CN104946895A - Rare earth compound recycling method utilizing waste rare earth polishing powder - Google Patents
Rare earth compound recycling method utilizing waste rare earth polishing powder Download PDFInfo
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Abstract
The invention discloses a rare earth compound recycling method utilizing waste rare earth polishing powder, which comprises the following steps: (1) the waste rare earth polishing powder is subjected to enrichment to prepare an enrichment material of a rare earth element; (2) the enrichment material of the rare earth element is roasted with concentrated sulfuric acid under a low temperature and is subjected to water leaching, and ammonium bicarbonate is used to realize double decomposition for neutralization and filtration cleaning, so that crude carbonic acid rare earth is prepared, and a high-purity rare earth compound is prepared by extraction separation. The invention has the advantages that (1) the separation efficiency is greatly improved, and the total rare earth oxide (TREO) is above 95%; (2) the novel technology is capable of realizing the aim of recycling the rare earth compound from the waste rare earth polishing powder in low cost and high efficiency;(3) the method is simple in operation, the manufacturing costs of required apparatuses are low, the product quality can be guaranteed, and industrial production can be realized; and (4) a lot of waste rare earth polishing powder is recycled so as to solve the problems of environment pollution and resource shortage.
Description
Technical field
The present invention relates to cyclic regeneration rare earth compound method, particularly relate to and utilize useless polishing powder from rare earth cyclic regeneration rare earth compound method.
Background technology
Along with the development of worldwide electronic technology and glass industry, the demand of the polishing material based on rare earth element is grown with each passing day.According to internal authority mechanism statistics, in the rare earth Application Areas of global range in 2013, the rare-earth usage for polishing industry accounts for total consumption more than 20%.And the usage quantity of the annual rare-earth polishing material of China is at 25000 tons.Especially along with the develop rapidly of China's mobile phone, liquid crystal display industry, rare-earth polishing material demand is increasing with the speed in year 15%.Become the Application Areas that of China's Rare-earth Industry is important, meanwhile, due to the special crystalline structure that rare-earth polishing material has, become irreplaceable unique fine polishing material in precise polished field, Application Areas is increasingly extensive.
But the consumption of domestic annual 25000 tons of polishing powder from rare earth can produce the discarded polishing powder from rare earth more than 77000 ton of total amount of rare earth 30wt%, containing rare earth oxide more than 23000 ton thereupon.And this solid waste is because the fluorine containing 1.7-1.8wt% can cause problem of environmental pollution.Recent domestic polishing powder from rare earth user is anxious for and addresses this problem.And developing in a large number year by year along with China's rare earth resources, be necessary rare earth waste to reclaim, regeneration.The recovery and treatment method having the useless polishing powder from rare earth that patent relates at present has:
1, will give up polishing powder from rare earth acid dissolve solvend, remove greasy dirt through more than 800 DEG C high-temperature roastings, then fine grinding, reach certain particle size, be reused for polishing.Regeneration polishing powder from rare earth after this method process, crystalline structure is bad, and polishing efficiency is low in actual use, work-ing life is short, can only become the low-level use of manual polishing simply, cannot meet extensive, the use of normal buff industry, so nobody adopts in this way so far.
2, useless polishing powder from rare earth is inserted in high speed dispersor, adopt per minute 3000-5000 to turn high speed dispersion, then separation, impurity removal, finally obtain rare earth rumbling compound finished product.This method can only under lab make a try, and cannot apply in large-scale industrial production.Its reason is batch mixing dispersion under the running up turned at per minute 3000-5000; industrial production is difficult to realize; its secondary through four times dispersion removal of impurities after can obtain concentrated rare earth rumbling compound finished product; and quality is not high; can only obtain the product of a mixed type, be thus also worthless in large-scale production.
Summary of the invention
The object of the present invention is to provide efficient, continuous, the cleanly production that can realize Rare Earth Production, the polishing powder from rare earth cyclic regeneration rare earth compound method and the utilization of reclaiming valuable element is given up comprehensively.
Object of the present invention is implemented by following technical scheme, utilizes the method for useless polishing powder from rare earth cyclic regeneration rare earth compound, and it comprises the steps: (1) gives up polishing powder from rare earth through enrichment, produces the enrichment material of rare earth element; (2) by the enrichment material of described rare earth element with the water logging of vitriol oil low-temperature bake, in bicarbonate of ammonia metathesis and filtering and impurity removing, prepare thick carbonated rare earth, extracting and separating high purity rare earth compound.Useless polishing powder from rare earth exists with oxyfluoride form, and water insoluble, being slightly soluble in acid, is first remove the organic impuritys such as dispersion agent in the weakly acid soln of 4 at pH.In secondary dedoping step, by silicon, aluminium, iron Ex-all, the useless polishing powder from rare earth material of TREO>80% after precipitation, can be obtained after filtration.Then, the useless polishing powder from rare earth material of TREO>80% is entered sulfuric acid decomposition operation.
Concrete, described step (1) is implemented as follows:
A, prepare slip: by the useless polishing powder from rare earth mixture of total amount of rare earth TREO=35wt%, add water soaking 5-10 minute and make slip, described stock quality concentration is 20%, hydrochloric acid is added again in described slip, described slip pH value is adjusted to 3-4, after then described slurry being stirred 20-25 minute in mixing agitator, enters spiral classifier by conduit; Control pH value well, acidity is too strong, dissolves and tides over height, will cause material pasty state, not easily filtering-depositing.
B, slip are through spiral classifier concentration and separation: the overflow outlet of mass rate through described spiral classifier top containing frivolous material 10% is overflowed, filter through 200 mesh filter screens, clear water after filtration is back to described mixing agitator through pump line and recycles, and the foreign material on filter screen are waste; Wherein, in the mass rate unit time, fluid passes through the fluid mass of closed conduct or open channel free area.Frivolous material comprises resin component, calcium, dispersion agent.
Isolated non-rare earth heavy element is discharged by described spiral classifier bottom waste outlet, and described non-rare earth heavy element has aluminium (Al
2o
3), silicon (SiO
2) also having the rare earth element mixing of about 2% wherein, described non-rare earth heavy element is deposited pending as byproduct enrichment after quiescent setting;
The enrichment material of isolated described rare earth element is exported by the major ingredient in the middle part of described spiral classifier discharges, the described slip of 60% mass percent is exported by described major ingredient and reclaims, after the enrichment material of described rare earth element reclaimed was filtered dry naturally through 24 hours, moisture content is at 10-15%, and the enrichment material Rare Earth Element Contents of described rare earth element is 60-80%.
Spiral classifier is shunted with spiral gravity, utilizes the distinctive proportion of rare earth element, controls the flow of slurries well, effectively isolates the impurity such as silicon, aluminium, iron.
Preferably, described hydrochloric acid is technical hydrochloric acid, and the concentration of described technical hydrochloric acid is greater than 36wt%.
Preferably, the rotating speed of described mixing agitator is 30-50 rev/min.Be uniformly mixed in process, rotating speed is not easily too high, reaches that slurry is evenly not stratified is advisable, and fully mix, be beneficial to filtering and impurity removing, the frivolous material such as the dispersion agent in feed liquid will be separated in overflow, and frivolous material comprises resin component, calcium, dispersion agent.
Concrete, described spiral classifier comprises agitation vat, stir shaft is provided with in described agitation vat, it is outside that one end of described stir shaft extends to described agitation vat by the top of described agitation vat or bottom up or down, the described stir shaft being positioned at described agitation vat is provided with agitating vane, the end being positioned at the described stir shaft outside described agitation vat is connected with motor, the top of described agitation vat is provided with described overflow outlet, the middle part of described agitation vat is provided with the outlet of described major ingredient, the bottom of described agitation vat is provided with described waste outlet, the top of described agitation vat is provided with opening for feed.
Preferably, described overflow outlet is arranged at apart from agitation vat At The Height described in described agitation vat top 20%, and described major ingredient outlet is arranged at apart from agitation vat At The Height described in described agitation vat top 70%, and described waste outlet is arranged bottom described agitation vat.
Concrete, described step (2) is implemented as follows:
A, prepare vitriol oil mixed slurry: in the enrichment material of the obtained described rare earth element of described step (1), add the vitriol oil in order to improve dispersiveness and the mobility of slurry, the enrichment material of described rare earth element mixes by weight the ratio for 1:0.6-1:0.7 with the described vitriol oil, obtained vitriol oil mixed slurry;
B, roasting: by described vitriol oil mixed slurry at 350 DEG C-400 DEG C roasting 1-1.5 hour, obtained baking mixes, by the water logging of described baking mixes normal temperature, washes off the described vitriol oil, obtained infusion;
C, prepare rare earth oxide: described infusion after neutralization is filtered routinely extracting process prepare mixed rare-earth oxide or single rare earth oxide compound.
Preferably, the described vitriol oil is technical grade, and concentration is not less than 90wt%, and described roasting is dynamic roasting, and dynamic roasting refers to that material is in flow state in roasting process.
Preferably, the optimum calcination temperature in described calcination steps is 360 DEG C, and best roasting time is 1.2 hours.
Adopt the policy of subsection harnessing, make circulation, efficient, continuously, the processing condition of cleanly production rare-earth products and parameter, and the product such as the various salt produced in comprehensive recovery process process and valuable element, realize cleaner production, the object of energy-saving and emission-reduction and comprehensive utilization of resources; This circulation and stress technology is applied to whole industry the most at last, optimizes and improve the level of the secondary resource comprehensive utilizations such as rare earth waste, promotes Industry Innovation level and building capability.
The invention has the advantages that, (1) by spiral classifier, enrichment is carried out to material, the enrichment material Rare Earth Element Contents forming rare earth element is 60-80%, moisture content is at 10-15%, and then separation is carried out to the enrichment material of rare earth element prepare mixed rare-earth oxide or single rare earth oxide compound, separation efficiency improves greatly, and rare earth (TREO) total recovery is more than 95%; (2) novel process achieves the object of low cost, high-level efficiency recovering rare earth compound from useless polishing powder from rare earth, solving discarded polishing powder from rare earth causes problem of environmental pollution on the one hand, on the other hand, discarded polishing powder from rare earth recycle, greatly reduce the exploitation to China's rare earth resources, reduce resource loss and waste; (3) the inventive method is simple to operate, required equipment low cost of manufacture, and quality product is secure, can realize suitability for industrialized production; (4) total consumption about 25000 tons/year of current China polishing powder from rare earth, and with the speedup in year 15% in cumulative year after year, be that the annual discarded polishing powder from rare earth produced is about 70000-80000 ton therewith accordingly.Owing to containing the impurity such as fluorine, aluminium, silicon in discarded polishing powder from rare earth, all having contaminative to surface soil, cause bad environments, is typical trade waste.A large amount of recovery is carried out to this refuse, has obvious effect to environmental protect; (5) rare earth is as non-renewable resource, and reserves are limited, realizes a large amount of recovery of industrially scalable, effectively economizes on resources, and recycling, will have a tremendous social and economic benefits.Calculate with year treatment capacity 6000 tons of discarded polishing powder from rare earth: recoverable material presses the rare earth grade of 35%, the rate of recovery can reach 96%, recyclable single rare earth product 2000 tons (TREO>99%), calculation of price by existing lanthanum cerium single rare earth oxide compound: 2000 tons × 12000 yuan/ton=24000000 yuan, economic benefit and social benefit remarkable.
Accompanying drawing explanation
Fig. 1 is spiral classifier structural representation.
Agitation vat 1, stir shaft 2, agitating vane 3, motor 4, overflow outlet 5, major ingredient outlet 6, waste outlet 7, opening for feed 8.
Embodiment:
Embodiment 1: the method utilizing useless polishing powder from rare earth cyclic regeneration rare earth compound, it comprises the steps: (1) gives up polishing powder from rare earth through enrichment, produces the enrichment material of rare earth element;
A, prepare slip: by the useless polishing powder from rare earth mixture of total amount of rare earth TREO=35wt%, add water soaking and make slip in 5 minutes, stock quality concentration is 20%, then adds technical hydrochloric acid in slip, and the concentration of technical hydrochloric acid is greater than 36wt%, slip pH value is adjusted to 3, control pH value well, acidity is too strong, dissolves and tides over height, material pasty state will be caused, not easily filtering-depositing.Then enter spiral classifier by conduit after slurry being stirred 20 minutes in mixing agitator, the rotating speed of mixing agitator is 30 revs/min; Be uniformly mixed in process, rotating speed is not easily too high, reaches that slurry is evenly not stratified is advisable, and fully mixes, is beneficial to filtering and impurity removing.
B, slip are through spiral classifier concentration and separation: the overflow outlet 5 of mass rate through spiral classifier top containing frivolous material 10% is overflowed, filter through 200 mesh filter screens, clear water after filtration is back to mixing agitator through pump line and recycles, and the foreign material on filter screen are waste; Wherein, in the mass rate unit time, fluid passes through the fluid mass of closed conduct or open channel free area.Frivolous material comprises resin component, calcium, dispersion agent.
Isolated non-rare earth heavy element is discharged by spiral classifier bottom waste outlet 7, and non-rare earth heavy element has aluminium (Al
2o
3), silicon (SiO
2) also having the rare earth element mixing of about 2% wherein, non-rare earth heavy element is deposited pending as byproduct enrichment after quiescent setting;
The enrichment material of isolated rare earth element exports 6 by the major ingredient in the middle part of spiral classifier and discharges, the slip of 60% mass percent exports 6 by major ingredient and reclaims, after the enrichment material of rare earth element reclaimed was filtered dry naturally through 24 hours, moisture content is at 10-15%, and the enrichment material Rare Earth Element Contents of rare earth element is 60%.
Spiral classifier is shunted with spiral gravity, utilizes the distinctive proportion of rare earth element, controls the flow of slurries well, effectively isolates the impurity such as silicon, aluminium, iron.
Spiral classifier comprises agitation vat 1, stir shaft 2 is provided with in agitation vat 1, it is outside that one end of stir shaft 2 extends to agitation vat 1 by the top of agitation vat 1 or bottom up or down, the stir shaft 2 being positioned at agitation vat 1 is provided with agitating vane 3, the end being positioned at the stir shaft 2 outside agitation vat 1 is connected with motor 4, the top of agitation vat 1 is provided with overflow outlet 5, and overflow outlet 5 is arranged at distance agitation vat 1 top 20% agitation vat 1 At The Height; The middle part of agitation vat 1 is provided with major ingredient outlet 6, and major ingredient outlet 6 is arranged at distance agitation vat 1 top 70% agitation vat 1 At The Height; The bottom of agitation vat 1 is provided with waste outlet 7, and waste outlet 7 is arranged bottom agitation vat 1; The top of agitation vat 1 is provided with opening for feed 8.
(2) by the enrichment material of rare earth element with the water logging of vitriol oil low-temperature bake, in bicarbonate of ammonia metathesis and filtering and impurity removing, prepare thick carbonated rare earth, extracting and separating high purity rare earth compound.Useless polishing powder from rare earth exists with oxyfluoride form, and water insoluble, being slightly soluble in acid, is first remove the organic impuritys such as dispersion agent in the weakly acid soln of 3 at pH.In secondary dedoping step, by silicon, aluminium, iron Ex-all, the useless polishing powder from rare earth material of TREO>80% can be obtained after drainage precipitation.Then, the useless polishing powder from rare earth material of TREO>80% is entered sulfuric acid decomposition operation.
Step (2) is implemented as follows:
A, prepare vitriol oil mixed slurry: in the enrichment material of the obtained rare earth element of step (1), add the vitriol oil in order to improve dispersiveness and the mobility of slurry, the enrichment material of rare earth element mixes by weight the ratio for 1:0.6 with the vitriol oil, obtained vitriol oil mixed slurry, the vitriol oil is technical grade, and concentration is not less than 90wt%;
B, roasting: by vitriol oil mixed slurry 350 DEG C of dynamic roastings 1.5 hours, obtained baking mixes, uses normal temperature water logging, is washed off by the vitriol oil by baking mixes, obtained infusion;
C, prepare rare earth oxide: infusion after neutralization is filtered routinely extracting process prepare mixed rare-earth oxide or single rare earth oxide compound.
Embodiment 2: the method utilizing useless polishing powder from rare earth cyclic regeneration rare earth compound, it comprises the steps: (1) gives up polishing powder from rare earth through enrichment, produces the enrichment material of rare earth element;
A, prepare slip: by the useless polishing powder from rare earth mixture of total amount of rare earth TREO=35wt%, add water soaking and make slip in 10 minutes, stock quality concentration is 20%, then adds technical hydrochloric acid in slip, and the concentration of technical hydrochloric acid is greater than 36wt%, slip pH value is adjusted to 4, control pH value well, acidity is too strong, dissolves and tides over height, material pasty state will be caused, not easily filtering-depositing.Then enter spiral classifier by conduit after slurry being stirred 25 minutes in mixing agitator, the rotating speed of mixing agitator is 50 revs/min; Be uniformly mixed in process, rotating speed is not easily too high, reaches that slurry is evenly not stratified is advisable, and fully mixes, is beneficial to filtering and impurity removing.
B, slip are through spiral classifier concentration and separation: the overflow outlet 5 of mass rate through spiral classifier top containing frivolous material 10% is overflowed, filter through 200 mesh filter screens, clear water after filtration is back to mixing agitator through pump line and recycles, and the foreign material on filter screen are waste; Wherein, in the mass rate unit time, fluid passes through the fluid mass of closed conduct or open channel free area.Frivolous material comprises resin component, calcium, dispersion agent.
Isolated non-rare earth heavy element is discharged by spiral classifier bottom waste outlet 7, and non-rare earth heavy element has aluminium (Al
2o
3), silicon (SiO
2) also having the rare earth element mixing of about 2% wherein, non-rare earth heavy element is deposited pending as byproduct enrichment after quiescent setting;
The enrichment material of isolated rare earth element exports 6 by the major ingredient in the middle part of spiral classifier and discharges, the slip of 60% mass percent exports 6 by major ingredient and reclaims, after the enrichment material of rare earth element reclaimed was filtered dry naturally through 24 hours, moisture content is at 10-15%, and the enrichment material Rare Earth Element Contents of rare earth element is 80%.
Spiral classifier is shunted with spiral gravity, utilizes the distinctive proportion of rare earth element, controls the flow of slurries well, effectively isolates the impurity such as silicon, aluminium, iron.
Spiral classifier comprises agitation vat 1, stir shaft 2 is provided with in agitation vat 1, it is outside that one end of stir shaft 2 extends to agitation vat 1 by the top of agitation vat 1 or bottom up or down, the stir shaft 2 being positioned at agitation vat 1 is provided with agitating vane 3, the end being positioned at the stir shaft 2 outside agitation vat 1 is connected with motor 4, the top of agitation vat 1 is provided with overflow outlet 5, and overflow outlet 5 is arranged at distance agitation vat 1 top 20% agitation vat 1 At The Height; The middle part of agitation vat 1 is provided with major ingredient outlet 6, and major ingredient outlet 6 is arranged at distance agitation vat 1 top 70% agitation vat 1 At The Height; The bottom of agitation vat 1 is provided with waste outlet 7, and waste outlet 7 is arranged bottom agitation vat 1; The top of agitation vat 1 is provided with opening for feed 8.
(2) by the enrichment material of rare earth element with the water logging of vitriol oil low-temperature bake, in bicarbonate of ammonia metathesis and filtering and impurity removing, prepare thick carbonated rare earth, extracting and separating high purity rare earth compound.Useless polishing powder from rare earth exists with oxyfluoride form, and water insoluble, being slightly soluble in acid, is first remove the organic impuritys such as dispersion agent in the weakly acid soln of 4 at pH.In secondary dedoping step, by silicon, aluminium, iron Ex-all, the useless polishing powder from rare earth material of TREO>80% can be obtained after drainage precipitation.Then, the useless polishing powder from rare earth material of TREO>80% is entered sulfuric acid decomposition operation.
Step (2) is implemented as follows:
A, prepare vitriol oil mixed slurry: in the enrichment material of the obtained rare earth element of step (1), add the vitriol oil in order to improve dispersiveness and the mobility of slurry, the enrichment material of rare earth element mixes by weight the ratio for 1:0.7 with the vitriol oil, obtained vitriol oil mixed slurry, the vitriol oil is technical grade, and concentration is not less than 90wt%;
B, roasting: by vitriol oil mixed slurry 400 DEG C of dynamic roastings 1 hour, obtained baking mixes, uses normal temperature water logging, is washed off by the vitriol oil by baking mixes, obtained infusion;
C, prepare rare earth oxide: infusion after neutralization is filtered routinely extracting process prepare mixed rare-earth oxide or single rare earth oxide compound.
Embodiment 3: the method utilizing useless polishing powder from rare earth cyclic regeneration rare earth compound, it comprises the steps: (1) gives up polishing powder from rare earth through enrichment, produces the enrichment material of rare earth element;
A, prepare slip: by the useless polishing powder from rare earth mixture of total amount of rare earth TREO=35wt%, add water soaking and make slip in 8 minutes, stock quality concentration is 20%, then adds technical hydrochloric acid in slip, and the concentration of technical hydrochloric acid is greater than 36wt%, slip pH value is adjusted to 3, control pH value well, acidity is too strong, dissolves and tides over height, material pasty state will be caused, not easily filtering-depositing.Then enter spiral classifier by conduit after slurry being stirred 22 minutes in mixing agitator, the rotating speed of mixing agitator is 40 revs/min; Be uniformly mixed in process, rotating speed is not easily too high, reaches that slurry is evenly not stratified is advisable, and fully mixes, is beneficial to filtering and impurity removing.
B, slip are through spiral classifier concentration and separation: the overflow outlet 5 of mass rate through spiral classifier top containing frivolous material 10% is overflowed, filter through 200 mesh filter screens, clear water after filtration is back to mixing agitator through pump line and recycles, and the foreign material on filter screen are waste; Wherein, in the mass rate unit time, fluid passes through the fluid mass of closed conduct or open channel free area.Frivolous material comprises resin component, calcium, dispersion agent.
Isolated non-rare earth heavy element is discharged by spiral classifier bottom waste outlet 7, and non-rare earth heavy element has aluminium (Al
2o
3), silicon (SiO
2) also having the rare earth element mixing of about 2% wherein, non-rare earth heavy element is deposited pending as byproduct enrichment after quiescent setting;
The enrichment material of isolated rare earth element exports 6 by the major ingredient in the middle part of spiral classifier and discharges, the slip of 60% mass percent exports 6 by major ingredient and reclaims, after the enrichment material of rare earth element reclaimed was filtered dry naturally through 24 hours, moisture content is at 10-15%, and the enrichment material Rare Earth Element Contents of rare earth element is 68%.
Spiral classifier is shunted with spiral gravity, utilizes the distinctive proportion of rare earth element, controls the flow of slurries well, effectively isolates the impurity such as silicon, aluminium, iron.
Spiral classifier comprises agitation vat 1, stir shaft 2 is provided with in agitation vat 1, it is outside that one end of stir shaft 2 extends to agitation vat 1 by the top of agitation vat 1 or bottom up or down, the stir shaft 2 being positioned at agitation vat 1 is provided with agitating vane 3, the end being positioned at the stir shaft 2 outside agitation vat 1 is connected with motor 4, the top of agitation vat 1 is provided with overflow outlet 5, and overflow outlet 5 is arranged at distance agitation vat 1 top 20% agitation vat 1 At The Height; The middle part of agitation vat 1 is provided with major ingredient outlet 6, and major ingredient outlet 6 is arranged at distance agitation vat 1 top 70% agitation vat 1 At The Height; The bottom of agitation vat 1 is provided with waste outlet 7, and waste outlet 7 is arranged bottom agitation vat 1; The top of agitation vat 1 is provided with opening for feed 8.
(2) by the enrichment material of rare earth element with the water logging of vitriol oil low-temperature bake, in bicarbonate of ammonia metathesis and filtering and impurity removing, prepare thick carbonated rare earth, extracting and separating high purity rare earth compound.Useless polishing powder from rare earth exists with oxyfluoride form, and water insoluble, being slightly soluble in acid, is first remove the organic impuritys such as dispersion agent in the weakly acid soln of 4 at pH.In secondary dedoping step, by silicon, aluminium, iron Ex-all, the useless polishing powder from rare earth material of TREO>80% can be obtained after drainage precipitation.Then, the useless polishing powder from rare earth material of TREO>80% is entered sulfuric acid decomposition operation.
Step (2) is implemented as follows:
A, prepare vitriol oil mixed slurry: in the enrichment material of the obtained rare earth element of step (1), add the vitriol oil in order to improve dispersiveness and the mobility of slurry, the enrichment material of rare earth element mixes by weight the ratio for 1:0.6 with the vitriol oil, obtained vitriol oil mixed slurry, the vitriol oil is technical grade, and concentration is not less than 90wt%;
B, roasting: by vitriol oil mixed slurry 360 DEG C of dynamic roastings 1.2 hours, obtained baking mixes, uses normal temperature water logging, is washed off by the vitriol oil by baking mixes, obtained infusion;
C, prepare rare earth oxide: infusion after neutralization is filtered routinely extracting process prepare mixed rare-earth oxide or single rare earth oxide compound.
Embodiment 4: the rare-earth products utilizing the reclaiming of embodiment 1-3 method, rare-earth yield is greater than 95%, and efficiency is high, and output is large, and earth solution can output carbonated rare earth or rare earth oxalate through precipitation, can directly as preparing rare-earth polishing material.
Claims (9)
1. utilize the method for useless polishing powder from rare earth cyclic regeneration rare earth compound, it is characterized in that, it comprises the steps: (1) gives up polishing powder from rare earth through enrichment, produces the enrichment material of rare earth element; (2) by the enrichment material of described rare earth element with the water logging of vitriol oil low-temperature bake, in bicarbonate of ammonia metathesis and filtering and impurity removing, prepare thick carbonated rare earth, extracting and separating high purity rare earth compound.
2. utilization according to claim 1 is given up polishing powder from rare earth cyclic regeneration rare earth compound method, and it is characterized in that, described step (1) is implemented as follows:
A, prepare slip: by the useless polishing powder from rare earth mixture of total amount of rare earth TREO=35wt%, add water soaking 5-10 minute and make slip, described stock quality concentration is 20%, hydrochloric acid is added again in described slip, described slip pH value is adjusted to 3-4, after then described slurry being stirred 20-25 minute in mixing agitator, enters spiral classifier by conduit;
B, slip are through spiral classifier concentration and separation: the overflow outlet of mass rate through described spiral classifier top containing frivolous material 10% is overflowed, filter through 200 mesh filter screens, clear water after filtration is back to described mixing agitator through pump line and recycles, and the foreign material on filter screen are waste;
Isolated non-rare earth heavy element is discharged by described spiral classifier bottom waste outlet, and described non-rare earth heavy element is deposited pending as byproduct enrichment after quiescent setting;
The enrichment material of isolated described rare earth element is exported by the major ingredient in the middle part of described spiral classifier discharges, the described slip of 60% mass percent is exported by described major ingredient and reclaims, after the enrichment material of described rare earth element reclaimed was filtered dry naturally through 24 hours, moisture content is at 10-15%, and the enrichment material Rare Earth Element Contents of described rare earth element is 60-80%.
3. utilization according to claim 2 is given up polishing powder from rare earth cyclic regeneration rare earth compound method, and it is characterized in that, described hydrochloric acid is technical hydrochloric acid, and the concentration of described technical hydrochloric acid is greater than 36wt%.
4. utilization according to claim 2 is given up polishing powder from rare earth cyclic regeneration rare earth compound method, and it is characterized in that, the rotating speed of described mixing agitator is 30-50 rev/min.
5. utilization according to claim 2 is given up polishing powder from rare earth cyclic regeneration rare earth compound method, it is characterized in that, described spiral classifier comprises agitation vat, stir shaft is provided with in described agitation vat, it is outside that one end of described stir shaft extends to described agitation vat by the top of described agitation vat or bottom up or down, the described stir shaft being positioned at described agitation vat is provided with agitating vane, the end being positioned at the described stir shaft outside described agitation vat is connected with motor, the top of described agitation vat is provided with described overflow outlet, the middle part of described agitation vat is provided with the outlet of described major ingredient, the bottom of described agitation vat is provided with described waste outlet, the top of described agitation vat is provided with opening for feed.
6. utilization according to claim 5 is given up polishing powder from rare earth cyclic regeneration rare earth compound method, it is characterized in that, described overflow outlet is arranged at apart from agitation vat At The Height described in described agitation vat top 20%, described major ingredient outlet is arranged at apart from agitation vat At The Height described in described agitation vat top 70%, and described waste outlet is arranged bottom described agitation vat.
7. utilization according to claim 1 is given up polishing powder from rare earth cyclic regeneration rare earth compound method, and it is characterized in that, described step (2) is implemented as follows:
A, prepare vitriol oil mixed slurry: in the enrichment material of the obtained described rare earth element of described step (1), add the vitriol oil, the enrichment material of described rare earth element mixes by weight the ratio for 1:0.6-1:0.7 with the described vitriol oil, obtained vitriol oil mixed slurry;
B, roasting: by described vitriol oil mixed slurry at 350 DEG C-400 DEG C roasting 1-1.5 hour, obtained baking mixes, by the water logging of described baking mixes normal temperature;
C, prepare rare earth oxide: described infusion after neutralization is filtered routinely extracting process prepare mixed rare-earth oxide or single rare earth oxide compound.
8. utilization according to claim 7 is given up polishing powder from rare earth cyclic regeneration rare earth compound method, and it is characterized in that, the described vitriol oil is technical grade, and concentration is not less than 90wt%, and described roasting is dynamic roasting.
9. utilization according to claim 7 is given up polishing powder from rare earth cyclic regeneration rare earth compound method, and it is characterized in that, the optimum calcination temperature in described calcination steps is 360 DEG C, and best roasting time is 1.2 hours.
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| CN201510367797.3A CN104946895B (en) | 2015-06-29 | 2015-06-29 | Rare earth compound recycling method utilizing waste rare earth polishing powder |
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| CN201510367797.3A CN104946895B (en) | 2015-06-29 | 2015-06-29 | Rare earth compound recycling method utilizing waste rare earth polishing powder |
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| CN104946895A true CN104946895A (en) | 2015-09-30 |
| CN104946895B CN104946895B (en) | 2017-04-26 |
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| CN201510367797.3A Active CN104946895B (en) | 2015-06-29 | 2015-06-29 | Rare earth compound recycling method utilizing waste rare earth polishing powder |
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| CN105489332A (en) * | 2016-01-05 | 2016-04-13 | 江苏南方永磁科技有限公司 | Permanent magnet material containing multiple rare earth phases and preparation method |
| CN106498173A (en) * | 2016-12-18 | 2017-03-15 | 赣州科源甬致科技有限公司 | A kind of rare earth waste reclaims the device that use can improve rare earth waste utilization rate |
| CN106521149A (en) * | 2016-12-18 | 2017-03-22 | 南昌诺义弘科技有限公司 | Rare earth oxide extraction equipment for rare earth waste recycling |
| CN107188215A (en) * | 2017-05-24 | 2017-09-22 | 中国北方稀土（集团）高科技股份有限公司 | The method that reaction end is automatically adjusted in carbonated rare earth continuous precipitation production process |
| CN107555799A (en) * | 2017-09-26 | 2018-01-09 | 东北大学 | A kind of method for preparing glass ceramics using discarded polishing powder from rare earth |
| CN106916941B (en) * | 2017-03-13 | 2018-06-05 | 北京科技大学 | A kind of method that production rare earth is separated using iron content rare-earth original ore |
| CN108372179A (en) * | 2017-12-28 | 2018-08-07 | 龙南县中利再生资源开发有限公司 | A kind of regeneration method of rare earth permanent-magnetic material |
| CN108559851A (en) * | 2018-06-22 | 2018-09-21 | 长沙中硅水泥技术开发有限公司 | A kind of System and method for of cement kiln synergic processing polishing powder from rare earth waste material |
| CN114381206A (en) * | 2022-01-07 | 2022-04-22 | 甘肃金阳高科技材料有限公司 | Method for preparing rare earth polishing powder by regenerating glass polishing waste residues |
| WO2022116870A1 (en) * | 2020-12-02 | 2022-06-09 | 北京工业大学 | Method for recovering rare earths from waste cerium-based rare-earth polishing powder by two-step acid leaching stepwise separation |
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| CN106498173A (en) * | 2016-12-18 | 2017-03-15 | 赣州科源甬致科技有限公司 | A kind of rare earth waste reclaims the device that use can improve rare earth waste utilization rate |
| CN106521149A (en) * | 2016-12-18 | 2017-03-22 | 南昌诺义弘科技有限公司 | Rare earth oxide extraction equipment for rare earth waste recycling |
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| CN106916941B (en) * | 2017-03-13 | 2018-06-05 | 北京科技大学 | A kind of method that production rare earth is separated using iron content rare-earth original ore |
| CN107188215A (en) * | 2017-05-24 | 2017-09-22 | 中国北方稀土（集团）高科技股份有限公司 | The method that reaction end is automatically adjusted in carbonated rare earth continuous precipitation production process |
| CN107555799A (en) * | 2017-09-26 | 2018-01-09 | 东北大学 | A kind of method for preparing glass ceramics using discarded polishing powder from rare earth |
| CN107555799B (en) * | 2017-09-26 | 2020-10-23 | 东北大学 | Method for preparing glass ceramic by using waste rare earth polishing powder |
| CN108372179A (en) * | 2017-12-28 | 2018-08-07 | 龙南县中利再生资源开发有限公司 | A kind of regeneration method of rare earth permanent-magnetic material |
| CN108559851A (en) * | 2018-06-22 | 2018-09-21 | 长沙中硅水泥技术开发有限公司 | A kind of System and method for of cement kiln synergic processing polishing powder from rare earth waste material |
| CN108559851B (en) * | 2018-06-22 | 2023-11-17 | 长沙中硅环保科技有限公司 | System and method for cooperatively disposing rare earth polishing powder waste by cement kiln |
| WO2022116870A1 (en) * | 2020-12-02 | 2022-06-09 | 北京工业大学 | Method for recovering rare earths from waste cerium-based rare-earth polishing powder by two-step acid leaching stepwise separation |
| CN114381206A (en) * | 2022-01-07 | 2022-04-22 | 甘肃金阳高科技材料有限公司 | Method for preparing rare earth polishing powder by regenerating glass polishing waste residues |
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Effective date of registration: 20200422 Address after: 014060 west side of Baofu railway bridge, Baotou City, Inner Mongolia Autonomous Region Patentee after: Baotou Haorui rare earth Co.,Ltd. Address before: 014010, the Inner Mongolia Autonomous Region C rare earth hi tech Zone Pioneering Center Software Park, block 506, Baotou Patentee before: BAOTOU NEW CENTURY RARE EARTH LTD. |
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Denomination of invention: Method for recycling rare earth compound using waste rare earth polishing powder Effective date of registration: 20220909 Granted publication date: 20170426 Pledgee: Shanghai Pudong Development Bank Co.,Ltd. Baotou Branch Pledgor: Baotou Haorui rare earth Co.,Ltd. Registration number: Y2022150000098 |