CN106319248A - Substance containing rare earth phosphate - Google Patents
Substance containing rare earth phosphate Download PDFInfo
- Publication number
- CN106319248A CN106319248A CN201510347681.3A CN201510347681A CN106319248A CN 106319248 A CN106319248 A CN 106319248A CN 201510347681 A CN201510347681 A CN 201510347681A CN 106319248 A CN106319248 A CN 106319248A
- Authority
- CN
- China
- Prior art keywords
- phosphate
- rare earth
- phosphoric acid
- material containing
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a substance containing rare earth phosphate. According to the substance containing rare earth phosphate, the rare earth phosphate at least contains a first phase structure and a second phase structure, the first phase structure is an amorphous phase, and the second phase structure comprises a monazite phase or/and a xenotime phase. The rare earth containing at least two phase structures enables high enrichment degree of the rare earth in the substance containing rare earth phosphate, the grade is high, and the subsequent comprehensive recovery and utilization for the rare earth can be convenient.
Description
Technical field
The present invention relates to rare earth and reclaim field, in particular to a kind of material containing RE phosphate.
Background technology
Rare-earth mineral in nature often together with the mineral intergrowth such as barite, calcite, apatite, silicate ore.By
Different in the one-tenth ore deposit reason of mineral, rare earth element occurrence status in mineral and content are the most different.The Rare Earth Mine currently exploited
In thing, the grade of rare earth oxide is a few percent.In order to meet the needs that rare earth metallurgy produces, must be first before smelting
Through beneficiation method, by rare earth and other ore separation, rare-earth mineral is made to be enriched with.In rare earth ore concentrate after beneficiation enrichment dilute
The content of soil oxide is usually 50%～70%.
Rare-earth mineral mainly has bastnaesite, monazite, xenotime and ion adsorption type rare earth ore etc..At present, monazite is reclaimed
The method of middle rare earth mainly has following two mode: (1) alkaline process resolution process monazite (is applicable to high-grade solitary stone ore),
Monazite is with liquid caustic soda course of reaction, and rare earth generates water-fast hydroxide, and phosphorus is changed into tertiary sodium phosphate, rare earth hydroxide
Thing obtains mixed chlorinated rare earth through excellent molten, the remove impurity of persalt again.If the impurity content such as ferrum, silicon is high in concentrate, be easily formed sodium silicate,
The colloidal materials such as hydrated ferric oxide., precipitation filters separation circuit and is difficult to, and therefore this technique cannot be properly functioning.(2) concentrated sulphuric acid
Roasting method decomposes solitary stone ore, and monazite concentrate and concentrated sulphuric acid are blended in 200-230 DEG C of decomposition, and concentrated sulphuric acid consumption is concentrate weight
1.7-2 times, with the water extraction of 7-10 times of concentrate weight after analyte cooling, leachate middle rare earth about 50g/L (REO),
25g/L P2O5, 2.5g/L Fe2O3, acidity is 2.5mol/L.This immersion acidity is high, and foreign matter of phosphor, thorium are high, uses sodium sulfate double salt
Precipitating rare earth and thorium, be then passed through alkali and transfer hydroxide to, then use acid preferentially to leach rare earth, extracting and separating rear earth, thorium.Should
Method complex process, solid-liquor separation step is many, and technique is discontinuous, and rare earth yield is low；It addition, soda acid cross-reference, chemical industry
Consumption of raw materials cost is high, and phosphorus enters waste water intractability greatly, and radioelement thorium is dispersed in slag and waste water and is difficult to efficient recovery.
Phosphorus ore is the primary raw material producing phosphorus chemical product, and world phosphate resource reserve is big, normal association trace rare-earth.Due to rare earth
Ionic radius (0.848～0.106nm) and Ca2+(0.106nm) very close to, rare earth is composed in isomorph mode and is stored in phosphorus ore,
Existing with Independent Mineral phase structures such as apatite phase, hydroxyapatite, rare earth is likely to be adsorbed in phosphorus ore with ionic state form simultaneously
In.At present, the method reclaiming phosphorus ore middle rare earth includes following technique: (1) hydrochloric acid, nitrate method process the phosphoric acid by wet process work of phosphorus ore
Skill, the rare earth of more than 95% enters in solution, then use solvent extraction, ion to exchange, precipitate, the mode recovering rare earth such as crystallization；
(2) sulfuric acid process processes the Wet Processes of Phosphoric Acid of phosphorus ore, and rare earth respectively enters in solution and ardealite, then uses sulfuric acid to leach phosphorus stone
Cream makes rare earth enter solution, the mode recovering rare earth such as the rare earth in solution can use solvent extraction, ion to exchange, precipitates, crystallization.
(3) phosphoric acid processes phosphorus ore technique, is mixed with phosphoric acid solution by the phosphorus concentrate containing rare earth and reacts, and makes by controlling process conditions
Phosphorus ore middle rare earth precipitates with fluoride form, and more than 85% rare earth enters in slag, then uses hydrochloric acid, nitric acid or sulfuric acid dissolution to reclaim
Rare earth in slag, but slag middle rare earth grade is the lowest, about 1%, foreign matter of phosphor, calcium, aluminum, silicon equal size are high, and rare earth fluoride
Being difficult to dissolve with acid, acid consumption height, the quantity of slag is big, and rare earth yield is low；It addition, in entrance leachate 15% rare earth in deliming
During easily enter in gypsum tailings and be difficult to reclaim.
Phosphorus ore containing mengite rare-earth is analogy mineral difficult to deal with, this contains multiple group containing mengite rare-earth phosphorus ore simultaneously
Point, including monazite, rare earth and phosphorus ore etc..Owing to monazite and phosphorus ore belong to phosphate mineral, both mineralogy
Being closer to, in the mineral of its symbiosis, monazite cloth embedding with phosphorus ore is in close relations.Reclaim this composite ore rare earth elements and phosphorus
During element, due in composite ore each material parcel to inlay difficulty of dissociating relatively big, physical upgrading is difficulty with the effective sorting to Ore.
Especially since decompose monazite to need relatively harsh condition, need higher temperature and acid-base value etc., use prior art
In sulfuric acid process wet treatment when containing the phosphorus ore of monazite, monazite often cannot be made to decompose completely, fail to realize it and effectively divide
From utilization.Therefore, how to separate containing the phosphorus in rare earth phosphate rock and rare earth, particularly this kind of quality of the phosphorus ore Han mengite rare-earth is relatively low,
Rare earth in the composite ore that mineralogical composition is more miscellaneous, has become as a technical problem urgently to be resolved hurrily of research staff.
Summary of the invention
Present invention is primarily targeted at a kind of material containing RE phosphate of offer, to provide one to separate from rare earth phosphate rock
The RE phosphate material that the content of rare earth that arrives is higher.
To achieve these goals, according to an aspect of the invention, it is provided a kind of material containing RE phosphate, this contains dilute
RE phosphate in the phosphatic material of soil at least contains the first phase structure and the second phase structure, and the first phase structure is amorphous phase,
Second phase structure includes monazite phase or/and xenotime phase.
Further, in terms of weight content, amorphous phase content in RE phosphate is more than 1%, preferably 5～40%.
Further, in the material containing RE phosphate, the weight ratio of the first phase structure and the second phase structure is 1:1～20.
Further, also including the impurity of iron content and/or aluminum in the material containing RE phosphate, in terms of oxide, ferrum and/or aluminum contain
Amount is 1～50wt%, preferably 3～25wt%.
Further, in the material containing RE phosphate, in terms of oxide, rare earth is 2～20 with the weight ratio of ferrum and/or aluminum:
1。
Further, the material containing RE phosphate is isolated from the phosphorus ore containing monazite and/or xenotime, from containing solitary
In the phosphorus ore of stone and/or xenotime, the method for the isolated material containing RE phosphate includes: step S1, with the solution of phosphoric acid
Phosphorus ore containing monazite and/or xenotime is leached, obtains leachate and rare earth acid leaching residue；Leachate contain rare earth ion,
Calcium ion and dihydrogen phosphate ions；Step S2, carries out ripening to leachate, solid-liquid separation obtain phosphoric acid rare-earth precipitation and
One-lime phosphate solution；And step S3, rare earth acid leaching residue is mixed with phosphoric acid rare-earth precipitation, obtains the material containing RE phosphate；
The reaction temperature of step S2 is higher than the reaction temperature of step S1.
Further, step S1 includes: at a temperature of 10 DEG C～60 DEG C, with the solution of phosphoric acid to containing monazite and/or phosphorus
The phosphorus ore in yttrium ore deposit leaches 0.5～8 hour, preferably 1～4 hour, obtains leachate and rare earth acid leaching residue.
Further, step S2 includes: to the first solution at 60 DEG C～150 DEG C, is aged at a temperature of preferably 80～120 DEG C
Processing 0.5～24 hour, preferably 1～8 hour, solid-liquid separation obtained phosphoric acid rare-earth precipitation and one-lime phosphate solution.
Further, the solution of phosphoric acid also comprises hydrochloric acid and/or nitric acid；Preferably, in terms of the molal quantity of anion, phosphorous
In the solution of acid, hydrochloric acid and/or the ratio shared by nitric acid are less than 30%, more preferably 2～15%.
Further, with P2O5Meter, in the solution of phosphoric acid, the mass concentration of phosphoric acid is 15%～50%, preferably 15%～30%.
Further, before step S1, method also include by the solution of phosphoric acid with containing monazite and/or xenotime phosphorus ore by
According to the step of the ratio mixing that liquid-solid ratio is 2～10L:1kg, preferably liquid-solid ratio is 3～6L:1kg.
Application technical scheme, by studying in detail the separation method of the phosphorus ore of alloy containing mixed rare earth, and therefrom
The material containing RE phosphate that a kind of rare earth grade of isolated is higher, the RE phosphate in this material at least contains first
Phase structure and the second phase structure, wherein, the first phase structure is amorphous phase, and the second phase structure includes monazite phase or/and xenotime
Phase.The above-mentioned material containing RE phosphate is rich in the rare earth of multiple phase structure, and rare-earth enrichment degree is high, of high grade, it is simple to dilute
Soil carries out comprehensive reutilization.
Accompanying drawing explanation
The Figure of description of the part constituting the application is used for providing a further understanding of the present invention, and the present invention's is schematic real
Execute example and illustrate for explaining the present invention, being not intended that inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows and contains dilute according to a preferred embodiment of the present invention isolated from the phosphorus ore containing monazite and/or xenotime
The phosphatic schematic flow sheet of soil；And
Fig. 2 shows the X-ray diffraction spectrogram of the material containing RE phosphate obtained according to embodiments of the invention 3.
Detailed description of the invention
It should be noted that in the case of not conflicting, the embodiment in the application and the feature in embodiment can be mutually combined.
The present invention is described in detail below in conjunction with embodiment.
In the following description, the molecular formula of monazite (English entitled Monazite) is (Ln, Th) PO4, in formula, Ln refers to remove
At least one in rare earth element beyond promethium.
As pointed by background technology, rare earth phosphate rock such as the composite ore containing multi mineral such as apatite, monazite and xenotimes
When using existing separation method to separate, it is difficult to efficiently separate this kind of composite ore rare earth elements and P elements obtains rare earth
The material that content is higher.In order to improve drawbacks described above of the prior art, inventor's separation to the most special above-mentioned composite ore
Method studies in detail, and the material containing RE phosphate that therefrom a kind of content of rare earth of isolated is of a relatively high.This
Invention proposes the most on this basis.
In a kind of typical embodiment of the present invention, it is provided that a kind of material containing RE phosphate, the rare earth in this material
Phosphate at least contains the first phase structure and the second phase structure, and wherein, the first phase structure is amorphous phase, and the second phase structure includes
Monazite phase is or/and xenotime phase.The above-mentioned material containing RE phosphate is rich in the rare earth of multiple phase structure, and rare-earth enrichment degree is high,
Of high grade, it is simple to rare earth is carried out comprehensive reutilization.
In the material containing RE phosphate comprising above-mentioned phase structure, amorphous phase is the phase structure that phosphoric acid rare-earth precipitation is formed, its
The height of content and rare earth phosphate rock middle rare earth occurrence patterns and content, and rare earth phosphate rock is relevant in the control condition leaching step.
But the height that the height of its content is sampled with the rare earth of the obtained material containing RE phosphate is closely related, and determines rare earth
Comprehensive reutilization rate, the material containing RE phosphate with above-mentioned multiple phase structure has had of a relatively high grade,
In order to improve its grade further, in one preferred embodiment of the present invention, in the above-mentioned material containing RE phosphate, without fixed
Shape content in RE phosphate is more than 1wt%, preferably 5～40wt%.When amorphous phase content is more than 1wt%, have
It is beneficial to the recovery of the follow-up material middle rare earth containing RE phosphate.And amorphous phase content is when being 5～40wt%, rare earth grade is relative
Higher, it is more beneficial for the comprehensive reutilization of rare earth element.
In above preferred embodiment, amorphous phase account for the content of RE phosphate within the above range time the thing containing RE phosphate
Matter rare earth grade has been of a relatively high, in order to improve the value of this material further, another kind of the most real in the present invention
Executing in example, in the above-mentioned material containing RE phosphate, the first phase structure is 1:1～20 with the weight ratio of the second phase structure.By above-mentioned
The first phase structure in material containing RE phosphate controls within the above range with the weight ratio of the second phase structure so that this contains dilute
The phosphatic material of soil is provided simultaneously with above two phase structure, thus has the advantage that rare earth is of high grade.Thing containing RE phosphate
Matter rare earth is of high grade, it is simple to rare earth carries out comprehensive reutilization, and has higher rare-earth yield.
In the above-mentioned material containing RE phosphate, due to association ferrum and/or aluminium mineral in rare earth phosphate rock, thus in separation process the most not
Can avoid impurity containing above-mentioned element kind, thus further comprises the impurity of iron content and/or aluminum.The content of this partial impurities
Height and the ferrum of rare earth phosphate rock institute association and/or the content of aluminum and acidleach process control are relevant.In a kind of preferably enforcement of the present invention
In example, in terms of oxide, the impurity of above-mentioned iron content and/or aluminum content in the material containing RE phosphate is 1～50wt%, excellent
Elect 3～25wt% as.The impurity content of iron content and/or aluminum in the above-mentioned material containing RE phosphate is controlled in 1～50wt% scope
In, there is content of rare earth of a relatively high, it is simple to rare earth reclaims；By impurity enriched in solid phase, reduce impurity element and enter leaching
In liquid, reduce follow-up phosphoric acid purification remove impurity burden, and the existence of ferrum aluminum in the material containing RE phosphate, be conducive to follow-up
Rare earth removal process plays the effect of solid phosphorus, and then is conducive to improving rare-earth yield and realizing the comprehensive utilization of ferrum aluminum；And by above-mentioned
In material containing RE phosphate, the content of the impurity of iron content and/or aluminum controls in the range of 3～25wt%, has content of rare earth high
Advantage, the material rare earth containing RE phosphate with above-mentioned impurity content is of high grade, it is simple to rare earth reclaims, and realizes impurity
The comprehensive utilization of ferrum aluminum.
Equally, control impurity content to enable to the material containing RE phosphate of the present invention within the above range and have higher dilute
Soil grade, in order to improve rare earth grade further, in another preferred embodiment of the present invention, above-mentioned containing RE phosphate
In material, in terms of oxide, rare earth is 2～20:1 with the weight ratio of ferrum and/or aluminum.By rare earth and ferrum and/or the weight ratio control of aluminum
System is within the above range, it is possible to make the material containing RE phosphate of the present invention have higher content of rare earth.Be conducive to follow-up
Sulfuric acid baking processes the process of recovering rare earth technique, can realize the comprehensive utilization of ferrum bauxite resource, and is enriched in by impurity iron aluminum solid
Xiang Zhong, reduces impurity element and enters in leachate, reduces follow-up phosphoric acid purification remove impurity burden.
In the above-mentioned material containing RE phosphate, according to the difference in rare earth source, can be from the phosphorus ore containing monazite and/or xenotime
Middle isolated.In one preferred embodiment of the present invention, from the phosphate mineral isolated phosphoric acid Han rare earth containing monazite
The method of the material of salt includes: step S1, leaches the phosphorus ore containing monazite and/or xenotime with the solution of phosphoric acid,
To the leachate containing rare earth ion, calcium ion and dihydrogen phosphate ions and rare earth acid leaching residue；Step S2, carries out old to leachate
Change processes, and solid-liquid separation obtains phosphoric acid rare-earth precipitation and one-lime phosphate solution；And step S3, rare earth acid leaching residue is dilute with phosphoric acid
Soil precipitation mixing, obtains the material containing RE phosphate；The reaction temperature of step S2 is higher than the reaction temperature of step S1.
Above-mentioned from phosphorus ore isolated containing RE phosphate material step in, under relatively low reaction temperature, pass through
The solution using phosphoric acid leaches containing monazite and/or the rare earth phosphate rock of xenotime, utilizes the hydrion dissolved phosphorus in phosphoric acid solution
Phosphorus in ore deposit forms one-lime phosphate solution, and rare earth element is also dissolved and enters in solution simultaneously, is formed containing rare earth ion, Ca2+
And H2PO4 -Leachate；And monazite does not dissolves during acidleach and is retained in slag, it is achieved that phosphorus separates with monazite.
Leachate is carried out ripening, is conducive to rare earth element being formed phosphoric acid rare-earth precipitation and realizing rare earth element and phosphorus unit further
The separation of element.Reaction temperature is less to the influence of extraction of P elements during acidleach, and phosphoric acid rare earth dissolubility at a lower temperature
Relatively large, the beneficially leaching of rare earth element, can effectively suppress the leaching of the impurity element such as ferrum, aluminum in phosphorus ore under low temperature simultaneously,
Make ferrum element and aluminium element leaching rate < 5%, significantly reduce follow-up phosphoric acid purification remove impurity burden.Thus, it is aged by control
The temperature processed is higher than the temperature of step of acid dipping, and phosphoric acid rare earth solubility product is little at a relatively high temperature, is conducive to making leachate
In rare earth element precipitate with RE phosphate form, realize efficiently separating of rare earth element and P elements further.From containing
The phosphorus ore of rare earth is to phosphoric acid rare-earth precipitation, and rare-earth enrichment multiple is up to tens times of even hundreds of times, phosphoric acid rare-earth precipitation middle rare earth product
Position up to more than 45%, even up to more than 55%, rare-earth yield reaches more than 80%, even up to more than 90%, improve dilute
Soil separation efficiency, it is achieved that the purpose of low-cost separation rare earth, it is simple to follow-up recycling further to rare earth element.
In above-mentioned steps S1, the purpose leached with the solution of phosphoric acid is by P elements in the phosphorus ore containing rare earth and rare earth element dissolution,
And by impurity element and phosphoric acid insoluble matter (rare earth of the xenotime phase in the rare earth of the monazite phase in monazite and/or xenotime)
It is retained in slag the acid leaching residue formed containing rare earth.Thus any can make rare earth element solvable in P elements and phosphorus ore as much as possible
The extract technology condition of dissolution is adapted to the present invention.In the preferred embodiment of the present invention, 10 DEG C～the temperature of 60 DEG C
Under degree, with the solution of phosphoric acid, the phosphorus ore containing monazite and/or xenotime is leached 0.5～8 hour, preferably 2～5 hours, obtain
Above-mentioned leachate and rare earth acid leaching residue.
The solution of above-mentioned employing phosphoric acid leaches in step, and by control reaction temperature in the range of 10 DEG C～60 DEG C, relatively low is anti-
Answer temperature to enable to P elements and solvable rare earth element in the phosphorus ore containing monazite and/or xenotime and dissolve completely as much as possible,
And can effectively suppress the leaching of the impurity element such as ferrum and/or aluminum in phosphorus ore so that and the leaching rate of ferrum element and/or aluminium element < 5%, energy
Enough significantly reduce follow-up remove impurity burden.It is highly preferred that extraction time is 2～5 hours.Select the extraction time of this scope,
Can make P elements and can the complete dissolution of dissolved rare earth, leaching cycle can be shortened again.
In the step of above-mentioned ripening, the concrete time of ripening and temperature can according to the phosphorus ore kind containing rare earth different enter
Row sum-equal matrix.In one preferred embodiment of the present invention, to leachate at 60 DEG C～150 DEG C, at a temperature of preferably 80～120 DEG C
Ripening 0.5～24 hours, preferably 1～8 hour, solid-liquid separation obtained phosphoric acid rare-earth precipitation and one-lime phosphate solution.?
Under high temperature, phosphoric acid rare earth solubility product is little, by using above-mentioned higher temperature, be conducive to making the rare earth ion that is dissolved in leachate with
RE phosphate form precipitates, thus realizes efficiently separating of rare earth element and P elements further.In above-mentioned digestion time scope
In, it is possible to make the rare earth element in leachate precipitate the most thorough, thus more effectively realize rare earth element and P elements point
From, and then in the material containing RE phosphate obtained, content of rare earth is the highest, is more beneficial for the recovery of follow-up rare earth element
Utilize.It is easily understood that one-lime phosphate solution not 100% solution being made up of calcium ion and dihydrogen phosphate ions herein,
But main body is one-lime phosphate solution, contain the solution of the foreign ions such as trace phosphoric acid one hydrogen radical ion, ferrum or aluminum simultaneously.
During the solution of above-mentioned phosphoric acid leaches the phosphorus ore containing monazite and/or xenotime, the solution of phosphoric acid includes phosphorus
Acid, it is possible to be suitably added hydrochloric acid and/or nitric acid according to practical situation.In one preferred embodiment of the invention, above-mentioned phosphoric acid
Solution also comprise hydrochloric acid and/or nitric acid.Hydrochloric acid in mixed acid solution or nitric acid are conducive to the decomposition of apatite, thus improve phosphorus
Leaching rate.And hydrochloric acid or nitric acid can provide hydrion H+, under the conditions of same acids amount, it is possible to decrease the content of phosphate radical, fall
The low leaching of system viscosity, beneficially phosphorus；Meanwhile, chloride ion or the existence of nitrate ion, be conducive to improving calcium ion and exist
The decomposition of the dissolubility in solution, beneficially apatite.In a kind of more preferred embodiment of the present invention, with anion mole
Number meter, the ratio shared by hydrochloric acid and/or nitric acid is less than 30% (not including 0), preferably 2～15%.Hydrochloric acid used in the present invention
Or the content of nitric acid is not limited to above-mentioned scope.But hydrochloric acid or nitric acid according to too high amount will increase phosphoric acid rare earth at this simultaneously
Dissolubility in system, makes rare earth more difficult Precipitation during above-mentioned ripening, causes rare earth cannot be enriched in phosphoric acid dilute
In soil precipitation, cause rare-earth yield on the low side.
In the solution of above-mentioned phosphoric acid, the mass concentration of phosphoric acid can become according to the phosphorus ore leached containing monazite and/or xenotime
The difference divided rationally selects.In one preferred embodiment of the invention, in the solution of above-mentioned phosphoric acid, with P2O5Meter,
The mass concentration of phosphoric acid is 15%～50%, preferably 15%～30%.P in the solution of used phosphoric acid2O5
Mass concentration is not limited to above-mentioned scope, is using P2O5Mass concentration within the above range time, higher acidity is conducive to phosphorus ore
Decomposition, thus improve the yield of phosphorus, but too high phosphorus acid content then exist viscosity height and causes the problems such as mass-transfer efficiency is low.
Before the solution of above-mentioned phosphoric acid leaches the phosphorus ore containing monazite and/or xenotime, the solution of phosphoric acid can be according to containing with phosphorus ore
Solution phosphoric acid concentration and the phosphorus ore composition difference of phosphoric acid carry out rational proportion, so that phosphorus and rare earth element dissolution.The one of the present invention
Planting in preferred embodiment, it is 2～10L:1kg that the solution of phosphoric acid mixes liquid-solid ratio with the phosphorus ore containing monazite and/or xenotime,
It is preferably 3～6L:1kg.By controlling acid consumption, be conducive in the case of reducing acid consumption, make phosphorus and calcium generate solubility
One-lime phosphate Ca (H2PO4)2Entering solution, under the conditions of highly acidity, the dissolubility of phosphoric acid rare earth is big, beneficially apatite middle rare earth leaching
Going out and enter solution, above-mentioned scope proportioning beneficially P elements is fully dissolved out with rare earth element, follow-up ripening, shape
Become phosphoric acid rare-earth precipitation enrichment rare earth.Insoluble monazite and/or xenotime will be left in slag.Thus realize rare earth element and phosphorus
Efficiently separating of element.
Beneficial effects of the present invention is further illustrated below with reference to embodiment.
It should be noted that the detection method of phase structure and content thereof is to be entered by X-ray diffraction (XRD) in the following example
Row detection, and the detection mode of constituent content is to be detected by the method for ICP or XRF to obtain.XRD in the following example
The peak figure of collection of illustrative plates is the most closely similar, referring specifically to the peak figure result of embodiment 3 as shown in Figure 2.
Embodiment 1
With 1000g monazite content as 23wt%, rare earth total content be the phosphorus ore of 16.4wt% be raw material, use mass concentration be
The phosphoric acid solution of 15% is (with P2O5Meter) this rare earth phosphate rock containing monazite is leached, controlling system liquid-solid ratio is 10:1,
At 10 DEG C, react 8h, after filtration, obtain the one-lime phosphate solution containing rare earth and 330g rare earth acid leaching residue.
One-lime phosphate solution containing rare earth is placed at 60 DEG C and carries out ripening 24h, make rare earth element with phosphoric acid rare-earth precipitation
Form come with one-lime phosphate solution separating, thus through solid-liquid separation, obtain one-lime phosphate solution and 13.6g phosphoric acid rare-earth precipitation.
Rare earth acid leaching residue is mixed with phosphoric acid rare-earth precipitation, obtains the material containing RE phosphate.
After testing, in the material containing RE phosphate, the content of amorphous phase is 4.27wt%, and ferrum and aluminum impurity content are (with oxidation
Thing meter) it is 9.2wt%, the first phase structure and the second phase structure weight ratio are 0.045, in terms of oxide, rare earth and ferrum and alumina matter
Weight ratio be 5.04.
Embodiment 2
With 1000g monazite content as 15wt%, rare earth total content be the phosphorus ore of 11.1wt% be raw material, use phosphoric acid and hydrochloric acid
Mixed acid solution leaches, and in mixed acid, the mass concentration of phosphoric acid is 50% (with P2O5Content meter), salt in terms of the molal quantity of anion
It is 2% that acid accounts for the ratio of mixed acid solution, and controlling system liquid-solid ratio is 2:1, reacts 0.5h at 60 DEG C, obtains and contain after filtration
There are one-lime phosphate solution and the 267g acid leaching residue of rare earth.
One-lime phosphate solution containing rare earth is placed at 150 DEG C and carries out ripening 0.5h, make rare earth element with phosphoric acid rare-earth precipitation
Form come with one-lime phosphate solution separating, thus through solid-liquid separation, obtain one-lime phosphate solution and 18.9g phosphoric acid rare-earth precipitation.
Rare earth acid leaching residue is mixed with phosphoric acid rare-earth precipitation, obtains the material containing RE phosphate.
After testing, in the material containing RE phosphate, ferrum and aluminum impurity content (in terms of oxide) as 1.9wt%, amorphous phase
Content be 8.82wt%；First phase structure and the second phase structure weight ratio are 0.097.In terms of oxide, rare earth and ferrum and alumina
The weight ratio of matter is 19.73.
Embodiment 3
With 1000g monazite content as 9.5wt, rare earth total content be the phosphorus ore of 7.4wt% sum be raw material, use phosphoric acid and hydrochloric acid
Mixed acid solution leaches, and in mixed acid, the mass concentration of phosphoric acid is 30% (with P2O5Content meter), in terms of the molal quantity of anion,
It is 25% that hydrochloric acid accounts for the ratio of mixed acid solution, and controlling system liquid-solid ratio is 8:1, reacts 1h at 20 DEG C, obtains and contain after filtration
There are one-lime phosphate solution and the 205g acid leaching residue of rare earth.
One-lime phosphate solution containing rare earth is placed at 80 DEG C and carries out ripening 8h, make rare earth element with phosphoric acid rare-earth precipitation
Form comes with one-lime phosphate solution separating, thus through solid-liquid separation, obtains one-lime phosphate solution and 15.6g phosphoric acid rare-earth precipitation.
Rare earth acid leaching residue is mixed with phosphoric acid rare-earth precipitation, obtains the material containing RE phosphate.
After testing, the X-ray diffraction spectrogram of the material containing RE phosphate of this embodiment is as shown in Figure 2.Can count from Fig. 2
Drawing, this contains in the material of RE phosphate, ferrum and aluminum impurity content (in terms of oxide) as 5.2wt%, amorphous phase
Content is 10.92wt%；First phase structure and the second phase structure weight ratio are 0.123.In terms of oxide, rare earth and ferrum and alumina matter
Weight ratio be 6.23.
Embodiment 4
With 1000g monazite content as 28wt%, rare earth total content be the phosphorus ore of 19.8wt% sum be raw material, use phosphoric acid, hydrochloric acid
Leaching with the mixed acid solution of nitric acid, in mixed acid, the mass concentration of phosphoric acid is 15% (with P2O5Content meter), rubbing with anion
Your number meter, hydrochloric acid and nitric acid accounts for the ratio of mixed acid solution and is 15%, and controlling system liquid-solid ratio is 6:1, reacts at 20 DEG C
4h, obtains the one-lime phosphate solution containing rare earth and 375g acid leaching residue after filtration.
One-lime phosphate solution containing rare earth is placed at 100 DEG C and carries out ripening 1h, make rare earth element with phosphoric acid rare-earth precipitation
Form come with one-lime phosphate solution separating, thus through solid-liquid separation, obtain one-lime phosphate solution and 21.7g phosphoric acid rare-earth precipitation.
Rare earth acid leaching residue is mixed with phosphoric acid rare-earth precipitation, obtains the material containing RE phosphate.
After testing, in the material containing RE phosphate, ferrum and aluminum impurity content (in terms of oxide) as 23wt%, amorphous phase
Content be 5.66wt%；First phase structure and the second phase structure weight ratio are 0.060.In terms of oxide, rare earth and ferrum and alumina
The weight ratio of matter is 2.10.
Embodiment 5
With 1000g xenotime content as 35.0wt, rare earth total content be the phosphorus ore of 24.5wt% sum be raw material, use phosphoric acid and hydrochloric acid
Mixed acid solution leach, in mixed acid, the mass concentration of phosphoric acid is 25% (with P2O5Content meter), in terms of the molal quantity of anion,
It is 20% (in terms of the molal quantity of anion) that hydrochloric acid accounts for the ratio of mixed acid solution, and controlling system liquid-solid ratio is 2:1, at 15 DEG C
Lower reaction 0.5h, obtains the one-lime phosphate solution containing rare earth and 463g acid leaching residue after filtration.
One-lime phosphate solution containing rare earth is placed at 75 DEG C and carries out ripening 2h, make rare earth element with phosphoric acid rare-earth precipitation
Form comes with one-lime phosphate solution separating, thus through solid-liquid separation, obtains one-lime phosphate solution and 19.3g phosphoric acid rare-earth precipitation.
Rare earth acid leaching residue is mixed with phosphoric acid rare-earth precipitation, obtains the material containing RE phosphate.
After testing, in the material containing RE phosphate, ferrum and aluminum impurity content (in terms of oxide) as 23wt%, amorphous phase
Content be 4.07wt%；First phase structure and the second phase structure weight ratio are 0.042.
Embodiment 6
With 1000g xenotime content as 3.5wt%, rare earth total content be the phosphorus ore of 3.3wt% sum be raw material, use phosphoric acid and hydrochloric acid
Mixed acid solution leach, in mixed acid, the mass concentration of phosphoric acid is 25% (with P2O5Content meter), in terms of the molal quantity of anion,
It is 10% (in terms of the molal quantity of anion) that hydrochloric acid accounts for the ratio of mixed acid solution, and controlling system liquid-solid ratio is 3:1, at 15 DEG C
Lower reaction 2h, obtains the one-lime phosphate solution containing rare earth and 143g acid leaching residue after filtration.
One-lime phosphate solution containing rare earth is placed at 120 DEG C and carries out ripening 2h, make rare earth element with phosphoric acid rare-earth precipitation
Form come with one-lime phosphate solution separating, thus through solid-liquid separation, obtain one-lime phosphate solution and 18.6g phosphoric acid rare-earth precipitation.
Rare earth acid leaching residue is mixed with phosphoric acid rare-earth precipitation, obtains the material containing RE phosphate.
After testing, in the material containing RE phosphate, ferrum and aluminum impurity content (in terms of oxide) as 5.8wt%, amorphous phase
Content be 28.66wt%；First phase structure and the second phase structure weight ratio are 0.402.In terms of oxide, rare earth and ferrum and alumina
The weight ratio of matter is 3.46.
Embodiment 7
With 1000g 2.0wt% Han monazite, rare earth total content be the phosphorus ore of 2.3wt% be raw material, use phosphoric acid and the mixing of hydrochloric acid
Acid solution leaches, and in mixed acid, the mass concentration of phosphoric acid is 30% (with P2O5Content meter), in terms of the molal quantity of anion, hydrochloric acid
The ratio accounting for mixed acid solution is 25% (in terms of the molal quantity of anion), controls system liquid-solid ratio 6:1, reacts at 15 DEG C
2h, obtains the one-lime phosphate solution containing rare earth and 124g phosphoric acid rare earth slag after filtration.
One-lime phosphate solution containing rare earth is placed at 120 DEG C and carries out ripening 2h, make rare earth element with phosphoric acid rare-earth precipitation
Form come with one-lime phosphate solution separating, thus through solid-liquid separation, obtain one-lime phosphate solution and 22.5g phosphoric acid rare-earth precipitation.
Rare earth acid leaching residue is mixed with phosphoric acid rare-earth precipitation, obtains the material containing RE phosphate.
After testing, in the material containing RE phosphate, ferrum and aluminum impurity content (in terms of oxide) as 5.6wt%, amorphous phase
Content be 49.56wt%；First phase structure and the second phase structure weight ratio are 0.983.In terms of oxide, rare earth and ferrum and alumina
The weight ratio of matter is 2.77.
Embodiment 8
With 1000g 35wt% Han monazite, rare earth total content be the phosphorus ore of 24.5wt% be raw material, use phosphoric acid and the mixing of hydrochloric acid
Acid solution leaches, and in mixed acid, the mass concentration of phosphoric acid is 25% (with P2O5Content meter), in terms of the molal quantity of anion, hydrochloric acid
The ratio accounting for mixed acid solution is 10% (in terms of the molal quantity of anion), controls system liquid-solid ratio 3:1, reacts at 90 DEG C
10h, obtains one-lime phosphate solution and 483g phosphoric acid rare earth slag after filtration.
After testing, containing in rare earth phosphoric acid slag, ferrum and aluminum impurity content (in terms of oxide) as 31wt%, the content of amorphous phase
For 3.6wt%；First phase structure and the second phase structure weight ratio are 0.037.In terms of oxide, rare earth and ferrum and the weight of alumina matter
Ratio is 2.20.
Embodiment 9
With 1000g 3.5wt% Han monazite, rare earth total content be the phosphorus ore of 3.3wt% be raw material, use phosphoric acid and the mixing of hydrochloric acid
Acid solution leaches, and in mixed acid, the mass concentration of phosphoric acid is 10% (with P2O5Content meter), in terms of the molal quantity of anion, hydrochloric acid
The ratio accounting for mixed acid solution is 30% (in terms of the molal quantity of anion), controls system liquid-solid ratio 3:1, reacts 2h at 5 DEG C,
The one-lime phosphate solution containing rare earth and 123g phosphoric acid rare earth slag is obtained after filtration.
One-lime phosphate solution containing rare earth is placed at 55 DEG C and carries out ripening 2h, make rare earth element with phosphoric acid rare-earth precipitation
Form comes with one-lime phosphate solution separating, thus through solid-liquid separation, obtains one-lime phosphate solution and 2.4g phosphoric acid rare-earth precipitation.
Rare earth acid leaching residue is mixed with phosphoric acid rare-earth precipitation, obtains the material containing RE phosphate.
After testing, in the material containing RE phosphate, ferrum and aluminum impurity content (in terms of oxide) as 1.3wt%, amorphous phase
Content be 3.7wt%；First phase structure and the second phase structure weight ratio are 0.038.In terms of oxide, rare earth and ferrum and alumina matter
Weight ratio be 19.90.
In the various embodiments described above, according to rare earth phosphate rock middle rare earth occurrence patterns and content and by the mistake of rare earth phosphate rock leaching process
Process control, amorphous phase content in RE phosphate is 5～40wt%, is more beneficial in the follow-up material containing RE phosphate
The recovery of rare earth；The impurity content of iron content and/or aluminum in the above-mentioned material containing RE phosphate is controlled in the range of 3～25wt%,
There is content of rare earth the highest, it is simple to rare earth reclaims, by impurity enriched in solid phase, reduce impurity element and enter in leachate,
Reduce follow-up phosphoric acid purification remove impurity burden, and the existence of ferrum aluminum in the material containing RE phosphate, be conducive to returning at follow-up rare earth
Receipts process plays the effect of solid phosphorus, and then is conducive to improving rare-earth yield and realizing the comprehensive utilization of ferrum aluminum.
After obtaining the material containing RE phosphate of the various embodiments described above, can further rare earth element therein be reclaimed
Utilizing, the concrete step recycled is as shown in Figure 1.In the material containing RE phosphate, add iron compound or add simultaneously
Enter the material of calcic and magnesium, and add the mass concentration concentrated sulphuric acid more than 90% and carry out acidizing fired, then with water to product of roasting
Leach, obtain rare earth infusion and water logging slag；The regulation pH value containing rare earth infusion, to 3.8～5, is filtrated to get sulphuric acid dilute
Soil solution and filtering residue, containing ferrum element, P elements and thorium element in this filtering residue；Use acidic phosphorus extractant to rare earth sulfate solution
Finally use and carry out extract and separate, mixed or single rare earth chloride；Or, in rare earth sulfate solution add carbonate or
Oxalate precipitation rare earth, it is thus achieved that rare earth carbonate or rare-earth oxalate；Further rare earth carbonate or rare-earth oxalate are forged
Burn, rare earth oxide can be obtained.
In like manner, the one-lime phosphate solution that obtains in above-described embodiment is sulfuric acid-treated obtains calcium sulfate and solution containing phosphate, and calcium sulfate can
To be used for preparing commercially available gypsum product, and the purified remove impurity of solution containing phosphate obtains phosphoric acid solution and can be further used for the acidleach of phosphorus ore
Step, thus realize recycling of material.
As can be seen from the above description, the application the above embodiments achieve following technique effect: the enforcement of the present invention
Example, by under relatively low reaction temperature, uses the solution of phosphoric acid to leach containing monazite and/or the rare earth phosphate rock of xenotime,
Utilizing the hydrion in phosphoric acid solution to dissolve the phosphorus in phosphorus ore and form one-lime phosphate solution, rare earth element is also dissolved and enters simultaneously
In solution, formed containing rare earth ion, Ca2+And H2PO4 -Leachate；And monazite does not dissolves during acidleach and is retained in slag
In from.Leachate is carried out ripening, is conducive to rare earth element being formed phosphoric acid rare-earth precipitation and realizing rare earth element further
Separate with P elements.Reaction temperature is less to the influence of extraction of P elements during acidleach, and phosphoric acid rare earth at a lower temperature
Dissolubility is relatively large, beneficially the leaching of rare earth element, can effectively suppress the impurity element such as ferrum, aluminum in phosphorus ore under low temperature simultaneously
Leaching so that the leaching rate of ferrum element and aluminium element < 5%, significantly reduce follow-up phosphoric acid purification remove impurity burden.Thus, pass through
Controlling the temperature temperature higher than step of acid dipping of ripening, phosphoric acid rare earth solubility product is little at a relatively high temperature, is conducive to
Make the rare earth element in leachate precipitate with RE phosphate form, realize effective point of rare earth element and P elements further
From.Thus, the material rare earth containing RE phosphate prepared by the above embodiment of the present invention is of high grade, after greatly facilitating
The continuous recycling to rare earth.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for those skilled in the art
For, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, any amendment of being made, etc.
With replacement, improvement etc., should be included within the scope of the present invention.
Claims (10)
1. the material containing RE phosphate, it is characterised in that the described material middle rare earth phosphate containing RE phosphate at least contains
First phase structure and the second phase structure, described first phase structure is amorphous phase, described second phase structure include monazite phase or
/ and xenotime phase.
Material containing RE phosphate the most according to claim 1, it is characterised in that in terms of weight content, described amorphous phase
Content in described RE phosphate is more than 1%, preferably 5～40%.
Material containing RE phosphate the most according to claim 1, it is characterised in that institute in the described material containing RE phosphate
The weight ratio stating the first phase structure and described second phase structure is 1:1～20.
Material containing RE phosphate the most according to claim 1, it is characterised in that in the described material containing RE phosphate
Also including the impurity of iron content and/or aluminum, in terms of oxide, ferrum and/or aluminum content are 1～50wt%, preferably 3～25wt%.
Material containing RE phosphate the most according to claim 1, it is characterised in that at the described material containing RE phosphate
In, in terms of oxide, rare earth is 2～20:1 with the weight ratio of ferrum and/or aluminum.
Material containing RE phosphate the most according to any one of claim 1 to 5, it is characterised in that described containing rare earth phosphorus
The material of hydrochlorate is isolated from the phosphorus ore containing monazite and/or xenotime, described from containing monazite and/or xenotime
The method of the material containing RE phosphate in phosphorus ore described in isolated includes:
Step S1, leaches the described phosphorus ore containing monazite and/or xenotime with the solution of phosphoric acid, obtains leachate
With rare earth acid leaching residue；Described leachate contains rare earth ion, calcium ion and dihydrogen phosphate ions；
Step S2, carries out ripening to described leachate, obtains phosphoric acid rare-earth precipitation and one-lime phosphate is molten through solid-liquid separation
Liquid；And
Step S3, mixes described rare earth acid leaching residue with described phosphoric acid rare-earth precipitation, obtains the described thing containing RE phosphate
Matter；
The reaction temperature of described step S2 is higher than the reaction temperature of described step S1.
Material containing RE phosphate the most according to claim 6, it is characterised in that described step S1 includes:
At a temperature of 10 DEG C～60 DEG C, with the solution of described phosphoric acid, the described phosphorus ore containing monazite and/or xenotime is soaked
Go out 0.5～8 hour, preferably 1～4 hour, obtain described leachate and described rare earth acid leaching residue.
Material containing RE phosphate the most according to claim 6, it is characterised in that described step S2 includes:
To described leachate at 60 DEG C～150 DEG C, ripening 0.5～24 hours at a temperature of preferably 80～120 DEG C,
Being preferably 1～8 hour, solid-liquid separation obtains described phosphoric acid rare-earth precipitation and described one-lime phosphate solution.
Material containing RE phosphate the most according to claim 7, it is characterised in that also comprise in the solution of described phosphoric acid
Hydrochloric acid and/or nitric acid；Preferably, in terms of the molal quantity of anion, in the solution of described phosphoric acid shared by hydrochloric acid and/or nitric acid
Ratio less than 30%, more preferably 2～15%.
10. according to the material containing RE phosphate according to any one of claim 7 to 9, it is characterised in that with P2O5Meter, institute
Stating the mass concentration of phosphoric acid in the solution of phosphoric acid is 15%～50%, preferably 15%～30%；The solution of described phosphoric acid
The step mixed according to the ratio that liquid-solid ratio is 2～10L:1kg with the described phosphorus ore containing monazite and/or xenotime, preferably
Described liquid-solid ratio is 3～6L:1kg.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510347681.3A CN106319248B (en) | 2015-06-19 | 2015-06-19 | Substance containing RE phosphate |
| AU2016279392A AU2016279392B2 (en) | 2015-06-19 | 2016-06-15 | Method for recovering phosphorus and rare earth from rare earth-containing phosphate ore, and substance containing rare earth phosphate |
| MYPI2017704874A MY173056A (en) | 2015-06-19 | 2016-06-15 | A method for recovering phosphorus and rare earth from rare earth-containing phosphorite and substance containing rare earth phosphate |
| PCT/CN2016/085827 WO2016202257A1 (en) | 2015-06-19 | 2016-06-15 | Method for recovering phosphorus and rare earth from rare earth-containing phosphate ore, and substance containing rare earth phosphate |
| ZA2018/00118A ZA201800118B (en) | 2015-06-19 | 2018-01-08 | A method for recovering phosphorus and rare earth from rare earth-containing phosphorite and substance containing rare earth phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510347681.3A CN106319248B (en) | 2015-06-19 | 2015-06-19 | Substance containing RE phosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106319248A true CN106319248A (en) | 2017-01-11 |
| CN106319248B CN106319248B (en) | 2019-05-07 |
Family
ID=57729038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510347681.3A Active CN106319248B (en) | 2015-06-19 | 2015-06-19 | Substance containing RE phosphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106319248B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102312089A (en) * | 2010-07-01 | 2012-01-11 | 北京矿冶研究总院 | Method for recovering rare earth from rare earth-containing phosphorite |
| CN102530904A (en) * | 2011-12-17 | 2012-07-04 | 赣州虔东稀土集团股份有限公司 | Preparation method of crystalline high-purity rare earth phosphate with controllable granularity |
| CN105331812A (en) * | 2014-07-31 | 2016-02-17 | 有研稀土新材料股份有限公司 | Method for comprehensively recycling phosphorus and rare earth from rare earth phosphorite containing monazite |
-
2015
- 2015-06-19 CN CN201510347681.3A patent/CN106319248B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102312089A (en) * | 2010-07-01 | 2012-01-11 | 北京矿冶研究总院 | Method for recovering rare earth from rare earth-containing phosphorite |
| CN102530904A (en) * | 2011-12-17 | 2012-07-04 | 赣州虔东稀土集团股份有限公司 | Preparation method of crystalline high-purity rare earth phosphate with controllable granularity |
| CN105331812A (en) * | 2014-07-31 | 2016-02-17 | 有研稀土新材料股份有限公司 | Method for comprehensively recycling phosphorus and rare earth from rare earth phosphorite containing monazite |
Non-Patent Citations (1)
| Title |
|---|
| 王良士等: "湿法磷酸生产过程中控制稀土走向的研究", 《中国稀土学报》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106319248B (en) | 2019-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105886798B (en) | The method that phosphorus and rare earth are recycled from containing rare earth phosphate rock | |
| JP5894262B2 (en) | Method for recovering rare earth elements from various ores | |
| AU2008286599B2 (en) | A metallurgical process for iron-rich monazite rare earth ore or concentrate | |
| US20150104361A1 (en) | Processes for recovering rare earth elements and rare metals | |
| JP2014508863A (en) | Method for recovering rare earth elements from aluminum-containing materials | |
| CN106319247B (en) | The method of phosphorus and rare earth is recycled from containing rare earth phosphate rock | |
| CN109518005A (en) | A kind of production method of battery grade cobalt sulfate crystal | |
| WO2009021389A1 (en) | A PROCESS OF SMELTING MONAZITE RARE EARTH ORE RICH IN Fe | |
| CN105483383A (en) | Process for recovering aluminium, iron and scandium from Bayer-process red mud powder | |
| Davris et al. | Current and alternative routes in the production of rare earth elements | |
| CN105331812B (en) | The method of synthetical recovery phosphorus and rare earth from phosphorus ore containing mengite rare-earth | |
| CN104726724A (en) | Method for extracting scandium from nickel laterite ores | |
| CN101831542A (en) | Method for extracting metallic elements of ferrum, magnesium and calcium from molybdenum milltailings | |
| WO2016202257A1 (en) | Method for recovering phosphorus and rare earth from rare earth-containing phosphate ore, and substance containing rare earth phosphate | |
| CN101760652B (en) | Technological method for treating refractory complex molybdenum ore by combined dressing and smelting process | |
| CN105441674B (en) | From the method for synthetical recovery phosphorus and rare earth in phosphorus ore containing monazite | |
| CN104862503B (en) | The method that scandium is extracted from lateritic nickel ore | |
| CN105002366B (en) | A kind of method of the recovering rare earth from neutralization slag caused by neodymium iron boron waste material recovering rare earth process | |
| CA2868363A1 (en) | Processes for recovering rare earth elements and rare metals | |
| AU2012395739A1 (en) | Processing of rare earth and uranium containing ores and concentrates | |
| CN107012342A (en) | A kind of method for extracting low-grade ion type rareearth raw ore rare earth elements | |
| CN106319248A (en) | Substance containing rare earth phosphate | |
| Xue et al. | Effect of K 2 SO 4 on solvent extraction of vanadium with D2EHPA/TBP. | |
| CN104975192A (en) | Method for extracting scandium from scandium-containing material | |
| CN109777972A (en) | A method of concentrated sulfuric acid activation, which is leached, from gangue extracts scandium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |