step (2), controlling the acid excess coefficient to be 1.2 and the liquid-solid ratio L/S to be 3:1, and leaching at the temperature of 40 ℃ to obtain heavy rare earth-enriched leaching solution and light rare earth-containing leaching residue; the extract can be used for extracting heavy rare earth raw materials and preparing apatite products (such as phosphate fertilizer or gypsum) by a fractional precipitation method; the REO grade of the leaching residue is 2.48 percent, and the operation recovery rate reaches 89 percent;
(4) scrubbing the leaching residue obtained in the step (3), then, size mixing to reach a concentration of 35%, adding modified water glass as an inhibitor, and performing primary and secondary fine flotation operation at normal temperature by using WR-80 as a collecting agent, wherein the consumption of the modified water glass in the primary flotation is 1500 g/t & ore feeding, the consumption of the collecting agent is 550 g/t & ore feeding, the consumption of the modified water glass in the scavenging operation is 400 g/t & ore feeding, the consumption of the collecting agent is 120 g/t & ore feeding, the fine flotation is blank fine flotation, and the rare earth concentrate with the REO grade of 30% and the operation recovery rate of 75% is obtained through flotation separation.
In the step (2) and the step (4), the inhibitor adopted in the flotation separation operation is modified water glass, and the collecting agent is WR-80; the modified water glass is prepared by compounding water glass with the modulus of 2.6 and sodium hexametaphosphate according to the mass ratio of 999: 1; WR-80 is sodium oleate and C7-9The mixture of the sodium hydroximate and the tween is compounded by the three materials according to the mass ratio of 90:9: 1.
Example 2
(1) Aiming at the condition that TREO (Total NOx emission) of deep sea sediments in a certain field of the Pacific ocean is 950ppm, desliming pretreatment is carried out through a cyclone, the TREO content in a product reaches 1280ppm, and the operation recovery rate is 68%;
(2) grinding the product subjected to the desliming pretreatment in the step (1), then carrying out size mixing until the concentration is 35%, adding modified water glass as an inhibitor, using WR-80 as a collecting agent, and carrying out rough and fine flotation operation at normal temperature, wherein the consumption of the rough-flotation modified water glass is 3000 g/t & ore feeding, the consumption of the collecting agent is 1800 g/t & ore feeding, the consumption of the scavenging operation modified water glass is 600 g/t & ore feeding, the consumption of the collecting agent is 500 g/t & ore feeding, the fine flotation is blank fine flotation, the grade of REO is 1.33% through flotation separation, and the operation recovery rate is 72% of the rough flotation concentrate;
(3) mixing and stirring dilute acid and the flotation rough concentrate obtained in the step (2), controlling the acid excess coefficient to be 1.5 and the liquid-solid ratio L/S to be 3:1, and leaching at the temperature of 60 ℃ to obtain heavy rare earth-enriched leaching solution and light rare earth-containing leaching residue; the extract can be used for extracting heavy rare earth raw materials and preparing apatite products (such as phosphate fertilizer or gypsum) by a fractional precipitation method; the REO grade of the leaching residue is 2.68 percent, and the operation recovery rate reaches 91.5 percent;
(4) scrubbing the leaching residue obtained in the step (3), then, size mixing to achieve a concentration of 35%, adding modified water glass as an inhibitor, using WR-80 as a collecting agent, and performing primary and secondary fine flotation operation at normal temperature, wherein the consumption of the modified water glass in the primary flotation is 1800 g/t & ore feeding, the consumption of the collecting agent is 750 g/t & ore feeding, the consumption of the modified water glass in the scavenging operation is 500 g/t & ore feeding, the consumption of the collecting agent is 150 g/t & ore feeding, the fine flotation is blank fine flotation, and the rare earth concentrate with the REO grade of 32.5% and the operation recovery rate of 76.8% is obtained through flotation separation.
In the step (2) and the step (4), the inhibitor adopted in the flotation separation operation is modified water glass, and the collecting agent is WR-80; the modified water glass is prepared by compounding water glass with the modulus of 2.6 and sodium hexametaphosphate according to the mass ratio of 999: 1; WR-80 is sodium oleate and C7-9The mixture of the sodium hydroximate and the tween is compounded by the three materials according to the mass ratio of 90:9: 1.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (4)
1. A method for extracting rare earth from deep sea sediments is characterized in that: the method comprises the following steps:
(1) carrying out desliming pretreatment on the deep-sea sediment;
(2) carrying out ore grinding and flotation separation on the product subjected to desliming pretreatment in the step (1) to obtain flotation rough concentrate;
(3) leaching the flotation rough concentrate obtained in the step (2) to obtain a leaching solution enriched with heavy rare earth and leaching residue containing light rare earth;
(4) scrubbing the leaching residue obtained in the step (3), and then performing flotation separation to obtain rare earth concentrate;
in the step (2) and the step (4), the inhibitor adopted in the flotation separation operation is modified water glass, and the collector is WR-80; the modified water glass is prepared by compounding water glass with the modulus of 2.6 and sodium hexametaphosphate according to the mass ratio of 999: 1; the WR-80 is a mixture of sodium oleate, C7-9 sodium hydroxamate and Tween, and the three materials are compounded according to the mass ratio of 90:9: 1.
2. The method for extraction of rare earths from deep sea sediments according to claim 1, characterized in that: in the step (1), desliming pretreatment is performed through a cyclone.
3. The method for extraction of rare earths from deep sea sediments according to claim 1, characterized in that: in the step (3), the flotation rough concentrate is leached after being mixed and stirred by dilute acid.
4. The method for extraction of rare earths from deep sea sediments according to claim 1, characterized in that: in the step (3), the immersion liquid is used for extracting heavy rare earth raw materials and preparing apatite products.
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| CN111359774B (en) * | 2020-03-17 | 2022-05-31 | 矿冶科技集团有限公司 | Method for recovering rare earth minerals from submarine sediments |
| CN115094230B (en) * | 2022-06-23 | 2024-03-08 | 中国地质科学院矿产综合利用研究所 | Method for extracting rare earth, phosphorus and manganese elements from deep sea rare earth-rich sediment |
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| CN1164367C (en) * | 2001-09-11 | 2004-09-01 | 上海第二工业大学 | Bastnaesite dressing process |
| CN1403204A (en) * | 2001-09-11 | 2003-03-19 | 上海第二工业大学 | RE mineral floating process |
| RU2438795C1 (en) * | 2010-07-13 | 2012-01-10 | Федеральное государственное унитарное предприятие "Государственный научно-исследовательский, проектный и конструкторский институт горного дела и металлургии цветных металлов" ФГУП "Гипроцветмет" | Method of flotation concentration of rare-earth metal and tin ores |
| EP2500102B1 (en) * | 2011-03-15 | 2015-11-11 | Primetals Technologies Germany GmbH | Flotation apparatus with a fluid distribution element for creating a fluid flow towards the froth collecting device |
| CN105331812B (en) * | 2014-07-31 | 2018-03-16 | 有研稀土新材料股份有限公司 | The method of synthetical recovery phosphorus and rare earth from phosphorus ore containing mengite 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 |
| CN106801153B (en) * | 2016-12-30 | 2019-01-29 | 包头稀土研究院 | A kind of method of low cost enrichment high-grade mixed rare earth concentrates |
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