CN108950187A - A kind of method that mischmetal mine is decomposed in sodium carbonate roasting - Google Patents
A kind of method that mischmetal mine is decomposed in sodium carbonate roasting Download PDFInfo
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- CN108950187A CN108950187A CN201810958705.2A CN201810958705A CN108950187A CN 108950187 A CN108950187 A CN 108950187A CN 201810958705 A CN201810958705 A CN 201810958705A CN 108950187 A CN108950187 A CN 108950187A
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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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
- 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
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The present invention relates to a kind of method that mischmetal mine is decomposed in sodium carbonate roasting, the methods are as follows: leach after mixing mischmetal mine with acid solution, after separation of solid and liquid, obtain leachate and slag；Slag and sodium carbonate are mixed and roasted, obtained product of roasting is leached with water, obtains infusion and water logging slag.The present invention increases the step of acid solution is except Ca, Ba, F and P before mischmetal sodium carbonate roasting, only rare earth ore concentrate can be enable to decompose by a high-temperature roasting, reduce the dosage of sodium carbonate, while solving the agglomeration problems in roasting process.Present invention reduces process flow, energy consumption is reduced, non-exhaust emission in entire process flow, radioactivity can be up to standard in waste residue, while realizing and carrying out comprehensive substep to rare earth, thorium, fluorine and phosphorus and recycle, with good economic efficiency and application prospect.
Description
Technical field
The present invention relates to ore smelting technical fields, and in particular to the side of mischmetal mine is decomposed in a kind of sodium carbonate roasting
A kind of sodium carbonate roasting decomposition technique for the mixed rare earth concentrates that method more particularly to calcium, barium preferentially remove.
Background technique
Rare earth has the title of industrial " gold " can be with other materials group since it is with physical characteristics such as excellent photoelectromagnetics
At different properties, new material various in style, most significant function is exactly to increase substantially the quality and property of other products
Energy.It has irreplaceable role in fields such as metallurgical industry, petrochemical industry, glass ceramics, agricultural and new materials.
China is the big rare earth resources state of the first in the world, assumes responsibility for the market supply in 90% or more the world.With answering for rare earth
With more and more extensive, rare earth resources also start gradually to move towards exhausted.Therefore, how Rare Earth Mine is more effectively exploited and sharp
With, to greatest extent effectively exploitation Rare Earth Mine and exploitation reducig during resource waste and pollution be also Rare Earth Mine recovery process
Middle problem to be solved.
The main smelting process for production of Rare Earth Mine is but this method but there are following using concentrated sulfuric acid high-temperature roasting at present
Problem, if iron, phosphorus, thorium most of " being burnt to death " are in slag, thoriated emissive industrial waste residue and it is fluorine-containing, sulphur exhaust gas environmental pollution is tight
Weight, valuable element are not comprehensively utilized, result in waste of resources.In addition, acid gas corrosion equipment, environmental protection is difficult, " the three of generation
It is useless " pollution problem becomes increasingly conspicuous with the increasing of Rare Earth Production amount.In order to overcome the above problem, pass through scientific and technical research in recent years
The effort of person has developed the new method that many Rare Earth Mines are smelted, such as soda processes roasting, concentrated sulfuric acid low-temperature bake and sodium carbonate
Roasting etc..
Mixed type rare-earth mineral and soda ash react at 600 DEG C -700 DEG C, are decomposed into rare earth oxide, and selection is suitable
Roasting condition can make rare-earth mineral decompose it is more complete.Compared with other method of roasting, sodium carbonate roasting is for subsequent rare earth
Extraction and separation process also has the advantages that prominent: can make to account for about half amount of total rare earth (TRE) in the pickle liquor of sodium carbonate roasting method
Cerium in the form of oxidation state tetravalence exist be convenient for later separation；Thorium does not enter back into waste residue but enters pickle liquor, subsequently into
Extraction and separation process is simultaneously recycled；Sodium carbonate roasting will not generate exhaust gas, and F and P can enter solution and further recycle, the three wastes
It is minimum to the pollution of environment.However, the direct sodium carbonate roasting method of rare earth ore concentrate is in firing stage, there are a technologies outstanding
Bottleneck is exactly the agglomeration problems in roasting process, and sodium carbonate amount much easier agglomerations；Another problem is exactly carbonic acid
Sodium dosage mostly problem at high cost.
In view of the above-mentioned problems, researcher has developed a series of from baking modes and roasting process design angle
The method of agglomeration problems during solution sodium carbonate roasting.Such as CN102424912A discloses a kind of miberal powder embedding flux preparation
Flux pelletizing is prepared in the method for pelletizing first；Then second of pelletizing is carried out, miberal powder is made to embed flux pelletizing；Again into
Row is dry, roasts, and obtains pelletizing, shortens calcining time, reduces energy consumption, and solves pelletizing and be easy in roasting process
The problem of bonding.CN104846188A discloses a kind of method of roasting for preventing mischmetal mine from agglomerating, first by mischmetal
Mine roasting direct in air, it is baking mixed with sodium carbonate again after sulfuric acid leaching.This method first step oxidizing roasting makes wherein
Bastnaesite decompose reaction, then sulfuric acid leaching, so that the fluorine and rare earth of wherein most are leached, subsequent
During sulfuric acid leaching slag sodium carbonate roasting, agglomeration problems are addressed.
In rare earth ore concentrate in addition to containing rare earth element, also contain a large amount of non-rare earth impurity, such as iron, calcium, fluorine, phosphorus, silicon
And radioactive element thorium.Baotou rare earth ore concentrate also contains a certain amount of fluorite (CaF2), barite (BaSO4) and apatite
(Ca3(PO4)2).During sodium carbonate roasting, fluorite, barite and apatite all can consume to some extent sodium carbonate:
CaF2+Na2CO3=CaCO3+2NaF
BaSO4+Na2CO3=BaCO3+Na2SO4
Ca3(PO4)2+3Na2CO3=3CaCO3+2Na3PO4
Especially at 555 DEG C or more, fluorite CaF2Eutectic mixture easily is formed with sodium carbonate and causes to agglomerate.The base of early period
Plinth research work (Sep.Purif.Technol., 2016,168,161-167) shows that the presence of Ca or F in mineral all can
Lead to the agglomeration during sodium carbonate roasting.In conjunction with the more serious problem of the more agglomerations of dosage of sodium carbonate, how in sodium carbonate
The dosage of sodium carbonate, becomes and effectively solves sodium carbonate when efficiently removing the Ca or F in mineral before roasting, while reducing roasting
The new approaches of agglomeration problems in roasting process.
CN104846188A discloses a kind of method of roasting for preventing mischmetal mine from agglomerating, and proposes that mineral roasting is divided into two
Step is walked, and is air roasting and sulfuric acid leaching first, this can remove most F in the process, therefore in sodium carbonate roasting below
During burning, agglomeration problems mitigate significantly.The present invention proposes, mineral first pass around the method deliming of the excellent leaching of acid solution, barium, fluorine and
Next phosphorus carries out sodium carbonate roasting to gained leached mud, due to the shifting of calcium, barium, fluorine and phosphorus during subsequent sodium carbonate roasting
It removes and the dosage of sodium carbonate substantially reduces, equally solves the agglomeration problems during sodium carbonate roasting.
Summary of the invention
In view of problems of the prior art, the purpose of the present invention is to provide a kind of sodium carbonate roasting decomposition mixing is dilute
The method of Tu Kuang carries out excellent leaching to mischmetal mine first with acid solution and removes calcium, barium, fluorine and phosphorus, then carries out sodium carbonate roasting
It burns, greatly reduces the dosage of sodium carbonate, the agglomeration problems being effectively prevented from during sodium carbonate roasting have good economy
Benefit and application prospect.
To achieve this purpose, the present invention adopts the following technical scheme:
The present invention provides a kind of methods that mischmetal mine is decomposed in sodium carbonate roasting, which is characterized in that the method packet
Include following steps:
(1) it is leached after mixing mischmetal mine with acid solution, after separation of solid and liquid, obtains leachate and slag；
(2) slag and sodium carbonate that step (1) obtains are mixed and is roasted, obtained product of roasting is soaked with water
Out, infusion and water logging slag are obtained.
The present invention removes Ca, Ba, F in mischmetal before mischmetal sodium carbonate roasting using the method that acid solution leaches
And P, sodium carbonate roasting then is carried out to the slag that leaching obtains.Due to the shifting of Ca, Ba, F and P during subsequent sodium carbonate roasting
Except so that the dosage of sodium carbonate substantially reduces.Due to the reduction of the dosage of the removal and sodium carbonate of Ca and F, solves sodium carbonate
The problem of roasting process agglomerates, while reducing production cost.
In addition, technique provided by the invention only needs an acidleach and primary roasting, that is, it can solve mischmetal conventional carbon
The agglomeration problems that sour sodium roasting technique faces, reduce energy consumption, while reducing the dosage of sodium carbonate, and then greatly reduce life
Produce cost.
When the present invention leaches mischmetal mine using acid solution, the method for selecting excellent leaching is carried out, i.e. control was leached
Journey acid liquid measure is insufficient, and Ca, Ba, F and P of part in mischmetal mine are only removed after acidleach, and rare earth and thorium hardly lose,
On the one hand reduce the residual of acid solution in solid phase slag after leaching, and then avoid remaining acid solution in subsequent sodium carbonate roasting
Sodium carbonate is consumed in journey；On the other hand the loss of rare earth and thorium is reduced.But non-to be only limitted to this, the present invention equally can use excess
Acid solution leach mischmetal mine, should be specifically chosen according to the actual situation.
According to the present invention, the solid-to-liquid ratio of step (1) the mischmetal mine and acid solution is (0.2-5): 1, such as can be
Specific point value between 0.2:1,0.5:1,0.8:1,1:1,2:1,3:1,4:1 or 5:1 and above-mentioned numerical value, as space is limited and
For concise consideration, the present invention no longer exclusive list.
The unit of solid-to-liquid ratio of the present invention is g/mL.
According to the present invention, step (1) acid solution is nitric acid and/or hydrochloric acid, preferably hydrochloric acid.
According to the present invention, the concentration of step (1) described acid solution be 5-30wt%, such as can be 5wt%, 10wt%,
Specific point value between 15wt%, 20wt%, 25wt% or 30wt% and above-mentioned numerical value, as space is limited and for simplicity
Consider, the present invention no longer exclusive list.
According to the present invention, the temperature of step (1) described leaching is 20-80 DEG C, such as can be 20 DEG C, 30 DEG C, 40 DEG C, 50
DEG C, 60 DEG C, 70 DEG C or the specific point value between 80 DEG C and above-mentioned numerical value, as space is limited and for concise consideration, the present invention
No longer exclusive list.
According to the present invention, the temperature of step (2) described roasting is 500-800 DEG C, such as can be 500 DEG C, 550 DEG C, 600
DEG C, 650 DEG C, 700 DEG C, 750 DEG C or the specific point value between 800 DEG C and above-mentioned numerical value, examining as space is limited and for concise
Consider, the present invention no longer exclusive list.
According to the present invention, the time of step (2) described roasting be 1-3h, but such as 1h, 1.3h, 1.5h, 1.8h, 2h,
Specific point value between 2.3h, 2.5h, 2.8h or 3h and above-mentioned numerical value, as space is limited and for concise consideration, the present invention
No longer exclusive list.
According to the present invention, the mass ratio of step (2) slag and sodium carbonate is (3-15): 1, such as can be 3:1,4:
1, specific between 5:1,6:1,7:1,8:1,9:1,10:1,11:1,12:1,13:1,14:1 or 15:1 and above-mentioned numerical value
Value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the solid-to-liquid ratio of step (2) the water logging process product of roasting and water is (0.2-5): 1, such as can
To be the specific point value between 0.2:1,0.5:1,0.8:1,1:1,2:1,3:1,4:1 or 5:1 and above-mentioned numerical value, it is limited to a piece
Width and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the temperature of step (2) described water logging is 20-80 DEG C, such as can be 20 DEG C, 30 DEG C, 40 DEG C, 50
DEG C, 60 DEG C, 70 DEG C or the specific point value between 80 DEG C and above-mentioned numerical value, as space is limited and for concise consideration, the present invention
No longer exclusive list.
The present invention adopts F in the infusion obtained with the conventional methods in the field to step (2) and P is recycled.
According to the present invention, the water logging slag obtained to step (2) carries out subsequent processing, the method are as follows: using nitric acid and/or
Hydrochloric acid carries out pickling to the water logging slag that step (2) obtains, and obtains pickling solution and pickling slag, then using sulfuric acid or hydrochloric acid to gained
Pickling slag is leached, and pickle liquor and acid leaching residue are obtained after separation of solid and liquid.
The present invention carries out acid to water logging slag before carrying out sulfuric acid or salt Ore Leaching to water logging slag, using nitric acid and/or hydrochloric acid
It washes, it is therefore an objective to remove remaining Ca, Ba, F, P in water logging slag, advantageously reduce the impurity element in subsequent pickle liquor.
According to the present invention, in the acid cleaning process, the solid-to-liquid ratio of water logging slag and nitric acid and/or hydrochloric acid is (0.2-5): 1, example
It such as can be the specific point value between 0.2:1,0.5:1,0.8:1,1:1,2:1,3:1,4:1 or 5:1 and above-mentioned numerical value, limit
In length and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the concentration of the nitric acid and/or hydrochloric acid be 5-30wt%, such as can be 5wt%, 10wt%,
Specific point value between 15wt%, 20wt%, 25wt% or 30wt% and above-mentioned numerical value, as space is limited and for simplicity
Consider, the present invention no longer exclusive list.
According to the present invention, the temperature of the pickling is 20-80 DEG C, such as can be 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60
DEG C, 70 DEG C or the specific point value between 80 DEG C and above-mentioned numerical value, as space is limited and for concise consideration, the present invention is no longer
Exclusive list.
According to the present invention, the solid-to-liquid ratio of the pickling slag and sulfuric acid or hydrochloric acid be (0.2-5): 1, for example, can be 0.2:1,
Specific point value between 0.5:1,0.8:1,1:1,2:1,3:1,4:1 or 5:1 and above-mentioned numerical value, as space is limited and for letter
Bright consideration, the present invention no longer exclusive list.
According to the present invention, the concentration of the sulfuric acid or hydrochloric acid be 3-6mol/L, such as can be 3mol/L, 3.5mol/L,
Specific point value between 4mol/L, 4.5mol/L, 5mol/L, 5.5mol/L or 6mol/L and above-mentioned numerical value, as space is limited and
For concise consideration, the present invention no longer exclusive list.
According to the present invention, in the leaching process temperature be 50-80 DEG C, such as can be 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C,
Specific point value between 70 DEG C, 75 DEG C or 80 DEG C and above-mentioned numerical value, as space is limited and for concise consideration, the present invention is not
Exclusive list again.
When the present invention selects concentration to leach for the hydrochloric acid of 3-6mol/L to pickling slag, leaching the cerium come is three
Valence.
Benefit of the invention with method known in this field to cerium, thorium and the trivalent rare earth in gained pickle liquor carry out separation and
Recycling, particular determination is not done to this.
According to the present invention, the acid of washing obtained after the washing of gained acid leaching residue is used to soak pickling slag with returning after acid solution
Out.
The operation that the present invention selects method commonly used in the art to be separated by solid-liquid separation, such as can be filtering, suction filtration, centrifugation
Deng, but it is non-be only limitted to this, other suitable solid-liquid separating methods are equally applicable to the present invention.
As a preferred technical solution, mischmetal mine of the present invention roasting decomposition process the following steps are included:
(1) according to (0.2-5): the nitric acid and/or salt acid-mixed that mischmetal mine and concentration are 5-30wt% by 1 solid-to-liquid ratio
It is leached at 20-80 DEG C after conjunction, after separation of solid and liquid, obtains leachate and slag；
(2) slag and sodium carbonate obtained step (1) is according to (3-15): 1 mass ratio mixing is warming up to 500-800
DEG C roasting 1-3h, then according to (0.2-5): 1 solid-to-liquid ratio leaches obtained product of roasting at 20-80 DEG C with water,
Infusion and water logging slag are obtained after separation of solid and liquid；
(3) according to (0.2-5): 1 solid-to-liquid ratio obtains step (2) using the nitric acid and/or hydrochloric acid that concentration is 5-30wt%
To water logging slag pickling is carried out at 20-80 DEG C, obtain pickling solution and pickling slag；
(4) it is carried out at 50-80 DEG C using the pickling slag that sulfuric acid or hydrochloric acid that concentration is 3-6mol/L obtain step (3)
It leaches, solid-to-liquid ratio is (0.2-5): 1, pickle liquor and acid leaching residue are obtained after separation of solid and liquid；By what is obtained after the washing of gained acid leaching residue
Acid is washed for being leached to pickling slag with returning after acid solution, cerium, thorium and the trivalent rare earth in gained pickle liquor are returned
It receives.
Compared with prior art, the present invention is at least had the advantages that
(1) present invention increases the step of acid solution is except Ca, Ba, F and P before mischmetal sodium carbonate roasting, only passes through one
Secondary high-temperature roasting can enable rare earth ore concentrate to decompose, and reduce the dosage of sodium carbonate, while solve the knot in roasting process
Block problem.
(2) present invention may be implemented to recycle F and P before recovering rare earth and thorium, using sulfuric acid or hydrochloric acid to pickling slag into
After one step leaches, can realize the extraction and separation of cerium, thorium and trivalent rare earth by subsequent operation, so realize to rare earth, thorium, fluorine and
The elements such as phosphorus carry out comprehensive substep and recycle.
(3) present invention reduces process flow, energy consumption is reduced, non-exhaust emission in entire process flow is put in waste residue
Penetrating property can be up to standard, with good economic efficiency and application prospect.
Detailed description of the invention
Fig. 1 is the process flow chart that a kind of specific embodiment of the present invention provides；
Fig. 2 is the pictorial diagram of the product of roasting obtained after 1 sodium carbonate roasting of the embodiment of the present invention；
Fig. 3 is the pictorial diagram of the product of roasting obtained after 3 sodium carbonate roasting of the embodiment of the present invention；
Fig. 4 is the pictorial diagram of the product of roasting obtained after 1 sodium carbonate roasting of comparative example of the present invention.
The present invention is described in more detail below.But following examples is only simple example of the invention, not generation
Table or limitation the scope of the present invention, protection scope of the present invention are subject to claims.
Specific embodiment
To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, of the invention is typical but non-limiting
Embodiment is as follows:
The present invention selects Baotou rare earth ore concentrate as mischmetal mine in specific embodiment part and handles.
Embodiment 1
A kind of method that mischmetal mine is decomposed in sodium carbonate roasting is present embodiments provided, as shown in Figure 1, the method packet
Include following steps:
(1) mischmetal mine is carried out at 50 DEG C after the mixed in hydrochloric acid of 30wt% with concentration according to the solid-to-liquid ratio of 2:1
It leaches, is filtered after the completion of leaching, obtain leachate and slag；
(2) slag and sodium carbonate obtained step (1) is mixed according to the mass ratio of 3:1, is warming up to 800 DEG C of roasting 3h,
Then obtained product of roasting is leached at 30 DEG C with water according to the solid-to-liquid ratio of 1:1, infusion and water is obtained after filtering
Phase analysis；
(3) the water logging slag obtained using the dilute hydrochloric acid that concentration is 10wt% to step (2) according to the solid-to-liquid ratio of 0.5:1 is 25
Pickling is carried out at DEG C, obtains pickling solution and pickling slag, and the leachate mixing that gained pickling solution and step (1) obtain merges place
Reason；
(4) the pickling slag obtained after step (3) pickling is leached at 75 DEG C using the sulfuric acid that concentration is 5mol/L,
Solid-to-liquid ratio is 2:1, obtains pickle liquor and acid leaching residue after filtering；It obtains washing acid and waste residue after washing gained acid leaching residue, it will
What is obtained washes acid for being leached to pickling slag with returning after acid solution；To cerium, thorium and the trivalent rare earth in gained pickle liquor
Further recycled.
After testing, the removal rate of Ca, Ba, F and P are 60% in the present embodiment step (1).As shown in Fig. 2, step (2)
Gained product of roasting is after middle sodium carbonate roasting almost without caking phenomenon.
Embodiment 2
Compared with Example 1, other than the temperature of sodium carbonate roasting in step (2) is adjusted to 650 DEG C, other steps and
Condition is identical with embodiment 1.
Embodiment 3
A kind of method that mischmetal mine is decomposed in sodium carbonate roasting is present embodiments provided, the method includes following steps
It is rapid:
(1) mischmetal mine is carried out at 40 DEG C after the mixed in hydrochloric acid of 20wt% with concentration according to the solid-to-liquid ratio of 1:2
It leaches, is filtered after the completion of leaching, obtain leachate and slag；
(2) slag and sodium carbonate obtained step (1) is mixed according to the mass ratio of 5:1, is warming up to 700 DEG C of roasting 3h,
Then obtained product of roasting is leached at 20 DEG C with water according to the solid-to-liquid ratio of 1.5:1, after filtering, obtain infusion and
Water logging slag；
(3) the water logging slag obtained using the dilute hydrochloric acid that concentration is 15wt% to step (2) according to the solid-to-liquid ratio of 2.5:1 is 30
Pickling is carried out at DEG C, obtains pickling solution and pickling slag, and the leachate mixing that gained pickling solution and step (1) obtain merges place
Reason；
(4) the pickling slag obtained after step (3) pickling is leached at 75 DEG C using the sulfuric acid that concentration is 5mol/L,
Solid-to-liquid ratio is 1:1, obtains pickle liquor and acid leaching residue after filtering；It obtains washing acid and waste residue after washing gained acid leaching residue, it will
What is obtained washes acid for being leached to pickling slag with returning after acid solution；To cerium, thorium and the trivalent rare earth in gained pickle liquor
Further recycled.
After testing, the removal rate of Ca, Ba, F and P are 40% in the present embodiment step (1).As shown in figure 3, step (2)
Gained product of roasting is after middle sodium carbonate roasting almost without caking phenomenon.
Embodiment 4
Compared with Example 3, other than the temperature of sodium carbonate roasting in step (2) is adjusted to 650 DEG C, other steps and
Condition is identical with embodiment 1.
Embodiment 5
A kind of method that mischmetal mine is decomposed in sodium carbonate roasting is present embodiments provided, the method includes following steps
It is rapid:
(1) it is carried out at 80 DEG C after mixing mischmetal mine with the nitric acid that concentration is 15wt% according to the solid-to-liquid ratio of 2:1
It leaches, is filtered after the completion of leaching, obtain leachate and slag；
(2) slag and sodium carbonate obtained step (1) is mixed according to the mass ratio of 10:1, is warming up to 750 DEG C of roasting 2h,
Then obtained product of roasting is leached at 35 DEG C with water according to the solid-to-liquid ratio of 1:1, infusion and water is obtained after filtering
Phase analysis；
(3) the water logging slag obtained using the nitric acid that concentration is 15wt% to step (2) according to the solid-to-liquid ratio of 1:1 is at 55 DEG C
Pickling is carried out, pickling solution and pickling slag are obtained, the leachate mixing that gained pickling solution and step (1) obtain carries out merging treatment；
(4) the pickling slag obtained after step (3) pickling is leached at 60 DEG C using the hydrochloric acid that concentration is 5mol/L,
Solid-to-liquid ratio is 3:1, obtains pickle liquor and acid leaching residue after filtering；It obtains washing acid and waste residue after washing gained acid leaching residue, it will
What is obtained washes acid for being leached to pickling slag with returning after acid solution, in gained pickle liquor thorium and trivalent rare earth return
It receives.
After testing, the removal rate of Ca, Ba, F and P are 28% in the present embodiment step (1).
Comparative example 1
(1) mischmetal green ore and sodium carbonate are mixed according to the mass ratio of 3:1, is warming up to 800 DEG C of roasting 3h, then
Obtained product of roasting is leached at 50 DEG C with water according to the solid-to-liquid ratio of 1:1, infusion and water logging slag are obtained after filtering；
(2) the water logging slag that step (2) obtains is carried out using the dilute hydrochloric acid that concentration is 10wt% according to the solid-to-liquid ratio of 0.2:1
The pickling at 45 DEG C obtains pickling solution and pickling slag, and the leachate mixing that gained pickling solution and step (1) obtain merges place
Reason；
(3) the pickling slag obtained after step (3) pickling is leached at 80 DEG C using the sulfuric acid that concentration is 5mol/L,
Solid-to-liquid ratio is 0.8:1, obtains pickle liquor and acid leaching residue after filtering；It obtains washing acid and waste residue after washing gained acid leaching residue,
Obtained acid of washing is used to leach pickling slag with returning after acid solution；To in gained pickle liquor cerium, thorium and trivalent it is dilute
Soil is further recycled.
As shown in figure 4, gained product of roasting caking phenomenon is serious after sodium carbonate roasting in step (1).
Comparative example 2
Compared with comparative example 1, other than the temperature of sodium carbonate roasting in step (1) is adjusted to 650 DEG C, other steps and
Condition is identical with comparative example 1.
Comparative example 3
Compared with comparative example 1, in addition to the mass ratio of mischmetal green ore and sodium carbonate in step (1) is adjusted to 5:1
Outside, other steps and condition are identical with comparative example 1.
Comparative example 4
Compared with comparative example 1, in addition to the mass ratio of mischmetal green ore and sodium carbonate in step (1) is adjusted to 5:1
Outside, the temperature of sodium carbonate roasting is adjusted to outside 650 DEG C, other steps and condition are identical with comparative example 1.
Comparative example 5
Compared with comparative example 1, in addition to the mass ratio of mischmetal green ore and sodium carbonate in step (1) is adjusted to 7.5:
Outside 1, other steps and condition are identical with comparative example 1.
Comparative example 6
Compared with comparative example 1, in addition to the mass ratio of mischmetal green ore and sodium carbonate in step (1) is adjusted to 7.5:
Outside 1, the temperature of sodium carbonate roasting is adjusted to outside 650 DEG C, other steps and condition are identical with comparative example 1.
The leaching rate of the oxygenation efficiency of cerium and rare earth in each embodiment and comparative example is tested, the results are shown in Table 1.
Table 1
Note: in embodiment 5, because selecting salt Ore Leaching pickling slag, cerium is trivalent, so its oxygenation efficiency is not meant to investigation
Parameter
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of method that mischmetal mine is decomposed in sodium carbonate roasting, which is characterized in that the described method comprises the following steps:
(1) it is leached after mixing mischmetal mine with acid solution, after separation of solid and liquid, obtains leachate and slag；
(2) slag and sodium carbonate that step (1) obtains are mixed and are roasted, obtained product of roasting is leached with water,
Infusion and water logging slag are obtained after separation of solid and liquid.
2. the method as described in claim 1, which is characterized in that carried out after mixing mischmetal mine with acid solution in step (1)
Excellent leaching；
Preferably, the solid-to-liquid ratio of step (1) the mischmetal mine and acid solution is (0.2-5): 1；
Preferably, step (1) acid solution is nitric acid and/or hydrochloric acid；
Preferably, the concentration of step (1) described acid solution is 5-30wt%；
Preferably, the temperature of step (1) described leaching is 20-80 DEG C.
3. such as the described in any item methods of claims 1 or 2, which is characterized in that the temperature of step (2) described roasting is 500-
800℃；
Preferably, the time of step (2) described roasting is 1-3h；
Preferably, the mass ratio of step (2) slag and sodium carbonate is (3-15): 1.
4. the method according to claim 1, which is characterized in that step (2) the water logging process product of roasting and
The solid-to-liquid ratio of water is (0.2-5): 1；
Preferably, the temperature of step (2) described water logging is 20-80 DEG C.
5. method according to any of claims 1-4, which is characterized in that carried out to the water logging slag that step (2) obtains subsequent
Processing, the method are as follows: pickling is carried out to the water logging slag that step (2) obtains using nitric acid and/or hydrochloric acid, obtains pickling solution and acid
Then washery slag leaches gained pickling slag using sulfuric acid or hydrochloric acid, pickle liquor and acid leaching residue is obtained after separation of solid and liquid.
6. method as claimed in claim 5, which is characterized in that in the acid cleaning process, water logging slag and nitric acid and/or hydrochloric acid
Solid-to-liquid ratio is (0.2-5): 1；
Preferably, the concentration of the nitric acid and/or hydrochloric acid is 5-30wt%；
Preferably, the temperature of the pickling is 20-80 DEG C.
7. such as method described in claim 5 or 6, which is characterized in that the solid-to-liquid ratio of the pickling slag and sulfuric acid or hydrochloric acid is
(0.2-5):1；
Preferably, the concentration of the sulfuric acid or hydrochloric acid is 3-6mol/L；
Preferably, temperature is 50-80 DEG C in the leaching process.
8. such as the described in any item methods of claim 5-7, which is characterized in that cerium, thorium and the trivalent in gained pickle liquor
Rare earth is recycled.
9. such as the described in any item methods of claim 5-8, which is characterized in that wash sour use for what is obtained after the washing of gained acid leaching residue
It is returned after matching acid solution and pickling slag is leached.
10. such as the described in any item methods of claim 1-9, which is characterized in that the described method comprises the following steps:
(1) according to (0.2-5): 1 solid-to-liquid ratio will be after the nitric acid that mischmetal mine and concentration are 5-30wt% and/or mixed in hydrochloric acid
It is leached at 20-80 DEG C, after separation of solid and liquid, obtains leachate and slag；
(2) slag and sodium carbonate obtained step (1) is according to (3-15): 1 mass ratio mixing is warming up to 500-800 DEG C of roasting
1-3h is burnt, then according to (0.2-5): 1 solid-to-liquid ratio leaches obtained product of roasting at 20-80 DEG C with water, solid-liquid
Infusion and water logging slag are obtained after separation；
(3) according to (0.2-5): 1 solid-to-liquid ratio obtains step (2) using the nitric acid and/or hydrochloric acid that concentration is 5-30wt%
Water logging slag carries out pickling at 20-80 DEG C, obtains pickling solution and pickling slag；
(4) it is soaked at 50-80 DEG C using the pickling slag that sulfuric acid or hydrochloric acid that concentration is 3-6mol/L obtain step (3)
Out, solid-to-liquid ratio is (0.2-5): 1, pickle liquor and acid leaching residue are obtained after separation of solid and liquid；It is washed what is obtained after the washing of gained acid leaching residue
Acid recycles cerium, thorium and the trivalent rare earth in gained pickle liquor for being leached to pickling slag with returning after acid solution.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113355537A (en) * | 2021-04-14 | 2021-09-07 | 中稀(常州)稀土新材料有限公司 | Novel fuzzy linkage flexible praseodymium-neodymium extraction novel process for mixed rare earth ore |
| CN114249308A (en) * | 2021-11-19 | 2022-03-29 | 四川大学 | Method for extracting phosphorus resource and rare earth resource in phosphorus-containing mixed rare earth concentrate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103397213A (en) * | 2013-07-22 | 2013-11-20 | 葛新芳 | Method for decomposing and extracting Baotou rare earth ore through mixed alkali roasting process |
| CN103540740A (en) * | 2012-07-12 | 2014-01-29 | 中国科学院过程工程研究所 | Clean separating method of Baotou rare-earth ore concentrate |
| CN104862502A (en) * | 2014-02-20 | 2015-08-26 | 中国科学院过程工程研究所 | Cleaning smelting technology of bastnaesite and monazite mixed rare earth ore concentrate |
| CN106048265A (en) * | 2016-08-17 | 2016-10-26 | 成都理工大学 | Extraction method of rare-earth elements from bastnaesite |
-
2018
- 2018-08-22 CN CN201810958705.2A patent/CN108950187A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103540740A (en) * | 2012-07-12 | 2014-01-29 | 中国科学院过程工程研究所 | Clean separating method of Baotou rare-earth ore concentrate |
| CN103397213A (en) * | 2013-07-22 | 2013-11-20 | 葛新芳 | Method for decomposing and extracting Baotou rare earth ore through mixed alkali roasting process |
| CN104862502A (en) * | 2014-02-20 | 2015-08-26 | 中国科学院过程工程研究所 | Cleaning smelting technology of bastnaesite and monazite mixed rare earth ore concentrate |
| CN106048265A (en) * | 2016-08-17 | 2016-10-26 | 成都理工大学 | Extraction method of rare-earth elements from bastnaesite |
Non-Patent Citations (2)
| Title |
|---|
| 肖桐 等: "四川矿纯碱焙烧制取氯化稀土工艺研究", 《稀土》 * |
| 黄礼煌: "《稀土提取技术》", 30 June 2006, 冶金工业出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113355537A (en) * | 2021-04-14 | 2021-09-07 | 中稀(常州)稀土新材料有限公司 | Novel fuzzy linkage flexible praseodymium-neodymium extraction novel process for mixed rare earth ore |
| CN114249308A (en) * | 2021-11-19 | 2022-03-29 | 四川大学 | Method for extracting phosphorus resource and rare earth resource in phosphorus-containing mixed rare earth concentrate |
| CN114249308B (en) * | 2021-11-19 | 2023-09-08 | 四川大学 | Method for extracting phosphorus resources and rare earth resources in phosphorus-containing mixed rare earth concentrate |
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