CN105568006A - Method for cleaning smelted mixed rare earth concentrate by concentrated sulfuric acid - Google Patents
Method for cleaning smelted mixed rare earth concentrate by concentrated sulfuric acid Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22B59/00—Obtaining rare earth metals
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- 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
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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Abstract
The invention relates to a method for cleaning smelted mixed rare earth concentrate by concentrated sulfuric acid. The method is characterized by comprising the following steps of chemically selecting and gathering mixed rare earth concentrate by use of a hydrochloric acid solution and a reinforced impurity remover, mixing the chemically-selected concrete with the concentrated sulfuric acid to roast at a low temperature, carrying out water leaching on roasted concentrate, carrying out resource recovery on a water leaching fluid, carrying out tail gas absorption, and recycling chemical-selected wastewater resources. The method has the advantages that the source of three wastes of a current concentrated sulfuric acid high-temperature roasting process is solved at the front end of concentrate treatment, so that various problems in a low-temperature acid method are solved, the follow-up three-waste treatment difficulty is greatly reduced, the rare earth direct recovery rate is increased, and the purpose of comprehensively recycling various resources in the concentrate and auxiliary materials is finally realized.
Description
Technical field
The present invention relates to a kind of vitriol oil and clean the method for smelting mixed rare earth concentrates, belong to field of hydrometallurgy.
Background technology
In baiyunebo concentrate thing product structure, rare earth grade is the concentrate of 50wt% ~ 65wt% is main products.At present, rare earth grade mainly adopts vitriol oil high-temperature roasting decomposition technique process (hereinafter referred to as " high temperature acid system ") close to the concentrate (being commonly called as " 50 concentrate ") of 50wt%, about has 100,000 tons of concentrate to adopt this art breading every year.This technique brings the three industrial wastes problems such as a large amount of magnesium sulfate waste water transition, sulphur fluorine silicon mixing high temperature acid gas, thoriated emissive industrial waste residue, and intractability is very big.Cause the P in concentrate, F, Th, Ca, Fe, undecomposed rare-earth mineral thus, and the SO in auxiliary material
4 2-, the valuable resource such as Mg enters Industrial " three Waste ", not only make a large amount of valuable resource waste, bring huge pressure also to enterprise and environmental administration.
In the case, some domestic research institutions propose various solution respectively.Such as: the nineties in last century, more domestic research institution proposes the technique of vitriol oil low-temperature bake decomposing Baotou mixed rare earth concentrates, and this technique considerably reduces concentrate decomposition temperature, and the radiothorium resource simultaneously in concentrate and rare earth are extracted in the lump.Problems existing is: in mixed rare earth concentrates, some impurity components form low-temperature eutectic thing at rotary kiln end generation ring formation at roasting process, causes roasting cannot serialization.After, also there is technician to attempt adding scraper plate at concentrate and sulfuric acid mixture opening for feed and solve ring formation problem, finally because ring formation thing hardness is large, cause long-play rear feeding mouth stopping property poor, ring formation problem does not thoroughly solve, and the effusion of kiln hood acid tail gas, cause work condition environment to worsen further.Zhao Zhihua equals the patent of invention (application number: 200510063032.7) disclosing " stepped sulfuric acid treatment and roasting process for decomposing Baotou RE ore concentrate " for 2006, propose and adopt low-temperature bake and high-temperature roasting process integration, being absorbed by exhaust gas component substep becomes fluorine silicon nitration mixture and sulfuric acid; In concentrate, thorium fixedly becomes the operational path of thorium pyrophosphate.This technique optimizes the intractability reducing rear end by front end, have clear and definite novelty.But Problems existing is: (1) low-temperature bake section, in concentrate, some impurity components easily form low-temperature eutectic thing, cause ring formation of rotary kiln, make technique cannot serialization; (2) high temperature calcination section, residual sulfuric acid is except part volatilization, and decomposition reaction occurs major part, effusion high density SO
2gas is difficult to process; (3) the emissive industrial waste residue quantity of slag is large, the wastings of resources such as phosphorus, iron, sulphur, calcium.University Of Science and Technology of the Inner Mongol professor Li Mei discloses " Bayan Obo rare earth ore concentrate prepares the novel method of rare earth chloride " (application number: 201110221839.4).Oxidizing roasting is combined with high alkali liquid decomposition technique by this technology, well achieve Bayan Obo mixed rare earth concentrates to decompose, but this process continuity is poor, the raw material concentrate grade used is at 60 ~ 68wt%, high-grade raw material not only can increase beneficiation cost and beneficiation wastewater quantum of output, meanwhile, the yield of technique of preparing is lower; In addition, in alkali waste water, fluorine, a reclamation of phosphorus resource difficult problem are never properly settled.Baotou tombar thite institute Cui foundation etc. discloses " a kind of recovery method to rare earth acid technological process waste residue middle-weight rare earths, thorium and iron " (application number 201310074514.7), solve the unleachable problem of thorium in generally acknowledged vitriol oil high temperature acid system technique waste residue, invent the extracting method of thorium, rare earth and iron in high temperature acid system technique waste residue, for the innovation of existing acid technological process is laid a good foundation.
In the face of increasingly severe environmental requirement, the certain measure that manufacturing enterprise's " three wastes " problem to existing acid technological process is taked.Such as: transition, magnesium sulfate waste water to be sized mixing neutralization by adding calcium oxide, and formation calcium sulfate and magnesium hydroxide mixed sludge, after reuse water heat exchange condensation, reuse is to water logging technique.This technology realizes reuse after eliminating a large amount of sulfate radical of waste water and magnesium ion, extenuate the difficult problem of environmental protection to a certain extent, but due to the circulation collection effect of the impurity such as aluminium, silicon, manganese in concentrate, iterative cycles has badly influenced the leaching effect of roasted ore middle-weight rare earths.Acid tail gas process aspect, current employing spraying and dedusting-multi-stage countercurrent spray-absorption-nitration mixture underpressure distillation separation-single sour multiple-effect evaporation beneficiation technologies is separated sulfuric acid in tail gas and fluorine silicon nitration mixture and prepares and become close to the sulfuric acid of 70% and the hydrofluoric acid of 40%, but because exhaust gas component and spray-absorption acid strength float large, vacuum distillation process is made to be difficult to control, in product, S and F carries secretly comparatively serious mutually, and the fluoric acid product index of recovery is defective.And vent gas treatment long flow path, processing costs is high.Emissive industrial waste residue aspect, often processes 1 ton of concentrate, by output 0.65 ~ 0.75 ton of dry slag, and about 1.1 tons of wet slags.At present, all wet slags are all stored in the special slag storehouse of environmental administration, also need the carrying cost paying 250 yuan/ton of wet slags.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, there is provided one the root of existing vitriol oil high-temperature roasting technique " three wastes " problem can be solved in concentrate process front end, thus the various difficult problems that solution low temperature acid system faces, significantly reduce follow-up " three wastes " intractability, improve straight yield of rare earth, and finally realize the vitriol oil that in concentrate and auxiliary material, various resource comprehensive utilization utilizes and clean the method for smelting mixed rare earth concentrates.
Realize thinking of the present invention to be described as follows:
Mixed rare earth concentrates, under the effect of hydrochloric acid with strengthening cleaner sulfuric acid, makes the elements such as the calcium in concentrate, iron, aluminium, manganese and a small amount of fluorine, phosphorus dissolve, and strengthening cleaner improves the dissolution rate of these impurity, and inhibits the stripping of rare earth, thorium.The benefit so brought is, the first, and the basic substance that calcium, fluorine, aluminium etc. easily form low-temperature eutectic thing does not exist, and the ring formation problem of low-temperature bake is solved, and can realize serialization running, and significantly reduce roasting process energy consumption; The second, the removal of calcium ion, makes the main component calcium sulfate of original emissive industrial waste residue to be formed, significantly reduces the emissive industrial waste residue quantity of slag; No longer there is the slow crystalline polamer of calcium sulfate in water logging process, rare earth dissolution rate and solubility rate increase, and make dissolution process high efficiency; Meanwhile, change and select the calcium ion in waste water can be removed by the mode adding sulfuric acid, form clean cold calcium sulfate by product, realize resource reclaim; 3rd, the removal of the impurity such as calcium, iron, aluminium, manganese, make to make the transition sulfate wastewater composition simply, there is not salinity crystallization in the modes such as membrane concentration, reduces waste water reclamation cost; 4th, pre-treatment eliminates various impurity, causes concentrate weight and grade to concentrate further, changes concentrate selection middle-weight rare earths salinity and more easily decomposes, significantly reduce acid, alkali consumption; 5th, fluorine, silicon are removed close to 50%, cause being difficult in tail gas form silicon tetrafluoride, and hydrogen fluoride generation significantly reduces.
After deliming concentrate mixes with the vitriol oil, select low-temperature bake but not high-temperature roasting, major advantage is, the first, low-temperature bake process, the vitriol oil does not decompose, exhaust gas component is single hydrofluoric acid, and without the need to being separated sulfuric acid and fluorine silicon nitration mixture through underpressure distillation, vent gas treatment difficulty and cost reduce; The second, change in concentrate selection and eliminate calcium, iron, lose phosphorus fixation effect, make phosphor resource no longer be mixed into emissive industrial waste residue and enter infusion, meanwhile, thorium also enters infusion, phosphorus, iron and thorium can be reclaimed respectively and form byproduct, the emissive industrial waste residue quantity of slag is significantly reduced again.Do not select the reason of high-temperature roasting to be that high-temperature calcination process can aggravate sulfuric acid decomposition, force phosphate radical to be combined with rare earth ion, reduce concentrate rate of decomposition.
After roasted ore mixes with water, roasted ore principal constituent is sulfuric acid rare earth, and foreign matter content is extremely low, and sulfuric acid rare earth leaching efficiency is high, without the need to through complex processes such as multistage pulp washing-pickling-washings.The radioactivity water logging slag quantity of slag reduces, composition is simple, it is obvious that the undecomposed rare earth ore concentrate of macrobead and concentrate decompose (being called for short " silicon barium the slag ") topographical difference such as rear remaining a small amount of silicate, tertiary iron phosphate, calcium sulfate, barium sulfate, the present invention is according to this phenomenon, introduce cyclone separation process, make the simple high efficiente callback of rare earth resources a small amount of in waste residue, further increase rare earth resources yield.Meanwhile, the present invention devises the radiosilicon barium slag and thorium oxalate byproduct mixed storage that are obtained on cyclonic separation upper strata, namely reduces thorium oxalate product radioactivity grade, is easy to deposit, be also convenient to the extraction of thorium resources in the future.
Based on above-mentioned thinking, method of the present invention comprises the steps:
(1) change and select enrichment: be that the hydrochloric acid soln of 1.0 ~ 4.0mol/L is mixed in proportion with strengthening cleaner by the mixed rare earth concentrates of 45%≤REO mass percentage≤68% and 2%≤CaO mass percentage≤15%, hydrogen ion substance withdrawl syndrome, the solid-liquid volume ratio of mixed rare earth concentrates and hydrochloric acid soln is 1:2 ~ 1:9; The ratio of strengthening cleaner and hydrochloric acid soln strengthens cleaner for adding 5 ~ 20 grams in often liter of hydrochloric acid soln, 85 DEG C≤temperature≤100 DEG C, 120min≤time≤180min heating condition under stirring and dissolving, after dissolving terminates, filter and obtain the change concentrate selection of 62%≤REO mass percentage≤80% and 0.5%≤CaO mass percentage≤2.0% and waste water is selected in change;
(2) concentrate selection low-temperature bake is changed: changing concentrate selection with the vitriol oil is after 1:1.2 ~ 1.4 mix according to weight ratio, and 250 DEG C≤temperature≤300 DEG C, under 1.5 ~ 5.0 hours time condition, continuous roasting, obtains roasted ore;
(3) roasted ore water logging: roasted ore and water are sized mixing and leached, according to REO content allotment infusion volume in roasted ore, REO content in infusion is made to remain on 40 ~ 60g/L, infusion and water logging slag is obtained after filtering separation, water logging slag weight is 5% ~ 15% of mixed rare earth concentrates weight, water logging slag uses water pulp washing again, cyclonic separation, solid-liquid separation, obtain the undecomposed mixed rare earth concentrates of upper layer of silicon barium slag and lower floor, silicon barium slag main component is barium sulfate and silicate, its weight is 3% ~ 10% of mixed rare earth concentrates weight, undecomposed mixed rare earth concentrates returns step 2 and continues roasting,
(4) infusion resource reclaim: infusion is that 1% ~ 5% primary amine solutions extracts thorium, oxalic acid back extraction is thorium oxalate byproduct with volumn concentration, and thorium oxalate deposits in radioactivity slag storehouse after mixing with silicon barium slag; Carry the amount of substance ratio (namely iron phosphorus compares) of the allotment of the raffinate ferric sulfate after thorium iron and phosphorus to 2 ~ 4:1, add neutralizing agent, oxygenant neutralizes, endpoint pH is regulated to stablize to 3.8 ~ 4.0 removal iron and phosphorus, ferrophosphorus slag pH value is 1.0 ~ 2.0, solid-liquid weight ratio is form tertiary iron phosphate byproduct after the dilute sulphuric acid washing of 1:2 ~ 4, and washings is back to step 3; Neutralizer is through transition, the single re chloride of separation preparation, and corresponding sulfate wastewater is after the enrichment of removal of impurities film, and Water circulation, to step 3, forms corresponding vitriol byproduct;
(5) tail gas absorption: tail gas forms silicofluoric acid byproduct by the spray-absorption that adds water, multiple-effect evaporation, and water of condensation is used for the hydrochloric acid soln in configuration step 1;
(6) change selects waste water resource to reclaim and recycle: change and select waste water continuation interpolation mass percentage to be the sulphuric acid soln of 60% ~ 99%, its add-on is according to H
2sO
4the stoichiometric ratio of reacting with CaO, add the sulphuric acid soln of theoretical amount 70 ~ 90%, prepare calcium sulfate byproduct, after solution after deliming supplements hydrochloric acid soln, the acidity of mixing solutions is more than or equal to formerization and selects hydrochloric acid soln acidity, for circular treatment mixed rare earth concentrates, its cycle index is limited to change CaO mass percentage≤2.0% in concentrate selection for the last time; Change after multiple stage circulation selects waste water through ammoniacal liquor or liquefied ammonia fractional neutralization, the first step: filter after endpoint pH reaches 1.0 ~ 1.5, reclaim phosphorus, rare earth, iron mixing slag; Second step: continuing to be neutralized to pH value is 4.5 ~ 5.0, recovery Calcium Fluoride (Fluorspan) byproduct, the ammonium chloride waste-water after neutralization reclaims ammonium chloride and distilled water by evaporation, phosphorus, rare earth, iron mixing slag and the baking mixed recovering rare earth of change concentrate selection, phosphorus, iron.
Strengthening cleaner described in step 1 is sulfuric acid;
The vitriol oil described in step 2 is the sulphuric acid soln that mass percent concentration is greater than 90%;
Neutralizing agent described in step 4 is magnesium oxide, and oxygenant is hydrogen peroxide;
Advantage of the present invention is: by the root of existing vitriol oil high-temperature roasting technique " three wastes " problem, solve in concentrate process front end, thus solve the various difficult problems that low temperature acid system faces, significantly reduce follow-up " three wastes " intractability, improve straight yield of rare earth, and finally realize the target that in concentrate and auxiliary material, various resource comprehensive utilization utilizes.
Select in wastewater treatment in change, concrete advantage of the present invention is: the first, although add sulfuric acid can form calcium sulfate byproduct, under highly acidity condition, reaction is also thorough.So the present invention adopts the change exceeding positive usual amounts to select hydrochloric acid soln process raw material concentrate, deliming process condition is weakened, is easy to realize serialization.The second, the calcium impurities that can continuing in the solution after sulfuric acid deliming circulates removes in next batch raw material and crystal of calcium sulfate phenomenon does not occur, achieves the target that calcium resource reclaim and deliming liquid recycle, reduces the acid and alkali consumption of this link.3rd, making full use of pH is under 1.0 ~ 1.5 conditions, and the characteristic of rare earth, phosphorus, iron preferential precipitation, devises fractional neutralization technology, and making selects the rare earth in waste water, phosphorus, iron three kinds of resources and the resource such as residual fluorine, calcium to reclaim respectively.
This shows, invention not only simplifies existing acid technological process, effectively reduce the cost such as acid and alkali consumption and energy consumption, also control all kinds of resource trend in concentrate and industrial chemicals respectively, improve rare earth resources yield, achieve and reclaim respectively, reach the clean target with comprehensive utilization of resources of smelting.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention;
Fig. 2 is one of energy spectrum analysis figure of silicon barium slag in embodiment 1;
Fig. 3 is the energy spectrum analysis figure bis-of silicon barium slag;
The energy spectrum analysis figure that Fig. 4 is phosphorus, rare earth, iron mix slag.
Embodiment
Embodiment one
Be that the hydrochloric acid soln of 3.5mol/L mixes with concentrated sulfuric acid solution by 100g mixed rare earth concentrates (REO mass percentage 48.68%, CaO mass percentage 13.2%), hydrogen ion substance withdrawl syndrome.The solid-liquid volume ratio of mixed rare earth concentrates and hydrochloric acid soln is 1:8; 15 grams of vitriol oils are added in often liter of hydrochloric acid soln.Stirring and dissolving 180min under DEG C condition of 93 DEG C≤temperature≤95.After dissolving terminates, filter and obtain the change concentrate selection 67.6g of REO mass percentage 69.85%, CaO mass percentage 0.83% and waste water is selected in change.
Change concentrate selection and the vitriol oil are that 1:1.4 mixes according to weight ratio, roasting 1.5 hours in 280 DEG C of retort furnaces.Roasted ore and water are sized mixing leaching 1 hour, filtration obtains infusion and water logging slag, in infusion, REO content is 48.3g/L, water logging slag uses water pulp washing, cyclonic separation, solid-liquid separation again, obtain upper layer of silicon barium slag 8.3g(and see Figure of description 2,3) and the undecomposed concentrate 0.9g of lower floor, in undecomposed concentrate, REO mass percentage is 64.3%.The silicon barium slag energy spectrum analysis figure test data corresponding with Figure of description 2 is table 1, and the silicon barium slag energy spectrum analysis figure test data corresponding with Figure of description 3 is table 2.
Table 1 silicon barium slag energy spectrum analysis table-1
| Element | Wt% | At% |
| OK | 28.21 | 45.77 |
| AlK | 01.00 | 00.96 |
| SiK | 33.94 | 31.38 |
| SK | 17.15 | 13.88 |
| BaL | 04.18 | 00.79 |
| FeK | 15.52 | 07.22 |
| Matrix | Correction | ZAF |
Table 2 silicon barium slag energy spectrum analysis table-2
| Element | Wt% | At% |
| OK | 13.31 | 42.94 |
| SK | 18.40 | 29.63 |
| BaL | 65.08 | 24.46 |
| FeK | 03.21 | 02.97 |
| Matrix | Correction | ZAF |
Infusion is with 5% primary amine-isooctyl alcohol for extraction agent, and O/A is that 1:5 extracts thorium, and oxalic acid back extraction is thorium oxalate byproduct, and thorium oxalate and silicon barium slag are mixed to form emissive industrial waste residue.The raffinate amount of substance ratio of ferric sulfate allotment iron and phosphorus (i.e. iron phosphorus than), to 4:1, adds magnesium oxide and regulates endpoint pH to stablize to 3.8 ~ 4.0, removal iron and phosphorus.Form tertiary iron phosphate byproduct after the dilute sulphuric acid washing that ferrophosphorus slag pH value is 1.0, solid-liquid weight ratio is 1:2, washings is back to water logging.Neutralizer is through transition, the single re chloride of separation preparation, and corresponding sulfate wastewater is after removal of impurities enrichment, and Water circulation, to water logging technique, forms corresponding vitriol byproduct.
Tail gas is by the spray-absorption that adds water, and multiple-effect evaporation forms silicofluoric acid byproduct, and water of condensation selects the hydrochloric acid soln of process for configuration.Change and select waste water continuation interpolation mass percentage to be the sulphuric acid soln of 92%, its add-on is according to H
2sO
4the stoichiometric ratio of reacting with CaO adds the sulphuric acid soln of theoretical amount 70%, prepares calcium sulfate byproduct.Solution acidity after deliming is 3.1mol/L, and for circular treatment mixed rare earth concentrates, in secondary concentrate selection, CaO mass percentage is 1.12%; After three circulations, solution acidity is 2.7mol/L, supplements hydrochloric acid to 3.5mol/L; After four circulations, changing CaO mass percentage in concentrate selection is 2.02%.Stop circulation, change and select waste water through ammoniacal liquor fractional neutralization, reaching the first step endpoint pH is 1.0 ~ 1.5 rear filtrations, reclaims phosphorus, rare earth, iron mixing slag (see Figure of description 4); Continuing to be neutralized to second step pH value is 4.5 ~ 5.0, reclaims Calcium Fluoride (Fluorspan) byproduct, and the ammonium chloride waste-water after neutralization reclaims ammonium chloride and distilled water by evaporation.Phosphorus, rare earth, iron mixing slag and the baking mixed recovering rare earth of change concentrate selection, phosphorus, iron.The phosphorus corresponding with Figure of description 4, rare earth, iron mixing slag energy spectrum analysis figure test data are table 3.
Table 3 phosphorus, rare earth, iron mixing slag energy spectrum analysis table
| Element | Wt% | At% |
| OK | 11.72 | 37.92 |
| PK | 16.08 | 26.87 |
| ClK | 00.54 | 00.78 |
| CaK | 01.06 | 01.37 |
| LaL | 13.06 | 04.87 |
| CeL | 27.05 | 09.99 |
| PrL | 02.82 | 01.03 |
| NdL | 14.94 | 05.36 |
| FeK | 12.73 | 11.80 |
| Matrix | Correction | ZAF |
Embodiment two
Be that the hydrochloric acid soln of 2.5mol/L mixes with concentrated sulfuric acid solution by 100g mixed rare earth concentrates (REO mass percentage 58.32%, CaO mass percentage 13.2%), hydrogen ion substance withdrawl syndrome.The solid-liquid volume ratio of mixed rare earth concentrates and hydrochloric acid soln is 1:5; The 8g vitriol oil is added in often liter of hydrochloric acid soln.Stirring and dissolving 150min under DEG C condition of 93 DEG C≤temperature≤95.After dissolving terminates, filter and obtain the change concentrate selection 76.3g of REO mass percentage 74.5%, CaO mass percentage 0.51% and waste water is selected in change.
Change concentrate selection and the vitriol oil are that 1:1.2 mixes according to weight ratio, roasting 3 hours in 250 DEG C of retort furnaces.Roasted ore and water are sized mixing and are leached 40min, filtration obtains infusion and water logging slag, in infusion, REO content is 54.7g/L, water logging slag uses water pulp washing, cyclonic separation, solid-liquid separation again, obtain upper layer of silicon barium slag 4.5g and the undecomposed concentrate 1.1g of lower floor, in undecomposed concentrate, REO percentage composition is 68.0%, can continue roasting recovering rare earth.Infusion is with 10% primary amine-isooctyl alcohol for extraction agent, and O/A is that 1:10 extracts thorium, and oxalic acid back extraction is thorium oxalate byproduct, and thorium oxalate and silicon barium slag are mixed to form emissive industrial waste residue.The raffinate amount of substance ratio of ferric sulfate allotment iron and phosphorus (i.e. iron phosphorus than), to 2:1, adds magnesium oxide and regulates endpoint pH to stablize to 3.8 ~ 4.0, removal iron and phosphorus.Form tertiary iron phosphate byproduct after the dilute sulphuric acid washing that ferrophosphorus slag pH value is 1.0, solid-liquid weight ratio is 1:3, washings is back to water logging.Neutralizer is through transition, the single re chloride of separation preparation, and corresponding magnesium sulfate waste water is after the enrichment of removal of impurities film, and Water circulation, to water logging technique, forms corresponding magnesium sulfate byproduct.
Tail gas is by the spray-absorption that adds water, and multiple-effect evaporation forms silicofluoric acid byproduct, and water of condensation selects the hydrochloric acid soln of process for configuration.Change and select waste water continuation interpolation mass percentage to be the sulphuric acid soln of 69%, its add-on is according to H
2sO
4the stoichiometric ratio of reacting with CaO adds the sulphuric acid soln of theoretical amount 75%, prepares calcium sulfate byproduct.Solution acidity after deliming is 2.2mol/L, for circular treatment mixed rare earth concentrates, CaO mass percentage≤0.95% in secondary concentrate selection, supplement hydrochloric acid to 2.5mol/L, carry out following cycle, after five circulations, changing CaO mass percentage in concentrate selection is 1.97%, changing selects waste water through ammoniacal liquor fractional neutralization, and reaching the first step endpoint pH is 1.0 ~ 1.5 rear filtrations, reclaims phosphorus, rare earth, iron mixing slag; Continuing to be neutralized to second step pH value is 4.5 ~ 5.0, reclaims Calcium Fluoride (Fluorspan) byproduct, and the ammonium chloride waste-water after neutralization reclaims ammonium chloride and distilled water by evaporation.Phosphorus, rare earth, iron mixing slag and the baking mixed recovering rare earth of change concentrate selection, phosphorus, iron.
Embodiment three
Be that the hydrochloric acid soln of 1.3mol/L mixes with concentrated sulfuric acid solution by 100g mixed rare earth concentrates (REO mass percentage 67.96%, CaO mass percentage 4.55%), hydrogen ion substance withdrawl syndrome.The solid-liquid volume ratio of mixed rare earth concentrates and hydrochloric acid soln is 1:4; The 5g vitriol oil is added in often liter of hydrochloric acid soln.Stirring and dissolving 120min under 85 DEG C of conditions.After dissolving terminates, filter and obtain change concentrate selection 84.1g that REO mass percentage is 78.4%, CaO mass percentage 1.32% and waste water is selected in change.
Change concentrate selection and the vitriol oil are that 1:1.4 mixes according to weight ratio, roasting 4.5 hours in 250 DEG C of retort furnaces.Roasted ore and water are sized mixing and are leached 30min, filtration obtains infusion and water logging slag, in infusion, REO content is 44.6g/L, water logging slag uses water pulp washing, cyclonic separation, solid-liquid separation again, obtain upper layer of silicon barium slag 3.3g and the undecomposed concentrate 0.4g of lower floor, in undecomposed concentrate, REO percentage composition is 72.35%, can continue roasting recovering rare earth.Infusion is with 1% primary amine-isooctyl alcohol for extraction agent, and O/A is that 1:2 extracts thorium, and oxalic acid back extraction is thorium oxalate byproduct, and thorium oxalate and silicon barium slag are mixed to form emissive industrial waste residue.The raffinate amount of substance ratio of ferric sulfate allotment iron and phosphorus (i.e. iron phosphorus than), to 3:1, adds magnesium oxide and regulates endpoint pH to stablize to 3.8 ~ 4.0, removal iron and phosphorus.Form tertiary iron phosphate byproduct after the dilute sulphuric acid washing that ferrophosphorus slag pH value is 2.0, solid-liquid weight ratio is 1:4, washings is back to water logging.Neutralizer is through transition, the single re chloride of separation preparation, and corresponding magnesium sulfate waste water is after the enrichment of removal of impurities film, and Water circulation, to water logging technique, forms corresponding magnesium sulfate byproduct.
Tail gas is by the spray-absorption that adds water, and multiple-effect evaporation forms silicofluoric acid byproduct, and water of condensation selects the hydrochloric acid soln of process for configuration.Change and select waste water continuation interpolation mass percentage to be the sulphuric acid soln of 98%, its add-on is according to H
2sO
4the stoichiometric ratio of reacting with CaO adds the sulphuric acid soln of theoretical amount 85%, prepares calcium sulfate byproduct.Solution acidity after deliming is 1.15mol/L, for circular treatment mixed rare earth concentrates, CaO mass percentage≤1.66% in secondary concentrate selection, supplement hydrochloric acid to 1.5mol/L, after four circulations, changing CaO mass percentage in concentrate selection is 1.88%, changes and selects waste water through ammoniacal liquor fractional neutralization, reaching the first step endpoint pH is 1.0 ~ 1.5 rear filtrations, reclaims phosphorus, rare earth, iron mixing slag; Continuing to be neutralized to second step pH value is 4.5 ~ 5.0, reclaims Calcium Fluoride (Fluorspan) byproduct, and the ammonium chloride waste-water after neutralization reclaims ammonium chloride and distilled water by evaporation.Phosphorus, rare earth, iron mixing slag and the baking mixed recovering rare earth of change concentrate selection, phosphorus, iron.
Claims (4)
1. the vitriol oil cleans a method of smelting mixed rare earth concentrates, it is characterized in that: comprise the steps:
(1) change and select enrichment: be that the hydrochloric acid soln of 1.0 ~ 4.0mol/L is mixed in proportion with strengthening cleaner by the mixed rare earth concentrates of 45%≤REO mass percentage≤68% and 2%≤CaO mass percentage≤15%, hydrogen ion substance withdrawl syndrome, the solid-liquid volume ratio of mixed rare earth concentrates and hydrochloric acid soln is 1:2 ~ 1:9; The ratio of strengthening cleaner and hydrochloric acid soln strengthens cleaner for adding 5 ~ 20 grams in often liter of hydrochloric acid soln, 85 DEG C≤temperature≤100 DEG C, 120min≤time≤180min heating condition under stirring and dissolving, after dissolving terminates, filter and obtain the change concentrate selection of 62%≤REO mass percentage≤80% and 0.5%≤CaO mass percentage≤2.0% and waste water is selected in change;
(2) concentrate selection low-temperature bake is changed: changing concentrate selection with the vitriol oil is after 1:1.2 ~ 1.4 mix according to weight ratio, and 250 DEG C≤temperature≤300 DEG C, under 1.5 ~ 5.0 hours time condition, continuous roasting, obtains roasted ore;
(3) roasted ore water logging: roasted ore and water are sized mixing and leached, according to REO content allotment infusion volume in roasted ore, REO content in infusion is made to remain on 40 ~ 60g/L, infusion and water logging slag is obtained after filtering separation, water logging slag uses water pulp washing, cyclonic separation, solid-liquid separation again, obtain the undecomposed mixed rare earth concentrates of upper layer of silicon barium slag and lower floor, silicon barium slag main component is barium sulfate and silicate, and undecomposed mixed rare earth concentrates returns step 2 and continues roasting;
(4) infusion resource reclaim: infusion is that 1% ~ 5% primary amine solutions extracts thorium, oxalic acid back extraction is thorium oxalate byproduct with volumn concentration, and thorium oxalate deposits in radioactivity slag storehouse after mixing with silicon barium slag; Carry the allotment of the raffinate ferric sulfate after thorium iron to compare to 2 ~ 4:1 with the amount of substance of phosphorus, add neutralizing agent, oxygenant neutralizes, endpoint pH is regulated to stablize to 3.8 ~ 4.0 removal iron and phosphorus, ferrophosphorus slag pH value is 1.0 ~ 2.0, solid-liquid weight ratio is form tertiary iron phosphate byproduct after the dilute sulphuric acid washing of 1:2 ~ 4, and washings is back to step 3; Neutralizer is through transition, the single re chloride of separation preparation, and corresponding sulfate wastewater is after the enrichment of removal of impurities film, and Water circulation, to step 3, forms corresponding vitriol byproduct;
(5) tail gas absorption: tail gas forms silicofluoric acid byproduct by the spray-absorption that adds water, multiple-effect evaporation, and water of condensation is used for the hydrochloric acid soln in configuration step 1;
(6) change selects waste water resource to reclaim and recycle: change and select waste water continuation interpolation mass percentage to be the sulphuric acid soln of 60% ~ 99%, its add-on is according to H
2sO
4the stoichiometric ratio of reacting with CaO, add the sulphuric acid soln of theoretical amount 70 ~ 90%, prepare calcium sulfate byproduct, after solution after deliming supplements hydrochloric acid soln, the acidity of mixing solutions is more than or equal to formerization and selects hydrochloric acid soln acidity, for circular treatment mixed rare earth concentrates, its cycle index is limited to change CaO mass percentage≤2.0% in concentrate selection for the last time; Change after multiple stage circulation selects waste water through ammoniacal liquor or liquefied ammonia fractional neutralization, the first step: filter after endpoint pH reaches 1.0 ~ 1.5, reclaim phosphorus, rare earth, iron mixing slag; Second step: continuing to be neutralized to pH value is 4.5 ~ 5.0, recovery Calcium Fluoride (Fluorspan) byproduct, the ammonium chloride waste-water after neutralization reclaims ammonium chloride and distilled water by evaporation, phosphorus, rare earth, iron mixing slag and the baking mixed recovering rare earth of change concentrate selection, phosphorus, iron.
2. the vitriol oil according to claim 1 cleans the method for smelting mixed rare earth concentrates, it is characterized in that: the strengthening cleaner described in step 1 is sulfuric acid.
3. the vitriol oil according to claim 1 cleans the method for smelting mixed rare earth concentrates, it is characterized in that: the vitriol oil described in step 2 is the sulphuric acid soln that mass percent concentration is greater than 90%.
4. the vitriol oil according to claim 1 cleans the method for smelting mixed rare earth concentrates, and it is characterized in that: the neutralizing agent described in step 4 is magnesium oxide, oxygenant is hydrogen peroxide.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106367621A (en) * | 2016-09-13 | 2017-02-01 | 南昌大学 | Method for recovering and recycling valuable elements from low-content rare earth solution and precipitation sludge |
| CN106756128A (en) * | 2016-12-10 | 2017-05-31 | 包头稀土研究院 | A kind of method that low acid consumption mixed rare earth concentrates concentrated sulfuric acid is decomposed |
| CN106801153A (en) * | 2016-12-30 | 2017-06-06 | 包头稀土研究院 | A kind of method of low cost enrichment high-grade mixed rare earth concentrates |
| CN107267784A (en) * | 2017-07-17 | 2017-10-20 | 中国恩菲工程技术有限公司 | The system for handling rare earth ore concentrate |
| JP2020521886A (en) * | 2017-07-17 | 2020-07-27 | チャイナ エンフィ エンジニアリング コーポレーション | Method and system for treatment of rare earth concentrates |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1384214A (en) * | 2001-04-29 | 2002-12-11 | 路远 | Carbon reducting roast process of producing RE chloride with mixed RE concentrate |
| CN1405337A (en) * | 2002-09-25 | 2003-03-26 | 包头稀土研究院 | Low-temperature roasting and decomposing process of rare earth heading concentrated sucfuric acid |
| CN1721559A (en) * | 2004-12-15 | 2006-01-18 | 北京有色金属研究总院 | Process for comprehensive recovery of rare earth and thorium from rare earth ore |
| CN102653820A (en) * | 2012-04-24 | 2012-09-05 | 包头稀土研究院 | Method for extracting scandium from baiyuneboite tailings |
| CN103103350A (en) * | 2013-02-05 | 2013-05-15 | 内蒙古科技大学 | Method for decomposing rare earth ore concentrate at low temperature through alkaline process |
| WO2013090817A1 (en) * | 2011-12-15 | 2013-06-20 | Reenewal Corporation | Rare earth recovery from phosphor |
-
2015
- 2015-12-31 CN CN201511023870.1A patent/CN105568006A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1384214A (en) * | 2001-04-29 | 2002-12-11 | 路远 | Carbon reducting roast process of producing RE chloride with mixed RE concentrate |
| CN1405337A (en) * | 2002-09-25 | 2003-03-26 | 包头稀土研究院 | Low-temperature roasting and decomposing process of rare earth heading concentrated sucfuric acid |
| CN1721559A (en) * | 2004-12-15 | 2006-01-18 | 北京有色金属研究总院 | Process for comprehensive recovery of rare earth and thorium from rare earth ore |
| WO2013090817A1 (en) * | 2011-12-15 | 2013-06-20 | Reenewal Corporation | Rare earth recovery from phosphor |
| CN102653820A (en) * | 2012-04-24 | 2012-09-05 | 包头稀土研究院 | Method for extracting scandium from baiyuneboite tailings |
| CN103103350A (en) * | 2013-02-05 | 2013-05-15 | 内蒙古科技大学 | Method for decomposing rare earth ore concentrate at low temperature through alkaline process |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106367621A (en) * | 2016-09-13 | 2017-02-01 | 南昌大学 | Method for recovering and recycling valuable elements from low-content rare earth solution and precipitation sludge |
| CN106756128A (en) * | 2016-12-10 | 2017-05-31 | 包头稀土研究院 | A kind of method that low acid consumption mixed rare earth concentrates concentrated sulfuric acid is decomposed |
| CN106801153A (en) * | 2016-12-30 | 2017-06-06 | 包头稀土研究院 | A kind of method of low cost enrichment high-grade mixed rare earth concentrates |
| CN107267784A (en) * | 2017-07-17 | 2017-10-20 | 中国恩菲工程技术有限公司 | The system for handling rare earth ore concentrate |
| JP2020521886A (en) * | 2017-07-17 | 2020-07-27 | チャイナ エンフィ エンジニアリング コーポレーション | Method and system for treatment of rare earth concentrates |
| CN112301220A (en) * | 2020-10-30 | 2021-02-02 | 包头市聚峰稀土有限责任公司 | Method for reducing iron content in rare earth sulfate water leaching solution |
| CN115029546A (en) * | 2022-05-07 | 2022-09-09 | 包头稀土研究院 | Method for treating mixed rare earth ore |
| CN115029546B (en) * | 2022-05-07 | 2024-01-23 | 包头稀土研究院 | Treatment method of mixed rare earth ore |
| WO2023240343A1 (en) * | 2022-06-13 | 2023-12-21 | His Majesty The King In Right Of Canada As Represented By The Minister Of Natural Resources | A process and system for extracting rare earth elements using high pulp density cracking |
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Application publication date: 20160511 |