CN109536746A - A kind of method that the pulp of low calcium high-grade mixed rare earth concentrates circulation is decomposed - Google Patents
A kind of method that the pulp of low calcium high-grade mixed rare earth concentrates circulation is decomposed Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
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- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/253—Halides
- C01F17/271—Chlorides
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- 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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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- 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
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/12—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic alkaline solutions
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
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Abstract
The present invention relates to the methods that a kind of circulation pulp of low calcium high-grade mixed rare earth concentrate is decomposed, and belong to field of hydrometallurgy.Including following procedure: using the sulfuric acid solution of absolute excessive low concentration, the bastnaesite in low calcium high-grade mixed concentrate is decomposed by pulp rapid reaction in a heated condition, after reaction, calcium sulfate and sulfuric acid rare earth are dissolved in infusion by acid leaching residue through water logging, and ferrophosphorus thorium slag is formed in infusion and after removal of impurities.Pickle liquor supplements the new mine of circular treatment after sulfuric acid；Water logging slag and ferrophosphorus thorium slag are decomposed with high alkali liquid.It is recycled after alkali waste water crystallization recycling sodium phosphate.The present invention is suitable for the processing of low calcium high-grade mixed rare earth concentrate, fluorine, phosphor resource in mixed rare earth concentrates can be separately recovered, and the consumption such as sulfuric acid, sodium hydroxide, the energy are reduced to theoretical consumption, the problems such as concentrated sulfuric acid consolidates solid phase reaction equipment ring formation with rare earth ore concentrate is evaded, it is easy to accomplish industrialization.
Description
Technical field
The present invention relates to one kind in hydrometallurgical technology, specifically, is related to a kind of low calcium high-grade mixed rare earth concentrates and follows
The method that ring pulp is decomposed.
Background technique
Packet header baiyuneboite contains abundant as current proved reserves and the maximum rare earth mineral deposit of yield in the world
Rare earth resources.The mixed rare earth concentrates obtained through ore dressing are made of bastnaesite and solitary stone ore, and ratio is generally in 9:1 to 3:
Between 2, due to the complexity of concentrate composition, so that there are many variations for the smelting separation process of concentrate.
The mixed rare earth concentrate decomposition technique of industrialization at present mainly has concentrated sulfuric acid high-temperature roasting decomposition technique and concentrated base
Liquid normal pressure decomposition technique.Concentrated sulfuric acid high-temperature roasting decomposition technique is that rare earth ore concentrate and the concentrated sulfuric acid are blended in 400~1000 DEG C of roastings
It burns, during the reaction, concentrate and the concentrated sulfuric acid can be rapidly converted into pure solid phase by solid-liquid mixed phase, when mineral grain is excessive, meeting
Internal-response is caused not exclusively to influence rare earth resolution ratio, and a large amount of high temperature mixing acid tail gas (SO of the technique output2、SO3、
H2SO4、HF、SiF4), transition sulfate wastewater and emissive industrial waste residue are difficult to handle, and cause entire environmental protection treatment engineering system huge
Greatly, cost is very high.It is 60% or so mixed rare earth concentrates that high alkali liquid decomposition technique, which handles REO grade, is needed through acidified choosing
By CaO in concentrate be reduced to 2% hereinafter, output hydrochloric acid deliming waste water and mixing sodium salt waste water (NaOH, Na3PO4、NaF、
Na2CO3、Na2SO4And NaCl) resource reclaim difficulty is big, cause excessive sodium hydroxide to waste, after simply can only mutually neutralizing
Row sea up to standard, can not recycle the resources such as fluorine, phosphorus.Simultaneously as sodium hydroxide price is almost 4-6 times of sulfuric acid price, although
Technical process does not have exhaust gas generation, but whole smelting cost is still very high.
In view of the foregoing, domestic many scholars carry out the exploitation of Novel smelting technology.Li Mei etc. discloses " Bayan Obo
Rare earth ore concentrate prepares the new method of rare earth chloride " (patent No.: 201110221839.4), this method is with high-grade RE concentrate
(REO grade is 60-68%) is raw material, will handle the oxidizing roasting technique of Sichuan bastnaesite in conjunction with high alkali liquid technique.First
By bastnaesite oxidizing roasting in mixed concentrate, hydrochloric acid extraction non-cerium trivalent rare earth, then is decomposed with high alkali liquid and extract residue four
Valence cerium and monazite minerals.But the problem is that alkali waste water contains NaOH, Na3PO4, NaF and NaCl etc., separating difficulty is big, alkali
Consumption is still higher；Meanwhile high-grade concentrate is by selecting iron to obtain, CaO content is still higher in concentrate, and caustic digestion acid is molten
The problems such as there is consumption sodium hydroxide and cause the risk of rare earth loss in process.Li Mei etc. discloses that " soda acid joint is low simultaneously
(application number: 201310044410.1), this method is in high-grade RE concentrate for the method that temperature decomposes Bayan Obo rare earth ore concentrate "
HCl and AlCl is added3, complexation leaching, after filtering, filtrate be added sodium sulphate carry out double salt precipitation, rare earth sulfuric acid sodium double salt and solely
Rock ballast is occupied using alkaline process microwave cycle heat resolve.Although this method reduces the spilling of pernicious gas, but still there are alkali to give up
NaOH, Na in water3PO4、Na2SO4Equal complicated components, waste water are difficult to the problems such as separating and recovering.
Chen Ji etc. disclose " a kind of process of decomposing Baotou rare earth mine " (application number:
And " a method of extraction and separation cerium, fluorine, phosphorus from Baotou rare earth mine sulphuric leachate " 201310018072.4)
(application number: 201510571527.4).This method is equally by oxidizing roasting technique in conjunction with high alkali liquid technique, not with above-mentioned technique
It is that mineral after oxidizing roasting use sulfuric acid molten technology obtains the mixing sulfuric acid of quadrivalent cerium and other trivalent rare earths entirely with place
Earth solution, then the complex compound that preferential extraction quadrivalent cerium and fluorine, phosphorus are formed produce cerium fluoride and cerous phosphate product mix.Although alkali
Consumption is declined, but equally exists the problems such as mixing sodium salt waste water and mixing cerium salt products application exploitation.Therefore, above-mentioned
The problems such as there is fluorine in technique, phosphor resource does not comprehensively utilize, and alkaline consumption is high, at high cost.
Cui Jianguo etc. disclose " method that a kind of soda acid joint decomposes mixed rare earth concentrate " (application number:
201710152285.5), Baotou rare earth ore concentrate is mixed with the concentrated sulfuric acid by 1:0.6-0.9, roasts 150- at 120-180 DEG C
300min obtains calcium sulfate and solitary stone ore mixing water phase analysis by water logging, is divided calcium sulfate and monazite using gravity separation technology
From rear to decompose solitary stone ore by lye.Low-temperature bake and lye are decomposed and are combined by the invention, to rare earth ore concentrate grade applicability
It is relatively strong, roasting energy consumption acid and alkali consumption is reduced, fluorine, phosphor resource synthetical recovery and soda cycling utilization of wastewater are realized.In the presence of
The problem of be that ring formation of rotary kiln is easily caused during low-temperature bake；Simultaneously because sulfuric acid acid amount is small, it is difficult that bastnaesite decomposes control
Degree increases；Gravity separation obtains a part of radioactivity calcium sulfate waste residues, while causing fine granularity rare earth to lose so that it cannot return
It receives.
The above several method respectively has the characteristics that, is all the improvement in prior art level, and in mischmetal essence
Mine decomposes aspect respectively and builds consensus.But it all can not thoroughly solve packet header mixed type Rare Earth Mine and smelt soda acid circulation benefit in separation
With the problems such as, energy consumption is big and equipment requirement is high and fluorine, reclamation of phosphorus resource.Meanwhile each technique is only to mixed rare earth concentrates
Middle rare earth grade claims, and does not claim to non-rare earth impurity calcium content, does not fully consider impurity element to decomposition
The influence of technique.
Summary of the invention
For various problems existing in the prior art, the present invention provides a kind of low calcium high-grade mixed rare earth concentrates
The consumption such as acid, alkali, energy is greatly reduced, when solving the concentrated sulfuric acid and rare earth ore concentrate solid-solid reaction in the method for pulp Cycle-decomposition
The problems such as equipment ring formation, and the valuable resources such as synthetical recovery fluorine, phosphorus, thorium.
Technical solution is as follows:
A kind of method of low calcium high-grade mixed rare earth concentrate pulp Cycle-decomposition, comprising:
(1) low calcium high-grade mixed rare earth concentrates are mixed in proportion with sulfuric acid solution, carries out pulp in a heated state
Reaction reacts the fluorine-containing mineral of main decomposition, forms fluorine silicon nitration mixture byproduct after tail gas absorption；After reaction, after separation of solid and liquid
Pickle liquor and acid leaching residue are obtained, acid leaching residue obtains water logging slag and infusion by water logging, and water logging slag is mainly with monazite minerals
Main, infusion forms ferrophosphorus thorium slag and rare earth sulfate solution after neutralizing；The calcium sulfate wherein generated is in a basic balance to be dissolved into
In infusion.Pickle liquor continues with new mixed rare earth concentrates by supplementing sulfuric acid；
(2) water logging slag and ferrophosphorus thorium slag and mass percentage are the sodium hydroxide solution of 45%-70% according to low calcium height
Grade mixed rare earth concentrate is that 1:0.1-0.8 is mixed with sodium hydroxide weight ratio, and pulp is decomposed at 130-180 DEG C；Alkaline hydrolysis
Mine after washing, forms a little acid dissolution slag, radioactive iron thorium slag and re chloride after being cleaned with dissolving with hydrochloric acid, neutralization；
Soda Waste water concentrating crystallizes out tertiary sodium phosphate byproduct, continues to decompose phosphorus ore containing and ferrophosphorus thorium after concentrate supplement sodium hydroxide
Slag.
Further, low calcium high-grade mixed rare earth concentrates are the concentrate of REO >=62%, CaO≤3%.
Further, sulfuric acid solution initial mass percentage concentration is 40%~70%.
Further, sulfuric acid solution is mixed with low calcium high-grade mixed rare earth concentrates according to 1.5~5:1 of mass ratio.
Further, pulp reaction is carried out at 100~150 DEG C, the reaction time is 0.5~5 hour.
Further, the supplement sulfuric acid, sulfuric acid magnitude of recruitment is according to sulfuric acid actual consumption in previous round pulp reaction
Amount supplement.
Further, the supplement sodium hydroxide, sodium hydroxide magnitude of recruitment is according to hydrogen-oxygen in previous round pulp decomposition
Change sodium actual consumption amount supplement.
The technology of the present invention effect includes:
The present invention reacts preferential by pulp and decomposes mixed type under the conditions of sulfuric acid is absolutely excessive, reaction temperature is lower
Bastnaesite in rare earth ore concentrate, then extracts sulfuric acid rare earth by water logging；It is low by sulfuric acid rare earth solubility, pass through a large amount of sulfuric acid
Re dip solution balance dissolves a small amount of calcium sulfate, and purer monazite minerals can be obtained without links such as ore dressings；Solitary stone ore
Object further uses the base extraction mineral recovering rare earth, and alkali waste water mainly based on sodium hydroxide and tertiary sodium phosphate, recycles
Dissolubility difference realization reclamation of phosphorus resource is recycled with remaining lye；To which the consumption such as acid, alkali, energy, solution be greatly reduced
It has determined the concentrated sulfuric acid and when rare earth ore concentrate solid-solid reaction the problems such as equipment ring formation, and the valuable resources such as synthetical recovery fluorine, phosphorus, thorium.
(1) it claims to mixed rare earth concentrates Minerals composition, specifies and mentioned using reducing calcium mineral content as target
High rare earth ore concentrate grade, and non-reduced iron mineral content is that target improves rare earth ore concentrate grade.By designing mineral composition, mention
Meet the mineral treatment processes of actual demand out.
(2) fractional decomposition technology is used to mixed type rare-earth mineral, sufficiently combines sulfuric acid pulp decomposition and lye slurry
Change the technological merit decomposed, thoroughly solve the equipment and technology problem of sulfuric acid low temperature roasting ring formation, acid, alkali consumption are reduced into famous dictum
Stoichiometric is horizontal, and has established Process ba- sis for serialization decomposition and control.
(3) low by sulfuric acid rare earth solubility during sulfuric acid rare earth is extracted in water logging, pass through a large amount of sulfuric acid rare earth leachates
The calcium sulfate that balance dissolution generates on a small quantity, can be obtained purer monazite minerals, caustic digestion exhausted water without links such as ore dressings
Without crystallization treatment sodium sulphate.
(4) sulfuric acid rare earth, phosphate radical for dissolving in pickle liquor etc. can greatly inhibit solitary stone ore by enrichment cycles
Object decomposes and the dissolution of sulfuric acid rare earth.
Detailed description of the invention
Fig. 1 is the process flow chart of the method for low calcium high-grade mixed rare earth concentrate pulp Cycle-decomposition in the present invention.
Specific embodiment
Be described below and specific embodiments of the present invention be fully shown, with enable those skilled in the art to practice and
It reproduces.
Embodiment 1
It is the mixed rare earth concentrates that 65.7%, CaO is 2.86% and the sulphur that mass percentage is 70% by the REO of 100g
Acid solution mixes (sulfuric acid: ore weight ratio 3.4:1) by liquid-solid ratio 3:1, and agitating and heating keeps the temperature 0.5h, tail gas at 150 DEG C
Byproduct fluorine, silicon nitration mixture are prepared through condensed absorbent.After reaction, after separation of solid and liquid, the acid leaching residue secondary leaching of 1500mL water,
Infusion forms ferrophosphorus thorium slag by neutralization and REO concentration is 31.6g/L rare earth sulfate solution.It is calculated with F in water logging slag, it is fluorine-containing
Mineral resolution ratio is 97.4%.Pickle liquor continues the concentrated sulfuric acid that additional mass percentage composition is 98% to circular treatment after 70% the
Two batches of concentrate.Keep reaction temperature, sour amount, acid concentration, reaction time etc. under first time uniform condition, the secondary leaching of 1500mL water
After out, infusion forms ferrophosphorus thorium slag by neutralization and REO concentration is 32.1g/L rare earth sulfate solution.In terms of F in water logging slag
It calculates, fluorine-containing mineral resolution ratio is 97.5%.Third batch mineral are handled, leachate REO concentration is 31.4g/L, in terms of F in water logging slag
It calculates, fluorine-containing mineral resolution ratio is 97.2%.After continuing with 5 batches of mineral, sulfuric acid magnitude of recruitment keeps stablizing, fluorine-containing mineral resolution ratio
Between 96.5%~97.6%.Finally, ferrophosphorus thorium slag washs recovering rare earth with 0.2mol/L sulfuric acid solution, cleaning solution is for roasting
Mineral water leaching is burnt, remaining iron thorium slag is thoriated emissive industrial waste residue.
Water logging slag and ferrophosphorus thorium slag are proportionally mixed with mass percentage for the sodium hydroxide solution of 45%-70%
It closes, is decomposed at 130-180 DEG C.Alkaline hydrolysis mine after washing, forms a little acid dissolution slag after being cleaned with dissolving with hydrochloric acid, neutralization, puts
Penetrating property iron thorium slag and re chloride.Alkali waste water goes out tertiary sodium phosphate byproduct through crystallisation by cooling, and remaining aqueous slkali continues to decompose
Phosphorus ore containing and ferrophosphorus thorium slag.
Embodiment 2
It is the mixed rare earth concentrates that 65.7%, CaO is 2.86% and the sulphur that mass percentage is 40% by the REO of 100g
Acid solution mixes (sulfuric acid: ore weight ratio 1.6:1) by liquid-solid ratio 3:1, and agitating and heating keeps the temperature 5h, tail gas warp at 110 DEG C
Condensed absorbent prepares byproduct fluorine, silicon nitration mixture.After reaction, after separation of solid and liquid, the acid leaching residue secondary leaching of 1500mL water, water
Immersion liquid forms ferrophosphorus thorium slag by neutralization and REO concentration is 21.5g/L rare earth sulfate solution.It is calculated with F in water logging slag, Fluoride-bearing Ore
Object resolution ratio is 73.4%.Pickle liquor continues the concentrated sulfuric acid that additional mass percentage composition is 98% to circular treatment second after 40%
Criticize concentrate.Keep reaction temperature, sour amount, acid concentration, reaction time etc. under first time uniform condition, the secondary leaching of 1500mL water
Afterwards, infusion forms ferrophosphorus thorium slag by neutralization and REO concentration is 20.8g/L rare earth sulfate solution.It is calculated with F in water logging slag,
Fluorine-containing mineral resolution ratio is 77.1%.Third batch mineral are handled, leachate REO concentration is 21.7g/L, it is calculated with F in water logging slag,
Fluorine-containing mineral resolution ratio is 76.7%.Finally, ferrophosphorus thorium slag washs recovering rare earth with 0.2mol/L sulfuric acid solution, cleaning solution is used for
Roasted ore water logging, remaining iron thorium slag are thoriated emissive industrial waste residue.
Water logging slag and ferrophosphorus thorium slag are proportionally mixed with mass percentage for the sodium hydroxide solution of 45%-70%
It closes, is decomposed at 130-180 DEG C.Alkaline hydrolysis mine after washing, forms a little acid dissolution slag after being cleaned with dissolving with hydrochloric acid, neutralization, puts
Penetrating property iron thorium slag and re chloride.Alkali waste water goes out tertiary sodium phosphate byproduct through crystallisation by cooling, and remaining aqueous slkali continues to decompose
Phosphorus ore containing and ferrophosphorus thorium slag.
Embodiment 3
It is the mixed rare earth concentrates that 67.9%, CaO is 1.96% and the sulphur that mass percentage is 70% by the REO of 100g
Acid solution mixes (sulfuric acid: ore weight ratio 5:1) by liquid-solid ratio 4.5:1, and agitating and heating keeps the temperature 1.5h, tail gas at 130 DEG C
Byproduct fluorine, silicon nitration mixture are prepared through condensed absorbent.After reaction, after separation of solid and liquid, the acid leaching residue secondary leaching of 1500mL water,
Infusion forms ferrophosphorus thorium slag by neutralization and REO concentration is 33.1g/L rare earth sulfate solution.It is calculated with F in water logging slag, it is fluorine-containing
Mineral resolution ratio is 96.7%.Pickle liquor continues the concentrated sulfuric acid that additional mass percentage composition is 98% to circular treatment after 70% the
Two batches of concentrate.Keep reaction temperature, sour amount, acid concentration, reaction time etc. under first time uniform condition, the secondary leaching of 1500mL water
After out, infusion forms ferrophosphorus thorium slag by neutralization and REO concentration is 33.3g/L rare earth sulfate solution.In terms of F in water logging slag
It calculates, fluorine-containing mineral resolution ratio is 96.9%.Third batch mineral are handled, leachate REO concentration is 33.5g/L, in terms of F in water logging slag
It calculates, fluorine-containing mineral resolution ratio is 97.5%.The 4th batch of mineral are handled, leachate REO concentration is 33.1g/L, in terms of F in water logging slag
It calculates, fluorine-containing mineral resolution ratio is 97.2%.After continuing with 5 batches of mineral, sulfuric acid magnitude of recruitment keeps stablizing, fluorine-containing mineral resolution ratio
Between 96.6%~98.2%.Finally, ferrophosphorus thorium slag washs recovering rare earth with 0.2mol/L sulfuric acid solution, cleaning solution is for roasting
Mineral water leaching is burnt, remaining iron thorium slag is thoriated emissive industrial waste residue.
Water logging slag and ferrophosphorus thorium slag are proportionally mixed with mass percentage for the sodium hydroxide solution of 45%-70%
It closes, is decomposed at 130-180 DEG C.Alkaline hydrolysis mine after washing, forms a little acid dissolution slag after being cleaned with dissolving with hydrochloric acid, neutralization, puts
Penetrating property iron thorium slag and re chloride.Alkali waste water goes out tertiary sodium phosphate byproduct through crystallisation by cooling, and remaining aqueous slkali continues to decompose
Phosphorus ore containing and ferrophosphorus thorium slag.
It should be understood that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention is not
It is confined to this, anyone skilled in the art in the technical scope disclosed by the present invention, can readily occur in variation
Or replacement, it should all be included within the scope of the present invention.Therefore, protection scope of the present invention should be with the claim
Protection scope subject to.
Claims (7)
1. a kind of method that the pulp of low calcium high-grade mixed rare earth concentrates circulation is decomposed, comprising the following steps:
Low calcium high-grade mixed rare earth concentrates are mixed in proportion with sulfuric acid solution, carry out pulp reaction in a heated state, instead
Fluorine-containing mineral should be decomposed, form fluorine silicon nitration mixture byproduct after tail gas absorption；After reaction, obtained after separation of solid and liquid pickle liquor and
Acid leaching residue, acid leaching residue obtain water logging slag and infusion by water logging, and infusion forms ferrophosphorus thorium slag after neutralizing and sulfuric acid is dilute
Native solution, wherein the sulfuric acid calcium balance generated is dissolved into infusion；Pickle liquor continues with new mixing by supplementing sulfuric acid
Rare earth ore concentrate；
Water logging slag and ferrophosphorus thorium slag are mixed with the sodium hydroxide solution that mass percentage is 45%-70% according to low calcium high-grade
Type rare earth ore concentrate is that 1:0.1-0.8 is mixed with sodium hydroxide mass ratio, and pulp is decomposed at 130-180 DEG C；Alkaline hydrolysis mine is by washing
After washing, with formation acid dissolution slag, radioactive iron thorium slag and re chloride after dissolving with hydrochloric acid, neutralization removal of impurities；Soda Waste water concentrating
Tertiary sodium phosphate byproduct is crystallized out, continues to decompose phosphorus ore containing and ferrophosphorus thorium slag after concentrate supplement sodium hydroxide.
2. method according to claim 1, it is characterised in that: low calcium high-grade mixed rare earth concentrates are REO >=62%, CaO
≤ 3% concentrate.
3. method according to claim 1, it is characterised in that: sulfuric acid solution initial mass percentage concentration is 40%~70%.
4. method according to claim 1, it is characterised in that: sulfuric acid solution and low calcium high-grade mixed rare earth concentrates are according to matter
Amount is mixed than 1.5~5:1.
5. method according to claim 1, it is characterised in that: progress pulp reaction, reaction time are at 100~150 DEG C
0.5~5 hour.
6. method according to claim 1, it is characterised in that: in supplement sulfuric acid process, sulfuric acid magnitude of recruitment is starched according to previous round
Change sulfuric acid consumption supplement in reaction.
7. method according to claim 1, it is characterised in that: supplement sodium hydroxide during, sodium hydroxide magnitude of recruitment according to
Sodium hydroxide consumption supplement in previous round pulp decomposition.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111235411A (en) * | 2020-03-02 | 2020-06-05 | 包头稀土研究院 | Process for removing calcium-containing minerals in rare earth concentrate and application of sulfuric acid solution |
| CN111285332A (en) * | 2020-02-19 | 2020-06-16 | 包头稀土研究院 | Integrated method for decomposing fluorine-containing rare earth mineral and recovering hydrofluoric acid |
| CN114380317A (en) * | 2021-10-24 | 2022-04-22 | 崇义章源钨业股份有限公司 | Method for recycling hydrochloric acid by recovering calcium sulfate from pickle liquor |
| CN114606383A (en) * | 2022-04-08 | 2022-06-10 | 昆明理工大学 | Method for comprehensively recovering valuable elements in industrial leaching residues of spodumene |
Citations (2)
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| CN106978531A (en) * | 2017-03-15 | 2017-07-25 | 包头稀土研究院 | The method that soda acid joint decomposes mixed rare earth concentrate |
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| CN102051477A (en) * | 2010-12-15 | 2011-05-11 | 内蒙古科技大学 | Method for chemically separating bastnaesite and urdite from mixed rare earth concentrate |
| CN106978531A (en) * | 2017-03-15 | 2017-07-25 | 包头稀土研究院 | The method that soda acid joint decomposes mixed rare earth concentrate |
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| CN111285332A (en) * | 2020-02-19 | 2020-06-16 | 包头稀土研究院 | Integrated method for decomposing fluorine-containing rare earth mineral and recovering hydrofluoric acid |
| CN111285332B (en) * | 2020-02-19 | 2023-03-28 | 包头稀土研究院 | Integrated method for decomposing fluorine-containing rare earth mineral and recovering hydrofluoric acid |
| CN111235411A (en) * | 2020-03-02 | 2020-06-05 | 包头稀土研究院 | Process for removing calcium-containing minerals in rare earth concentrate and application of sulfuric acid solution |
| CN114380317A (en) * | 2021-10-24 | 2022-04-22 | 崇义章源钨业股份有限公司 | Method for recycling hydrochloric acid by recovering calcium sulfate from pickle liquor |
| CN114380317B (en) * | 2021-10-24 | 2023-10-24 | 崇义章源钨业股份有限公司 | Method for recycling hydrochloric acid by recovering calcium sulfate from pickle liquor |
| CN114606383A (en) * | 2022-04-08 | 2022-06-10 | 昆明理工大学 | Method for comprehensively recovering valuable elements in industrial leaching residues of spodumene |
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