CN104404243A - Method for low-temperature decomposition of low-grade Weishan rare earth ore concentrate through acid-alkali combination - Google Patents
Method for low-temperature decomposition of low-grade Weishan rare earth ore concentrate through acid-alkali combination Download PDFInfo
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Abstract
本发明公开了一种酸碱联合低温分解低品位微山稀土精矿的方法，包括将稀土精矿进行氧化焙烧的步骤，用于除去稀土精矿中的水分，使稀土精矿转变为氧化稀土和氟化稀土。本发明采用上述技术方案，大大提高了微山稀土精矿的回收率，回收率可达95%以上；采用酸碱分步分解微山稀土精矿，精矿粉经焙烧后稀土化学存在形式由REFCO3转变为REOF和RE2O3,经盐酸溶解后氟元素转变为RE2F3，以渣态形式存在，少量氟与铝、四价铈等形成络合物进入溶液中，没有氟以气态形式溢出，降低了环境污染。
The invention discloses a method for decomposing low-grade Weishan rare earth concentrate with acid-base combination at low temperature, which includes the step of oxidizing and roasting the rare earth concentrate to remove moisture in the rare earth concentrate and transform the rare earth concentrate into oxidized rare earth and rare earth fluorides. The present invention adopts the above-mentioned technical scheme, greatly improves the recovery rate of Weishan rare earth concentrate, and the recovery rate can reach more than 95%; uses acid and alkali to decompose Weishan rare earth concentrate step by step, and the chemical existence form of rare earth after the concentrate powder is roasted is changed from REFCO 3 is transformed into REOF and RE 2 O 3 , and the fluorine element is transformed into RE 2 F 3 after being dissolved in hydrochloric acid, which exists in the form of slag. A small amount of fluorine forms complexes with aluminum and tetravalent cerium and enters the solution. The gaseous form overflows, reducing environmental pollution.
Description
Technical field
The present invention relates to the method for a kind of soda acid associating low-temperature decomposition low-grade Weishan rare earth ore concentrate, belong to technical field of rare-earth hydrometallurgy.
Background technology
Namely Weishan rare-earth mineral tiny ore deposit fat, seamedly deposit, and stroll all, within the scope of 0.85 square of axiom, known dimensions mineral ore more than 60, verifies rare earth oxide reserves more than 400 ten thousand tons, workable reserve 2,550,000 tons, mine life 100 years.Mining area belongs to single hamartite, light rare earths type, be characterized in ore and gangue mineral simpler, rare-earth mineral is based on hamartite, mineral contain 17 kinds of rare earth elements, its kind of LaCePrNd four kinds of elements account for rare-earth mineral more than 98% (lanthanum 34%, cerium is 49%, praseodymium 4%, neodymium 11%), geologic reserve is large, and objectionable impurities is from the superficial to the deep, washability is good, easily exploits.But Weishan rare earth ore concentrate grade is lower, and concentrate content of rare earth is about 40%, and foreign matter content is high, concentrate intractability is large, and the rate of recovery is lower.
The main technique of current industrial process rare earth ore concentrate has vitriol oil high-temperature roasting method and soda processes.
The Weishan rare-earth mineral smelting enterprise of more than 90% adopts vitriol oil high temperature roast method, this flow process is carried out in rotary kiln, react at 500 DEG C-600 DEG C after rare earth ore concentrate mixes with the vitriol oil, rare earth ore concentrate and sulfuric acid reaction generate rare earth sulfate, then leaching sulfuric acid rare earth with cold water makes rare earth enter infusion, the purer rare earth sulfate solution obtained after regulator solution PH, finally obtains mixed rare earth carbonate with carbon ammonium precipitation, or abstraction and type-reverting is rare earth chloride.
The taste of aforesaid method to concentrate is less demanding, and industry is easy to control continuously, and chemical reagent consumption is few, and running cost is lower, is easy to scale operation.But, roasting is carried out after aforesaid method needs rare earth ore concentrate to mix with the vitriol oil, decomposition temperature is higher, higher to the requirement of equipment, in roasting process, fluorine overflows with HF, what vitriol oil decomposition releasing was a large amount of contains S acid waste gas, and process 1 ton of rare earth ore concentrate and produce 80kgHF and 360kg containing S acid waste gas, the rate of recovery can only reach 86%.
Soda processes is that concentrate is first through acid soak, by chemical mineral processing deliming, then decompose with caustic soda and make rare earth generate the water insoluble oxyhydroxide being soluble in mineral acid, fluorine and phosphate radical then generate water-soluble Sodium Fluoride and sodium phosphate with alkali, make it separate with rare earth, be recycled.
In aforesaid method after caustic digestion products in water washing, rare earth hydrate water insoluble and and magazins' layout, namely obtain re chloride after the rare earth hydrate dissolving with hydrochloric acid after washing, removal of impurities, reclaim Th simultaneously.Caustic soda decomposition technique produces without obnoxious flavour, waste residue amount little and be easy to process, NaF, Na in waste water
3pO
4available causticizing process is recycled, and reduces fluorine to the pollution of environment.
But this technique Problems existing is, the first, first caustic soda must carry out deliming before decomposing Weishan rare earth ore concentrate, wastes a large amount of hydrochloric acid and causes rare earth to lose.The second, discontinuous in production process, operating process batch operation, and mineral decomposition temperature must reach more than 140 DEG C, the resolving time is long, and rare earth, Th, F etc. all compare dispersion, rare earth yield can only reach 70%, and the rate of recovery is lower, thus limits its large-scale application.
In order to solve the pollution problem of mixed rare earth concentrates decomposition course, the researcher of China has made a lot of effort.Such as: Chinese patent CN102251106A discloses a kind of method of alkaline process decomposing Baotou rare earth ore concentrate, this technique uses the HCL of 0.5-2mol/L, removes the most of calcium in concentrate at 80-95 DEG C.Concentrate after washing mixes by weight 1:1.2-1:1.6 with sodium hydroxide; Then heat this mixture to 120-200 DEG C, carry out reaction 10-60min; Reaction product is washed to neutrality, after the alkali cake dissolving with hydrochloric acid after washing, and is 4-5.5 with alkali cake readjustment pH value, obtains pure re chloride.
Chinese patent CN101392332A discloses a kind of sulfuric acid rare earth roasted ore and directly transforms Extraction of rare earth process for cleanly preparing, for the sulfuric acid process roasting production technology that Baotou Iron Ore Concentrate is raw material, technical process of the present invention is according to replacement(metathesis)reaction conversion process in chemical process, according to the mutual transforming principle of different solubility product solid matters, the direct conversion realizing vitriol is produced.Carry out low cost to rare earth compound etc. entirely to reclaim, water can realize recycle to extinction utilization simultaneously, takes the materials such as the non-rare earth Ca of intermediate impurity removal process recovering rare earth mineral.
Chinese patent CN101824531A discloses a kind of liquid alkali low-temperature roasting decomposition process of caustic soda liquid of mixed rare earth concentrates, relate to a kind of liquid alkali low-temperature roasting decomposition process of caustic soda liquid of mixed rare earth concentrates, comprise following process: (1), mixed rare earth concentrates and sodium hydroxide are mixed by weight 1:0.5 ~ 1:1.5; (2), by mixed rare-earth mineral roasting is carried out, maturing temperature 150 DEG C ~ 550 DEG C, roasting time 0.5 ~ 4 hour; (3), the roasted ore that roasting obtains is washed to neutrality; (4), washing after alkali cake dissolving with hydrochloric acid, control PH=4 ~ 5, obtain re chloride; (5) the thorium enriched thing washing rear enclosed, after dissolving with hydrochloric acid is stored up or is dissolved further and extracts thorium and rare earth.
Above several method can only be applicable to carrying out scale process to higher-grade baotite, cannot solve the problem that the Weishan low-grade rare earth ore concentrate rate of recovery is low.
Summary of the invention
The technical problem to be solved in the present invention is for the deficiencies in the prior art, provides one can reduce environmental pollution, energy efficient, the method for the decomposition that the rate of recovery is high low-grade Weishan rare earth ore concentrate.
For solving the problem, the present invention is by the following technical solutions: the method for a kind of soda acid associating low-temperature decomposition low-grade Weishan rare earth ore concentrate, it is characterized in that: comprise the step of rare earth ore concentrate being carried out oxidizing roasting, for removing the moisture in rare earth ore concentrate, rare earth ore concentrate is made to change rare earth oxide and rare earth fluoride into.
Below further improvement of the present invention:
In described oxidizing roasting step, maturing temperature is 400-600 DEG C, and roasting time is 1-2 hour.
Further improvement:
Also comprise and the rare earth ore concentrate after oxidizing roasting step is carried out acid-soluble step, the rare earth ore concentrate after oxidizing roasting is added dissolving with hydrochloric acid, rare earth oxide and fluorine rare earth oxide are dissolved, and rare earth fluoride slag making, heat filtering obtains filtrate and acid dissolution slag.
Further improvement:
Described concentration of hydrochloric acid is 9.5-10.0mol/L, and extraction temperature is 80 DEG C-95 DEG C, and liquid-solid mass ratio is 2:1.
Further improvement:
Also comprise the step of the acid dissolution slag obtained in acid-soluble step being carried out caustic digestion, in described acid dissolution slag, add sodium hydroxide decompose, produce rare earth hydrate.
Further improvement:
Decomposition temperature during caustic digestion step is 100-120 DEG C.
Further improvement:
Also comprise the step of being carried out by the rare earth hydrate obtained in caustic digestion step washing, the water of described hydroxide soil through 60 DEG C-80 DEG C is carried out being washed to PH<9 repeatedly.
Further improvement:
Also comprise the step of the filtrate obtained in acid-soluble step and the rare earth hydrate after water-washing step being carried out adjusting back, rare earth hydrate add water-washing step in described filtrate after is adjusted back, filter, obtain rare earth chloride liquid and filter residue, obtain final rare earth chloride product by after described rare earth chloride liquid removal of impurities.
Further improvement:
Readjustment temperature in described readjustment step is 85 DEG C-95 DEG C, and readjustment PH is 4-4.5.
Further improvement:
Also comprise and the filter residue obtained in readjustment step is carried out the excellent molten step of hydrochloric acid, adopt the excellent molten recovery of hydrochloric acid to obtain rare earth chloride liquid and filter residue described filter residue.
The present invention adopts technique scheme, substantially increases the rate of recovery of Weishan rare earth ore concentrate, and the rate of recovery can reach more than 95%; Adopt soda acid fractional decomposition Weishan rare earth ore concentrate, fine ore after roasting rare earth chemistry existence form by REFCO
3change REOF and RE into
2o
3, after dissolving with hydrochloric acid, fluorine element changes RE into
2f
3, exist with slag state form, a small amount of fluorine and aluminium, quadrivalent cerium etc. form complex compound and enter in solution, do not have fluorine to overflow in a gaseous form, reduce environmental pollution; After roasting, acid-soluble two-step pretreatment, the acid dissolution slag of generation accounts for 1/3 of total concentrate, and directly adopts compared with sodium hydroxide decomposes, reduce the usage quantity of sodium hydroxide, saved cost, minimizing 2/3 compared with wastewater discharge decomposes with alkaline process, greatly reduces energy consumption.
Below in conjunction with accompanying drawing, the present invention is further described.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the low-grade rare earth ore concentrate in soda acid of the present invention associating low-temperature decomposition Weishan.
Embodiment
Embodiment 1, the method for a kind of soda acid associating low-temperature decomposition low-grade Weishan rare earth ore concentrate, step is as follows:
(1), by the Weishan rare earth ore concentrate of low taste carry out oxidizing roasting removing moisture, make rare earth by REFCO simultaneously
3change rare earth oxide RE into
2o
3with rare earth fluoride REFO, maturing temperature is at 400-600 DEG C, and roasting time is 1-2 hour.The oxidation being all unfavorable for rare earth too high or too low for temperature during roasting, the time is too short, is oxidized insufficient, long, there is crystalline transformation problem, therefore selects suitable time and temperature that rare earth ore concentrate can be made fully oxidized, improves the rate of decomposition of concentrate.
During roasting, principal reaction equation is as follows:
(2), by the rare earth ore concentrate after oxidizing roasting add dissolving with hydrochloric acid, rare earth oxide and fluorine rare earth oxide are dissolved, rare earth fluoride slag making, heat filtering obtains filtrate I and acid dissolution slag I;
Leaching condition is: concentration of hydrochloric acid is 9.5-10.0mol/L, and extraction temperature is 80 DEG C-95 DEG C, and liquid-solid mass ratio is 2:1, at the uniform velocity stirs filtered while hot after 60min simultaneously.Concentration of hydrochloric acid is adopted to be that 9.5-10.0mol/L can to make after roasting RE in concentrate
2o
3dissolve more abundant with REOF, dissolution rate can reach 75%.
Principal reaction equation is as follows:
(3), in acid dissolution slag I, add sodium hydroxide decomposition, produce rare earth hydrate II;
Decomposition temperature is 100-120 DEG C, and this step makes rare earth generate the water insoluble rare earth hydrate being soluble in mineral acid, and fluorine wherein and carbonate then generate water-soluble Sodium Fluoride and sodium carbonate with alkali, make it separate with rare earth, are recycled.Adding of sodium hydroxide is decomposition in order to rare earth fluoride, makes rare earth fluoride be converted into rare earth hydrate, is convenient to dissolving with hydrochloric acid.
Principal reaction equation is as follows:
(4), the water of rare for hydroxide II soil through 60 DEG C-80 DEG C is carried out being washed to PH<9 repeatedly, when rare earth hydrate washes with water, because rare earth hydrate II is water insoluble and be separated with soluble impurity, namely the rare earth hydrate II after washing obtains re chloride after being used as readjustment agent dissolving, removal of impurities.
Rare earth hydrate is washed repeatedly, effectively can remove F and CO
3 2-, fluorine enters waste water with free state, and waste water is through effluent treatment plant process, and discharge water Oil repellent is up to standard, does not pollute the environment; Meanwhile, can prevent from regenerating rare earth fluoride precipitation during readjustment, reduce the rate of recovery, the buck produced after washing can effectively reduce the usage quantity of water by Reusability, uses the hot wash of 60 DEG C more than-80 DEG C to be raising Na simultaneously
3cO
3with the solubleness of NaF, be convenient to be separated.
(5), in filtrate I, add the qualified rare earth hydrate II of washing carry out readjustment filtration and obtain rare earth chloride liquid II and filter residue III, after rare earth chloride liquid II is added Sodium Sulphide removal of impurities, obtain final rare earth chloride product.
Described readjustment temperature is 85 DEG C-95 DEG C, and readjustment PH is 4-4.5, because the filtrate I after dissolving with hydrochloric acid is containing a large amount of non-rare earth impurities, adopts rare earth hydrate II to adjust back pH value, effectively can lower the amount of bringing into of non-rare earth impurity.
(6), the excellent row that dissolves into of hydrochloric acid is adopted to recycle to the filter residue III obtained in upper step, obtain rare earth chloride liquid IV and filter residue IV, rare earth chloride liquid IV can be mixed into unification in filtrate I and carry out readjustment step, also can adjust back separately, filter residue IV be washed rear dress storehouse and seal up for safekeeping.
(7), the water lotion that upper step washing filter residue IV obtains is squeezed into making beating recycling in rare earth hydrate II.
Experimental verification is carried out to the method for above-mentioned soda acid associating low-temperature decomposition low-grade Weishan rare earth ore concentrate, carries out lab scale, pilot scale respectively and try with the rate of recovery determining Weishan rare-earth mineral greatly.
Embodiment 2, carries out small scale experiments to Weishan Lake rare-earth mineral.
Experimental installation: retort furnace, iron pan, balance, beaker, graduated cylinder, filter, iron crucible, electric furnace, glass stick, electric mixer etc.
Experimental raw: 40% rare earth ore concentrate, concentrated hydrochloric acid, sodium hydroxide etc.
Experimentation:
1, get the low-grade rare earth ore concentrate in 1000g Weishan, heat 2 hours at 600 DEG C of temperature with retort furnace, after taking-up, weigh to obtain 884g;
2, drop in 1.2L hydrochloric acid by the rare-earth mineral after roasting, be heated to 95 DEG C, be incubated 30 minutes while stirring, filter after reaction, obtain filtrate 1.14L, acid dissolution slag is 405g;
3, acid dissolution slag is put into iron crucible, add 180g sodium hydroxide, and add suitable quantity of water and be adjusted to atherosclerotic, be heated to about 110 DEG C with electric furnace, constantly stir lower insulation 2 hours, obtain rare earth hydrate;
4, the water of 80 DEG C is adopted to wash the rare earth hydrate that previous step obtains, be about 9 to pH, obtain rare earth hydrate, the rare earth hydrate after washing is added in filtrate and regulates pH value to 4-4.5, obtain rare earth chloride liquid and filter residue, rare earth chloride liquid concentration is 1.702mol/l;
5, the filter residue obtained in step 4 is carried out the excellent molten process of hydrochloric acid, concentration of hydrochloric acid is 1.0mol/l, temperature >90 DEG C, excellent solution adds soda ash readjustment, readjustment liquid is mixed in the filtrate obtained in step 2, and final that rare earth chloride liquid volume is 1.71L, concentration is 1.25mol/L.
Material balance:
In rare-earth mineral used, rare-earth oxidation amount is:
1000×40%×（1-7%）=372g
In final gained rare earth chloride liquid, rare-earth oxidation amount is:
1.25mol/L×1.71L× 169g/L=361g
The last rate of recovery is:
361g÷372g=97.0%
Embodiment 3, in order to determine the rate of recovery in Weishan Lake rare-earth mineral small scale experiments further, the popularization that will feed intake carries out pilot scale.
Experimental installation: platform balance, large beaker, filter, iron crucible, electric furnace, glass stick etc.
Experimental raw: rare-earth mineral grade (46.5%) after rotary kiln baking, concentrated hydrochloric acid, sodium hydroxide etc.
Experimentation:
1, get rare-earth mineral after 10kg rotary kiln baking, drop in 16L concentrated hydrochloric acid, be heated to 95 DEG C, be incubated 30 minutes while stirring, filtration after reaction, obtain filtrate 15.4L, rare earth concentration is 1.21mol/L, and acid dissolution slag is 4.3kg;
2, filter residue is put into stainless steel metal bucket, add 1.5kg sodium hydroxide, and add suitable quantity of water and be adjusted to atherosclerotic, be heated to about 110 DEG C with electric furnace, constantly stir lower insulation 2 hours, obtain rare earth hydrate;
3, being adopted by the rare earth hydrate that previous step obtains the water of 80 DEG C to carry out being washed to pH is about 9;
4, the rare earth hydrate after washing is added in filtrate and adjusts back pH to 4-4.5, after filtration, obtain rare earth chloride liquid and filter residue;
5, the filter residue in step 4 is carried out the excellent molten process of hydrochloric acid, readjustment, filtration, mixed that rare earth chloride liquid volume is 23.0L with former rare earth chloride liquid, concentration is 1.15mol/L.
Material balance:
In rare-earth mineral used, rare-earth oxidation amount is:
10000×46.5%=4650g
In final gained rare earth chloride liquid, rare-earth oxidation amount is:
1.15mol/L×23.0L× 169g/L=4473g
The last rate of recovery is:
4473g÷4650g=96.2%
Embodiment 4, from lab scale and pilot-scale experiment, smelted Weishan Lake rare-earth mineral by this technique, total rare earth recovery rate is very high, and gained strength of solution is also very high, very applicable, in order to better investigate technological effect, carries out the large examination of production line.
Experimental installation: rotary kiln, graphite retort, plate-and-frame filter press, readjustment tank, alkali turns tank etc.
Experimental raw: Weishan Lake rare-earth mineral (grade 40%), concentrated hydrochloric acid, sodium hydroxide etc.
Experimentation:
1, getting 1t Weishan Lake rare-earth mineral drops in rotary kiln, roasting 2 hours under 600 DEG C of temperature;
2, dropped in the ore deposit after roasting in 1.6 cubes of concentrated hydrochloric acids, logical steam, is heated to 95 DEG C, is incubated 60 minutes, and filter after reaction, obtain filtrate 1.65 cubes, rare earth concentration is 1.12mol/L, and acid dissolution slag is 418kg;
3, acid dissolution slag is put into alkali and turn tank, add 150kg sodium hydroxide, and add suitable quantity of water and be stirred to atherosclerotic, with about eddy heating for heating to 110 DEG C, insulation 4 hours under continuous stirring, obtain rare earth hydrate, the rare earth hydrate obtained being adopted the washing of >70 degree Celsius, is about 9 to pH;
4, the rare earth hydrate after washing is added in filtrate and adjusts back pH to 4-4.5, after filtration, obtain rare earth chloride liquid and filter residue;
That 5, the filter residue in step 4 is carried out the excellent molten process of hydrochloric acid arrives rare earth chloride liquid, and mixed that rare earth chloride liquid volume is 2.15 cubes with former rare earth chloride liquid, concentration is 1.05mol/L.
Material balance:
In rare-earth mineral used, rare-earth oxidation amount is:
1t×40%=4.0×10
5g
In final gained rare earth chloride liquid, rare-earth oxidation amount is:
1.05mol/L×2.15×10
3L× 169g/L=3.81×10
5g
The last rate of recovery is:
3.81×10
5g÷4.0×10
5g =95.4%
Known by above-mentioned experiment, the rare earth rate of decomposition adopting soda acid of the present invention to combine the method for low-temperature decomposition low-grade Weishan rare earth ore concentrate can reach more than 95%, and rate of decomposition significantly improves.
Last it is noted that obviously, above-described embodiment is only for example of the present invention is clearly described, and the restriction not to embodiment.For those of ordinary skill in the field, other multi-form change or variations can also be made on the basis of the above description.Here exhaustive without the need to also giving all embodiments; And thus the apparent change of amplifying out or variation be still among protection scope of the present invention.
Claims (10)
1. a method for soda acid associating low-temperature decomposition low-grade Weishan rare earth ore concentrate, is characterized in that: comprise the step of rare earth ore concentrate being carried out oxidizing roasting, for removing the moisture in rare earth ore concentrate, making rare earth ore concentrate change rare earth oxide and rare earth fluoride into.
2. the method for a kind of soda acid associating low-grade Weishan of low-temperature decomposition according to claim 1 rare earth ore concentrate, it is characterized in that: in described oxidizing roasting step, maturing temperature is 400-600 DEG C, roasting time is 1-2 hour.
3. the method for a kind of soda acid associating low-grade Weishan of low-temperature decomposition according to claim 1 rare earth ore concentrate, it is characterized in that: also comprise and the rare earth ore concentrate after oxidizing roasting step is carried out acid-soluble step, rare earth ore concentrate after oxidizing roasting is added dissolving with hydrochloric acid, rare earth oxide and fluorine rare earth oxide are dissolved, rare earth fluoride slag making, heat filtering obtains filtrate and acid dissolution slag.
4. the method for a kind of soda acid associating low-grade Weishan of low-temperature decomposition according to claim 3 rare earth ore concentrate, it is characterized in that: described concentration of hydrochloric acid is 9.5-10.0mol/L, extraction temperature is 80 DEG C-95 DEG C, and liquid-solid mass ratio is 2:1.
5. the method for a kind of soda acid associating low-temperature decomposition low-grade Weishan rare earth ore concentrate according to claim 3 or 4, it is characterized in that: also comprise the step of the acid dissolution slag obtained in acid-soluble step being carried out caustic digestion, in described acid dissolution slag, add sodium hydroxide decompose, produce rare earth hydrate.
6. the method for a kind of soda acid associating low-grade Weishan of low-temperature decomposition according to claim 5 rare earth ore concentrate, is characterized in that: decomposition temperature during caustic digestion step is 100-120 DEG C.
7. the method for a kind of soda acid associating low-grade Weishan of low-temperature decomposition according to claim 6 rare earth ore concentrate, is characterized in that: also comprise the step of being carried out by the rare earth hydrate obtained in caustic digestion step washing,
The water of described hydroxide soil through 60 DEG C-80 DEG C is carried out being washed to PH<9 repeatedly.
8. the method for a kind of soda acid associating low-grade Weishan of low-temperature decomposition according to claim 7 rare earth ore concentrate, it is characterized in that: also comprise the step of the filtrate obtained in acid-soluble step and the rare earth hydrate after water-washing step being carried out adjusting back, rare earth hydrate add water-washing step in described filtrate after is adjusted back, filter, obtain rare earth chloride liquid and filter residue, obtain final rare earth chloride product by after described rare earth chloride liquid removal of impurities.
9. the method for a kind of soda acid associating low-grade Weishan of low-temperature decomposition according to claim 8 rare earth ore concentrate, it is characterized in that: the readjustment temperature in described readjustment step is 85 DEG C-95 DEG C, readjustment PH is 4-4.5.
10. the method for a kind of soda acid associating low-grade Weishan of low-temperature decomposition according to claim 9 rare earth ore concentrate, it is characterized in that: also comprise and the filter residue obtained in readjustment step is carried out the excellent molten step of hydrochloric acid, adopt the excellent molten recovery of hydrochloric acid to obtain rare earth chloride liquid and filter residue described filter residue.
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| CN108715928A (en) * | 2018-06-19 | 2018-10-30 | 四川江铜稀土有限责任公司 | Bastnaesite smelts the recycling of separation middle rare earth and utilizes technique with the heavy Sewage treatment of carbon |
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| CN113652560A (en) * | 2021-07-14 | 2021-11-16 | 四川省冕宁县方兴稀土有限公司 | Method for efficiently recovering rare earth from rare earth molten salt waste residues |
| CN114752788A (en) * | 2022-04-24 | 2022-07-15 | 华卫国 | Roasting method of rare earth ore concentrate added with active agent |
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| CN106978531B (en) * | 2017-03-15 | 2018-12-14 | 包头稀土研究院 | The method that soda acid joint decomposes mixed rare earth concentrate |
| CN107774270A (en) * | 2017-10-17 | 2018-03-09 | 内蒙古科技大学 | The preparation method of modified RE concentrate SCR denitration |
| CN107774270B (en) * | 2017-10-17 | 2020-06-16 | 内蒙古科技大学 | Preparation method of modified rare earth concentrate SCR denitration catalyst |
| CN108715928A (en) * | 2018-06-19 | 2018-10-30 | 四川江铜稀土有限责任公司 | Bastnaesite smelts the recycling of separation middle rare earth and utilizes technique with the heavy Sewage treatment of carbon |
| CN108715928B (en) * | 2018-06-19 | 2019-11-15 | 四川江铜稀土有限责任公司 | Bastnaesite smelts rare earth recovery and the heavy Sewage treatment of carbon in separation and utilizes technique |
| CN113652560A (en) * | 2021-07-14 | 2021-11-16 | 四川省冕宁县方兴稀土有限公司 | Method for efficiently recovering rare earth from rare earth molten salt waste residues |
| CN113652560B (en) * | 2021-07-14 | 2022-11-08 | 四川省冕宁县方兴稀土有限公司 | Method for efficiently recovering rare earth from rare earth molten salt waste residues |
| CN114752788A (en) * | 2022-04-24 | 2022-07-15 | 华卫国 | Roasting method of rare earth ore concentrate added with active agent |
| CN115058608A (en) * | 2022-06-20 | 2022-09-16 | 淄博灵芝化工有限公司 | Method for recovering rare earth from rare earth lead sulfide zinc slag |
| CN115058608B (en) * | 2022-06-20 | 2024-05-31 | 淄博灵芝化工有限公司 | Method for recovering rare earth from rare earth lead-zinc sulfide slag |
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