CN104498739A - Method for separating and recycling uranium, thorium and rare earth in rare earth mineral decomposition residue - Google Patents
Method for separating and recycling uranium, thorium and rare earth in rare earth mineral decomposition residue Download PDFInfo
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Abstract
The invention discloses a method for separating and recycling uranium, thorium and rare earth in rare earth mineral decomposition residue. The method comprises the following steps: carrying out acid leaching, carrying out pressure filtration, absorbing and recycling uranium by using anion resin, separating and recycling thorium and rare earth by suing cationic resin. The method specifically comprises the following steps: leaching rare earth mineral decomposition residue by using inorganic acid; carrying out pressure filtration on the leached slag, washing the leached slag to obtain a clear material solution, absorbing uranium element of the leached material solution by using 201*7 type resin, separating elements thorium and rare earth of an uranium-removal material by using 001*7 type resin, separating and purifying uranium, thorium and rare earth, then washing, complexing, eluting, precipitating and concentrating to obtain products comprising heavy oleate, thorium nitrate and rare earth carbonate and obtain products which comprise high-purity uranium, thorium and rare earth. The extracting and recycling process is simple in device structure, low in investment, low in energy consumption and easy to operate; the industrialization is liable to implement; the direct recovery rate is 99%; precious resources can be recycled; the waste is reduced; the environment is protected.
Description
Technical field
The present invention relates to the comprehensive recovering process that a kind of rare-earth mineral decomposes valuable element in recrement, be specifically related to the separation and recovery method that a kind of rare-earth mineral decomposes uranium, thorium, rare earth in recrement.
Background technology
The laudatory title that rare earth has " industrial VITAMIN ", has now become extremely important strategic resource.At present, rare-earth mineral mainly contains monazite, bastnasite, xenotime etc., and monazite is mainly distributed in coastal area, and bastnasite is mainly distributed in Sichuan, and xenotime is mainly distributed in southern six provinces.The baotite of northern China is the composite ore of bastnasite and monazite.Monazite belongs to light rare earths ore deposit, and current production technique is: monazite concentrate, through caustic digestion, extracts useful rare earth and phosphorus from feed liquid, in remaining solid product containing have an appointment 1 ~ 30% ThO
2(thorium dioxide), 0.1 ~ 1.5% U(uranium) and 1 ~ 20% REO(rare earth oxide), the valuable minerals such as the monazite be not decomposed in addition, zircon, rutile.Although monazite content is low in the composite ore of packet header, still have excessive radionuclide to exist after disaggregating treatment, not being recovered of the thorium resources that wherein content is maximum, is unfavorable for that environmental protection manages, and wastes valuable natural resources.
CN103014359A disclosed a kind of separation and recovery method of solitary rock ballast for 04 month 03 day in 2013, comprised the following steps: acidleach, press filtration, washing, the extraction of valuable constituent, filter residue process.There is following defect in it: acidity is low, and leaching yield is on the low side, and leach liquor volume is very large, causes cost of investment to increase; What adopt is P204 and N1923 extracting and separating thorium and rare earth, and extracting process can cause extraction three phases, affects extracting operation, and extracting system is open type, concerning containing radioactive body series, larger on the impact of operator; The extraction agent high expensive that extracting process uses; Extracting and separating thorium and rare earth are extensive style, and thorium reclaims with thorium hydroxide enriched substance form, and utility value is on the low side.
Summary of the invention
Technical problem to be solved by this invention is, provides a kind of less investment, easy to operate, less on the impact of operator, and the rare-earth mineral reaching efficient recovery decomposes the separation and recovery method of uranium, thorium, rare earth in recrement.
The technical solution adopted for the present invention to solve the technical problems is: a kind of rare-earth mineral decomposes the separation and recovery method of uranium, thorium, rare earth in recrement, comprises the following steps:
(1) acidleach: decomposing the quality of recrement and the volume ratio of inorganic acid solution according to rare-earth mineral is the ratio of 1:0.5-20, unit: kg/L, rare-earth mineral is decomposed recrement and join that to be loaded with concentration be in the reactor of the inorganic acid solution of 1-5mol/L, stir 1-5 hour; It is 0.5-5 ‰ polyacrylamide solution that the ratio being 1-100:2000 in the volume ratio of polyacrylamide solution and leach liquor adds massfraction, flocculation sediment, and leave standstill clarification, siphon supernatant liquor, obtains the solution containing uranium, thorium, rare earth valuable element;
Slip pump after siphon supernatant liquor is squeezed into wind big gun, enters plate-and-frame filter press press filtration by wind big gun, flow out to absence of liquid, add water washing to pH=2.0-5.5, merging filtrate, washings and siphon supernatant liquor, obtain the limpid aqueous solution containing uranium, thorium, rare earth;
(2) uranium is carried: adopt 201*7 type anion exchange absorbing method to extract uranium from the limpid aqueous solution of step (1) gained, the limpid aqueous solution of thorium, rare earth must be contained, with the mixed aqueous solution of sulfuric acid and sodium-chlor, drip washing is carried out to resin, obtain leacheate, then basic hydrolysis is carried out to leacheate, filter, washing, dry, obtain solid diuranate;
(3) thorium and Rare Earth Separation: with the inorganic acid solution acidifying 001*7 type Zeo-karb of 0.1-1.0mol/L, with thorium, rare earth and part non-rare earth impurity in the limpid aqueous solution containing thorium, rare earth of good resin isolation step (2) gained of acidifying, feed liquid flows through resin with 1-100mm/min flow velocity, first non-rare earth flows out and drains at a low price, in time having rare earth element to flow out with feed liquid, stop charging, wash adsorption column with the HCl of 0.1-2.0mol/L, and collect scrub stream fluid; With the EDTA solution drip washing adsorption column of 0.01-0.1mol/L, drip washing speed control 1-100mm/min, drip washing effluent liquid beaker separately connects, and ThO analyzed by each cup all censorship
2and TREO, reach the object of thorium and Rare Earth Separation purification;
(4) thorium and rare-earth products: according to ThO
2with the analytical data of TREO, feed liquid identical for purity merged, the thorium feed liquid of merging adjusts pH=0.5-1.0, and Precipitation EDTA recycles, solution carbon ammonium precipitation, filters, obtains the carbonate of thorium, the carbonate of thorium uses nitric acid dissolve again, condensing crystal, obtains six water thorium nitrate 99.99004323A8urity products; The rare earth feed liquid merged adjusts pH=0.5-1.0, and Precipitation EDTA recycles, then uses carbon ammonium precipitation, filters, obtains the carbonate products of rare earth.
Further, in step (1), described inorganic acid solution is hydrochloric acid, nitric acid or sulfuric acid.
Further, in step (2), in the mixed aqueous solution of described sulfuric acid and sodium-chlor, the concentration of sodium-chlor is the preferred 1mol/L of 0.10-1.5mol/L(), the massfraction of sulfuric acid is 1-10%(preferably 5%).
Further, in step (2), alkaline hydrolysis process is, by gained leacheate heated and stirred to 95-105 DEG C, adds ammoniacal liquor to pH=10, has ammonium diuranate Precipitation, and constant temperature stirs 25-35min, leaves standstill 25-35min.
Further, in step (3), inorganic acid solution is hydrochloric acid, nitric acid or sulfuric acid.
The present invention, for improving valuable element uranium, thorium, rare earth leaching yield, after acidleach, adds polyacrylamide flocculation sediment, and leave standstill clarification, siphon supernatant liquor obtains the solution containing uranium, thorium, rare earth valuable element; Slip pump after siphon supernatant liquor is squeezed into wind big gun, and compress into plate-and-frame filter press press filtration by wind big gun high pressure and flow out to without solution, the supernatant liquor of filtrate and siphon merges.Wherein, add polyacrylamide flocculant, sedimentation effect is better, and can meet and leach under comparatively highly acidity condition, leaching yield is higher; Wind big gun high pressure filter press, press filtration better effects if, speed of filter pressing is faster; The water content of press cake can be reduced, improve leaching yield; Enhance productivity.
The leaching process of uranium of the present invention, thorium and rare earth all adopts ion exchange resin to carry out separating-purifying; Wherein when thorium and Rare Earth Separation, it is the 001*7 type Zeo-karb of the inorganic acid solution acidifying adopting 0.1-1.0mol/L, feed liquid flows through resin with 1-100mm/min flow velocity, first non-rare earth flows out and drains at a low price, in time having rare earth element to flow out with feed liquid, stop charging, wash adsorption column with 0.1-2.0mol/L HCl, and the solution of collecting belt thorium and rare earth; With the EDTA solution drip washing adsorption column of 0.01-0.10mol/L, drip washing speed control 1-100mm/min, drip washing effluent liquid beaker separately connects, and reaches the object of thorium and Rare Earth Separation purification.
The feed liquid classification precipitation of the different purity that step (3) produces, obtains the product salt needed, the leacheate that purity is low, after precipitation, dissolves, enter next fractionation by adsorption flow process.
The present invention adopts polyacrylamide flocculation sediment, and leave standstill clarification, liquid phase is easily separated with solid phase; Adopt wind big gun to enter plate-and-frame filter press press filtration to flow out to without solution, feed liquid is separated more thorough with filter cake, ensure product yield; The extraction of uranium, thorium and rare earth all adopts ion exchange resin to carry out separating-purifying; Whole separation-extraction technology system is closed, and not only reduces waste, and reduces the impact of radioactivity on operating environment; Whole technique safety and reliability, whole flow sheet equipment simple structure, less investment, low, easy to operate, the easy industrialization of power consumption, straight gyrus yield are greater than 99%.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
embodiment 1
The rare-earth mineral of the present embodiment decomposes the separation and recovery method of uranium, thorium, rare earth in recrement, comprises the following steps:
(1) acidleach: decomposing the quality of recrement and the volume ratio of sulphuric acid soln in rare-earth mineral is the ratio of 1:5, unit: kg/L, decomposes recrement and joins that to be loaded with concentration be in the reactor of the sulphuric acid soln of 1mol/L, stir 2 hours by rare-earth mineral; It is 2 ‰ polyacrylamide solutions that the ratio being 1:1000 in the volume ratio of polyacrylamide solution and leach liquor adds massfraction, flocculation sediment, and leave standstill clarification, siphon supernatant liquor, obtains the solution containing uranium, thorium, rare earth valuable element;
Slip pump after siphon supernatant liquor is squeezed into wind big gun, enters plate-and-frame filter press press filtration by wind big gun, flow out to absence of liquid, add water washing to pH=4, merging filtrate, washings and siphon supernatant liquor, obtain the limpid aqueous solution containing uranium, thorium, rare earth; Sampling analysis, the leaching rate of uranium is 82%, and the leaching rate of thorium is 88%, and the leaching rate of rare earth is 75%;
(2) uranium is carried: adopt 201*7 type anion exchange absorbing method to extract uranium from the limpid aqueous solution of step (1) gained, the limpid aqueous solution of thorium, rare earth must be contained, with the mixed aqueous solution of sulfuric acid and sodium-chlor, drip washing is carried out to resin, obtain leacheate, then basic hydrolysis is carried out to leacheate, filter, washing, dry, obtain solid diuranate;
Plastic resin treatment: get 201*7 type resin anion(R.A), with pure water to after colourless, soaks 24h with pure water, period timing agitation; With massfraction be 5% NaOH solution soak 24h, period timing agitation, wash away the caustic solubility impurity in resin, be washed till neutrality with pure water; Be the H of 5% with massfraction
2sO
4solution soaking 24h, period timing agitation, wash away the acid soluble impurities in resin, be washed till neutrality with pure water; With the H of 0.15mol/L
2sO
4solution soaking resin is to acid, and resin is respectively charged in two series winding pillars of (Ф 500mm, long 1200mm) stand-by, resin height is 850mm;
Resin absorption: by the limpid aqueous solution containing uranium, thorium, rare earth of step (1) gained, flow through in resin with the linear velocity of 5mm/min from storage tank, adsorption uranium is saturated to resin, effluent liquid be containing rare earth and thorium except uranium material;
Washing: with the H of 0.25mol/L
2sO
4rare earth free in solution washing resin and thorium, to scrub stream fluid sampling analysis without thorium and rare earth, merge washings and effluent liquid, the limpid aqueous solution containing thorium, rare earth obtained, thorium to be separated and rare earth;
Drip washing: the mixed aqueous solution of preparation sulfuric acid and sodium-chlor, wherein the concentration of sodium-chlor is 1mol/L, and the massfraction of sulfuric acid is 5%, and the uranium in drip washing resin, terminates to leacheate without yellow;
Hydrolysis and oven dry: by gained leacheate heated and stirred to 100 DEG C, add ammoniacal liquor to pH=10, have ammonium diuranate Precipitation, constant temperature stirs 30min, leaves standstill 30min, filters; With 70 DEG C of hot wash ammonium diuranate throw outs, centrifuge dehydration obtains crystal sodium diuranate, and crystal ammonium diuranate is dried at 100 DEG C, obtains solid sodium diuranate product, and the direct yield of uranium is 99.5%;
(3) thorium and Rare Earth Separation
Plastic resin treatment: get 001*7 type resin cation (R.C.), with pure water to after colourless, soaks 24h with pure water, period timing agitation; Be the H of 5% with massfraction
2sO
4solution soaking 24h, period timing agitation, wash away the acid soluble impurities in resin, be washed till neutrality with pure water; With massfraction be 5% NaOH solution soak 24h, period timing agitation, wash away the caustic solubility impurity in resin, be washed till neutrality with pure water; With the H of 0.2mol/L
2sO
4solution soaking resin is to acid, and resin is respectively charged in two series winding pillars of (Ф 500mm, long 1200mm) stand-by, resin height is 850mm;
Thorium and Rare Earth Separation: by the limpid aqueous solution containing thorium, rare earth of step (2) gained, flow through in resin with the linear velocity of 4mm/min from storage tank, first non-rare earth flows out and drains at a low price, in time having rare earth element to flow out with feed liquid, stop charging, wash adsorption column with the HCl of 1mol/L, and collect scrub stream fluid, be merged in raw material and do raw material use; With EDTA solution (disodium ethylene diamine tetraacetate) the drip washing adsorption column of 0.02mol/L, drip washing speed control 5mm/min, drip washing effluent liquid beaker separately connects (because " thorium, rare earth " is different from the complexation constant of EDTA, different by the sequencing washed out, rare earth first out, the object of separation is out reached after thorium), ThO analyzed by each cup all censorship
2and TREO, reach the object of thorium and Rare Earth Separation purification;
(4) thorium and rare-earth products
According to ThO
2with the analytical data of TREO, feed liquid identical for purity is merged (ThO
2the merging together that purity is greater than 99%, 97-98% merges together, and TREO merges same ThO
2), the thorium feed liquid of merging adjusts pH=1.0, and Precipitation EDTA recycles, solution carbon ammonium precipitation, filter, obtain the carbonate of thorium, the carbonate of thorium uses nitric acid (commercially available industrial concentrated acid again, mass concentration is 67.5%) dissolve, through condensing crystal, obtain six water thorium nitrate 99.99004323A8urity products; The rare earth feed liquid merged adjusts pH=0.8, and Precipitation EDTA recycles, solution carbon ammonium precipitation, filters, obtains the carbonate products of rare earth; The straight comprehensive yield 99% of thorium and rare earth.
The filter residue that the present embodiment step (1) obtains mainly undecomposed rare-earth original ore, again can proceed to the process of rare earth ore concentrate treatment process, realize circulation and stress.
embodiment 2
In the present embodiment step (1), decomposing the quality of recrement and the volume ratio of sulphuric acid soln in rare-earth mineral is the ratio of 1:8, unit: kg/L, rare-earth mineral is decomposed recrement and joins that to fill concentration be in the reactor of 1.2mol/L sulphuric acid soln, stir 2 hours; Then it is 2 ‰ polyacrylamide solution flocculation sediments that the ratio being 1:800 in the volume ratio of polyacrylamide solution and leach liquor adds massfraction, and leave standstill clarification, siphon supernatant liquor, obtains the solution containing uranium, thorium, rare earth valuable element;
Slip pump after siphon supernatant liquor is squeezed into wind big gun, enters plate-and-frame filter press press filtration by wind big gun, flow out to without solution, add water washing to pH=4, merging filtrate, washings and siphon supernatant liquor, obtain the limpid aqueous solution containing uranium, thorium, rare earth; Sampling analysis, the leaching rate of uranium is 89%, and the leaching rate of thorium is 91%, and the leaching rate of rare earth is 80%;
In the present embodiment step (3), the linear velocity of the limpid aqueous solution with 5mm/min from storage tank containing thorium, rare earth of step (2) gained is flowed through resin, first non-rare earth flows out and drains at a low price, in time having rare earth element to flow out with feed liquid, stop charging, wash adsorption column with 0.5mol/L HCl, and collect scrub stream fluid, be merged in raw material and do raw material use; With the EDTA solution drip washing adsorption column of 0.018mol/L, drip washing speed control 8mm/min, drip washing effluent liquid beaker separately connects, and ThO analyzed by each cup all censorship
2and TREO, reach the object of thorium and Rare Earth Separation purification; The straight comprehensive yield 99% of thorium and rare earth;
All the other are with embodiment 1.
embodiment 3
In the present embodiment step (1), decomposing the quality of recrement and the volume ratio of sulphuric acid soln in rare-earth mineral is the ratio of 1:12, unit: kg/L, rare-earth mineral is decomposed recrement and joins that to be loaded with concentration be in the reactor of 1.5mol/L sulphuric acid soln, stir 5 hours; Then it is 2 ‰ polyacrylamide solution flocculation sediments that the ratio being 1:700 in the volume ratio of polyacrylamide solution and leach liquor adds massfraction, and leave standstill clarification, siphon supernatant liquor, obtains the solution containing uranium, thorium, rare earth valuable element;
Slip pump after siphon supernatant liquor is squeezed into wind big gun, enters plate-and-frame filter press press filtration by wind big gun, flow out to without solution, add water washing to pH=4, merging filtrate, washings and siphon supernatant liquor, obtain the limpid aqueous solution containing uranium, thorium, rare earth; Sampling analysis, the leaching rate of uranium is 90%, and the leaching rate of thorium is 95%, and the leaching rate of rare earth is 83%;
In the present embodiment step (3), the linear velocity of the limpid aqueous solution with 3mm/min from storage tank containing thorium, rare earth of step (2) gained is flowed through resin, first non-rare earth flows out and drains at a low price, in time having rare earth element to flow out with feed liquid, stop charging, wash adsorption column with 0.8mol/L HCl, and collect scrub stream fluid; With the EDTA solution drip washing adsorption column of 0.022mol/L, drip washing speed control 3mm/min, drip washing effluent liquid beaker separately connects, and ThO analyzed by each cup all censorship
2and TREO, reach the object of thorium and Rare Earth Separation purification; The straight comprehensive yield of thorium and rare earth is greater than 99%;
Remaining with embodiment 1.
embodiment 4
In the present embodiment step (1), decomposing the quality of recrement and the volume ratio of sulphuric acid soln in rare-earth mineral is the ratio of 1:15, unit: kg/L, rare-earth mineral is decomposed recrement and joins that to be loaded with concentration be in the reactor of 3mol/L sulphuric acid soln, stir 1 hour; Then it is 2 ‰ polyacrylamide solution flocculation sediments that the ratio being 1:500 in the volume ratio of polyacrylamide solution and leach liquor adds massfraction, and leave standstill clarification, siphon supernatant liquor, obtains the solution containing uranium, thorium, rare earth valuable element;
Slip pump after siphon supernatant liquor is squeezed into wind big gun, enters plate-and-frame filter press press filtration by wind big gun, flow out to without solution, add water washing to pH=4, merging filtrate, washings and siphon supernatant liquor, obtain the limpid aqueous solution containing uranium, thorium, rare earth; Sampling analysis, the leaching rate of uranium is 91%, and the leaching rate of thorium is 95%, and the leaching rate of rare earth is 83%;
In the present embodiment step (3), the linear velocity of the limpid aqueous solution with 10mm/min from storage tank containing thorium, rare earth of step (2) gained is flowed through resin, first non-rare earth flows out and drains at a low price, in time having rare earth element to flow out with feed liquid, stop charging, wash adsorption column with 2mol/L HCl, and collect scrub stream fluid; With the EDTA solution drip washing adsorption column of 0.018mol/L, drip washing speed control 15mm/min, drip washing effluent liquid beaker separately connects, and ThO analyzed by each cup all censorship
2and TREO, reach the object of thorium and Rare Earth Separation purification; The straight comprehensive yield 95% of thorium and rare earth;
Remaining with embodiment 1.
embodiment 5
In the present embodiment step (1), decomposing the quality of recrement and the volume ratio of sulphuric acid soln in rare-earth mineral is the ratio of 1:9, unit: kg/L, rare-earth mineral is decomposed recrement and joins that to be loaded with concentration be in the reactor of 1.8mol/L sulphuric acid soln, stir 3 hours; Then it is 2 ‰ polyacrylamide solution flocculation sediments that the ratio being 1:900 in the volume ratio of polyacrylamide solution and leach liquor adds massfraction, and leave standstill clarification, siphon supernatant liquor, obtains the solution containing uranium, thorium, rare earth valuable element;
Slip pump after siphon supernatant liquor is squeezed into wind big gun, enters plate-and-frame filter press press filtration by wind big gun and flow out to without solution, add water washing to pH=4, merging filtrate, washings and siphon supernatant liquor, obtain the limpid aqueous solution containing uranium, thorium, rare earth; Sampling analysis, the leaching rate of uranium is 92%, and the leaching rate of thorium is 94%, and the leaching rate of rare earth is 86%;
In the present embodiment step (3), the linear velocity of the limpid aqueous solution with 4.5mm/min from storage tank containing thorium, rare earth of step (2) gained is flowed through resin, first non-rare earth flows out and drains at a low price, in time having rare earth element to flow out with feed liquid, stop charging, wash adsorption column with 0.7mol/L HCl, and collect scrub stream fluid; With the EDTA solution drip washing adsorption column of 0.018mol/L, drip washing speed control 4.5mm/min, drip washing effluent liquid beaker separately connects, and ThO analyzed by each cup all censorship
2and TREO, reach the object of thorium and Rare Earth Separation purification; The straight comprehensive yield of thorium and rare earth is greater than 99%;
Remaining with embodiment 1.
Claims (5)
1. rare-earth mineral decomposes a separation and recovery method for uranium, thorium, rare earth in recrement, it is characterized in that, comprises the following steps:
(1) acidleach: decomposing the quality of recrement and the volume ratio of inorganic acid solution according to rare-earth mineral is the ratio of 1:0.5-20, unit: kg/L, rare-earth mineral is decomposed recrement and join that to be loaded with concentration be in the reactor of the inorganic acid solution of 1-5mol/L, stir 1-5 hour; It is 0.5-5 ‰ polyacrylamide solution that the ratio being 1-100:2000 in the volume ratio of polyacrylamide solution and leach liquor adds massfraction, flocculation sediment, and leave standstill clarification, siphon supernatant liquor, obtains the solution containing uranium, thorium, rare earth valuable element;
Slip pump after siphon supernatant liquor is squeezed into wind big gun, enters plate-and-frame filter press press filtration by wind big gun, flow out to absence of liquid, add water washing to pH=2.0-5.5, merging filtrate, washings and siphon supernatant liquor, obtain the limpid aqueous solution containing uranium, thorium, rare earth;
(2) uranium is carried: adopt 201*7 type anion exchange absorbing method to extract uranium from the limpid aqueous solution of step (1) gained, the limpid aqueous solution of thorium, rare earth must be contained, with the mixed aqueous solution of sulfuric acid and sodium-chlor, drip washing is carried out to resin, obtain leacheate, then basic hydrolysis is carried out to leacheate, filter, washing, dry, obtain solid diuranate;
(3) thorium and Rare Earth Separation: with the inorganic acid solution acidifying 001*7 type Zeo-karb of 0.1-1.0mol/L, with thorium, rare earth and part non-rare earth impurity in the limpid aqueous solution containing thorium, rare earth of good resin isolation step (2) gained of acidifying, feed liquid flows through resin with 1-100mm/min flow velocity, first non-rare earth flows out and drains at a low price, in time having rare earth element to flow out with feed liquid, stop charging, wash adsorption column with the HCl of 0.1-2.0mol/L, and collect scrub stream fluid; With the EDTA solution drip washing adsorption column of 0.01-0.1mol/L, drip washing speed control 1-100mm/min, drip washing effluent liquid beaker separately connects, and ThO analyzed by each cup all censorship
2and TREO, reach the object of thorium and Rare Earth Separation purification;
(4) thorium and rare-earth products: according to ThO
2with the analytical data of TREO, feed liquid identical for purity merged, the thorium feed liquid of merging adjusts pH=0.5-1.0, and Precipitation EDTA recycles, solution carbon ammonium precipitation, filters, obtains the carbonate of thorium, the carbonate of thorium uses nitric acid dissolve again, condensing crystal, obtains six water thorium nitrate 99.99004323A8urity products; The rare earth feed liquid merged adjusts pH=0.5-1.0, and Precipitation EDTA recycles, then uses carbon ammonium precipitation, filters, obtains the carbonate products of rare earth.
2. rare-earth mineral according to claim 1 decomposes the separation and recovery method of uranium, thorium, rare earth in recrement, and it is characterized in that: in step (1), described inorganic acid solution is hydrochloric acid, nitric acid or sulfuric acid.
3. rare-earth mineral according to claim 1 and 2 decomposes the separation and recovery method of uranium, thorium, rare earth in recrement, it is characterized in that: in step (2), in the mixed aqueous solution of described sulfuric acid and sodium-chlor, the concentration of sodium-chlor is 0.10-1.5mol/L, and the massfraction of sulfuric acid is 1-10%.
4. rare-earth mineral according to claim 1 and 2 decomposes the separation and recovery method of uranium, thorium, rare earth in recrement, it is characterized in that: in step (2), alkaline hydrolysis process is, by gained leacheate heated and stirred to 95-105 DEG C, add ammoniacal liquor to pH=10, have ammonium diuranate Precipitation, constant temperature stirs 25-35min, leaves standstill 25-35min.
5. rare-earth mineral according to claim 1 and 2 decomposes the separation and recovery method of uranium, thorium, rare earth in recrement, and it is characterized in that: in step (3), inorganic acid solution is hydrochloric acid, nitric acid or sulfuric acid.
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| WO2018227674A1 (en) * | 2017-06-16 | 2018-12-20 | 苏州大学 | Method for removing radioactive thorium element in rare earth mineral |
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| 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 |
| CN110261210A (en) * | 2019-07-31 | 2019-09-20 | 核工业二三O研究所 | The alpha energy spectrum method of testing of the method for separating and concentrating of uranium and uranium in sample of sandstone |
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| CN114410973A (en) * | 2021-12-31 | 2022-04-29 | 湖南长宏新能源材料有限责任公司 | Method for recycling and degrading rare earth slag |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101484226A (en) * | 2006-07-03 | 2009-07-15 | 阿海珐核循环公司 | Method for separating a chemical element from uranium (VI) using an aqueous nitric phase, in a uranium extraction cycle |
| CN101870506A (en) * | 2010-06-08 | 2010-10-27 | 龙南县南裕稀土资源综合利用有限责任公司 | Technique for recycling rare earth from rare earth mining wastewater by resin adsorption method |
| CN102899485A (en) * | 2012-10-31 | 2013-01-30 | 吉林吉恩镍业股份有限公司 | Method for extracting scandium from scandium-containing material by resin-in-pulp method |
| CN103014359A (en) * | 2012-11-27 | 2013-04-03 | 益阳鸿源稀土有限责任公司 | Separation and recovery method of monazite slag |
| CN103509943A (en) * | 2013-10-25 | 2014-01-15 | 武汉工程大学 | Method for recovering rare earth from weathering crust elution-deposited rare earth ore residual liquid |
| CN103589866A (en) * | 2013-11-29 | 2014-02-19 | 上海交通大学 | Separation and recovery method for thorium and uranium by using silicon-based anion exchange resin |
-
2014
- 2014-12-02 CN CN201410716752.8A patent/CN104498739B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101484226A (en) * | 2006-07-03 | 2009-07-15 | 阿海珐核循环公司 | Method for separating a chemical element from uranium (VI) using an aqueous nitric phase, in a uranium extraction cycle |
| CN101870506A (en) * | 2010-06-08 | 2010-10-27 | 龙南县南裕稀土资源综合利用有限责任公司 | Technique for recycling rare earth from rare earth mining wastewater by resin adsorption method |
| CN102899485A (en) * | 2012-10-31 | 2013-01-30 | 吉林吉恩镍业股份有限公司 | Method for extracting scandium from scandium-containing material by resin-in-pulp method |
| CN103014359A (en) * | 2012-11-27 | 2013-04-03 | 益阳鸿源稀土有限责任公司 | Separation and recovery method of monazite slag |
| CN103509943A (en) * | 2013-10-25 | 2014-01-15 | 武汉工程大学 | Method for recovering rare earth from weathering crust elution-deposited rare earth ore residual liquid |
| CN103589866A (en) * | 2013-11-29 | 2014-02-19 | 上海交通大学 | Separation and recovery method for thorium and uranium by using silicon-based anion exchange resin |
Non-Patent Citations (1)
| Title |
|---|
| 蔡瑞清: "关于稀土中钍的去除问题", 《北京理工大学学报》 * |
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| 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 |
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| CN110261210A (en) * | 2019-07-31 | 2019-09-20 | 核工业二三O研究所 | The alpha energy spectrum method of testing of the method for separating and concentrating of uranium and uranium in sample of sandstone |
| CN111410231A (en) * | 2020-04-24 | 2020-07-14 | 核工业北京化工冶金研究院 | Method for preparing triuranium octoxide from excellent slag |
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