CN106319248B - Substance containing RE phosphate - Google Patents
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- CN106319248B CN106319248B CN201510347681.3A CN201510347681A CN106319248B CN 106319248 B CN106319248 B CN 106319248B CN 201510347681 A CN201510347681 A CN 201510347681A CN 106319248 B CN106319248 B CN 106319248B
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Abstract
The present invention provides a kind of substances containing RE phosphate.RE phosphate at least contains the first phase structure and the second phase structure in the substance containing RE phosphate, and the first phase structure is amorphous phase, and the second phase structure includes monazite phase or/and xenotime phase.At least contain the rare earth of above two phase structure, rare-earth enrichment degree in the substance of RE phosphate is high, and grade is high, convenient for the subsequent comprehensive reutilization to rare earth so that this contains.
Description
Technical field
The present invention relates to rare earth recovery fields, in particular to a kind of substance containing RE phosphate.
Background technique
Rare-earth mineral is in nature often with the mineral intergrowths such as barite, calcite, apatite, silicate ore one
It rises.Different due to mineral are at mine, occurrence status and content of the rare earth element in mineral are also different.Currently exploited
In rare-earth mineral, the grade of rare earth oxide is a few percent.In order to meet the needs of rare earth metallurgy production, in smelting
Before first rare-earth mineral must be made to be enriched with rare earth and other ore separations through beneficiation method.Rare earth essence after beneficiation enrichment
The content of mine middle rare earth is usually 50%~70%.
Rare-earth mineral mainly has bastnaesite, monazite, xenotime and ion adsorption type rare earth ore etc..Currently, recycling is only
Occupy method there are mainly two types of the mode of rare earth in stone: (1) alkaline process resolution process monazite (is suitable for high-grade monazite
Mine), monazite is with liquid alkaline reaction process, and rare earth generates hydroxide not soluble in water, and phosphorus is changed into tertiary sodium phosphate, rare earth hydrogen
Oxide obtains mixed chlorinated rare earth using the excellent molten, removal of impurities of hydrochloric acid.If the impurity contents such as iron, silicon are high in concentrate, silicon is easily formed
The colloidal materials such as sour sodium, iron hydroxide, precipitating is separated by filtration process and is difficult to carry out, therefore the technique is unable to operate normally.(2) dense
Sulfuric acid roasting method decomposes solitary stone ore, monazite concentrate and the concentrated sulfuric acid is blended in 200-230 DEG C of decomposition, concentrated sulfuric acid dosage is essence
1.7-2 times of mine weight uses the water extraction of 7-10 times of concentrate weight, rare earth about 50g/L in leachate after decomposition product is cooling
(REO), 25g/L P2O5, 2.5g/L Fe2O3, acidity 2.5mol/L.The immersion liquid acidity is high, and foreign matter of phosphor, thorium are high, using sulfuric acid
Then sodium double salt precipitation rare earth and thorium switch to hydroxide by alkali, then use the preferential leaching rare earth of acid, extracting and separating rear earth,
Thorium.This method complex process, solid-liquor separation step is more, and technique is discontinuous, and rare earth yield is low；In addition, soda acid cross-reference, changes
Work consumption of raw materials is at high cost, and to enter wastewater treatment difficulty big for phosphorus, and radioactive element thorium, which is dispersed in slag and waste water, to be difficult to effectively
Recycling.
Phosphorus ore is the primary raw material for producing phosphorus chemical product, and world phosphate resource reserve is big, normal association trace rare-earth.Due to
The ionic radius (0.848~0.106nm) and Ca of rare earth2+(0.106nm) very close to, rare earth in a manner of isomorph preservation in phosphorus
In mine, with the presence of the Independent Minerals phase structure such as apatite phase, hydroxyapatite, while rare earth may also be adsorbed in the form of ionic state
In phosphorus ore.Currently, the method for rare earth includes following technique in recycling phosphorus ore: (1) the wet process phosphorus of hydrochloric acid, nitrate method processing phosphorus ore
Sour technique, 95% or more rare earth enter in solution, then are recycled using the modes such as solvent extraction, ion exchange, precipitating, crystallization dilute
Soil；(2) Wet Processes of Phosphoric Acid of sulfuric acid process processing phosphorus ore, rare earth respectively enter in solution and ardealite, then use sulfuric acid to leach
Ardealite makes rare earth enter solution, and the rare earth in solution can be used the modes such as solvent extraction, ion exchange, precipitating, crystallization and recycle
Rare earth.(3) phosphoric acid handles phosphorus ore technique, and the phosphorus concentrate containing rare earth is mixed with phosphoric acid solution and is reacted, control technique is passed through
Condition precipitates rare earth in phosphorus ore with fluoride form, and 85% or more rare earth enters in slag, then molten using hydrochloric acid, nitric acid or sulfuric acid
Rare earth in solution recycling slag, but rare earth grade is very low in slag, about 1%, foreign matter of phosphor, calcium, aluminium, silicon equal size are high, and are fluorinated
Rare earth is difficult to use acid dissolution, and acid consumption is high, and the quantity of slag is big, and rare earth yield is low；In addition, being removed into 15% rare earth in leachate
Easily enter in gypsum tailings during calcium and is difficult to recycle.
Phosphorus ore containing mengite rare-earth is one kind than mineral difficult to deal with, and this phosphorus ore containing mengite rare-earth contains simultaneously
Various ingredients, including monazite, rare earth and phosphorus ore etc..Since monazite and phosphorus ore belong to phosphate mineral, the two mineral
It learns property to be closer to, monazite and the embedding cloth of phosphorus ore are in close relations in the mineral of its symbiosis.Recycle rare earth in this composite ore
When element and P elements, since substance each in composite ore package is inlayed, dissociation difficulty is larger, and physical upgrading is difficult to realize to ore
Effective sorting.Especially since decomposing monazite needs relatively harsh condition, higher temperature and pH value etc. are needed,
When containing the phosphorus ore of monazite using sulfuric acid process wet-treating in the prior art, monazite can not often decomposed completely, not
It is able to achieve it and efficiently separates utilization.Therefore, how to separate containing the phosphorus and rare earth in rare earth phosphate rock, especially phosphorus containing mengite rare-earth
This kind of quality of mine is lower, the rare earth in the more miscellaneous composite ore of mineralogical composition, have become one of research staff it is urgently to be resolved
Technical problem.
Summary of the invention
The main purpose of the present invention is to provide a kind of substances containing RE phosphate, to provide one kind from rare earth phosphate rock
The higher RE phosphate substance of isolated content of rare earth.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of substance containing RE phosphate, is somebody's turn to do
RE phosphate in substance containing RE phosphate at least contains the first phase structure and the second phase structure, and the first phase structure is nothing
Shape phase, and the second phase structure includes monazite phase or/and xenotime phase.
Further, in terms of weight content, content of the amorphous phase in RE phosphate be greater than 1%, preferably 5~
40%.
Further, the weight ratio of the first phase structure and the second phase structure is 1:1~20 in the substance containing RE phosphate.
Further, further include the impurity of iron content and/or aluminium in the substance containing RE phosphate, in terms of oxide, iron and/
Or aluminium content is 1~50wt%, preferably 3~25wt%.
Further, in the substance containing RE phosphate, in terms of oxide, rare earth is 2 with the weight ratio of iron and/or aluminium
~20:1.
Further, the substance containing RE phosphate is isolated from the phosphorus ore containing monazite and/or xenotime, from
The method of the isolated substance containing RE phosphate includes: step S1 in phosphorus ore containing monazite and/or xenotime, and use is phosphorous
The solution of acid leaches the phosphorus ore containing monazite and/or xenotime, obtains leachate and rare earth acid leaching residue；Leachate contains
Rare earth ion, calcium ion and dihydrogen phosphate ions；Step S2 carries out ripening to leachate, and separation of solid and liquid obtains 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 phosphorus containing rare earth
The substance of hydrochlorate；The reaction temperature of step S2 is higher than the reaction temperature of step S1.
Further, step S1 include: 10 DEG C~60 DEG C at a temperature of, with the solution of phosphoric acid to containing monazite and/
Or the phosphorus ore of xenotime leaches 0.5~8 hour, preferably 1~4 hour, obtains leachate and rare earth acid leaching residue.
Further, step S2 includes: old at a temperature of 60 DEG C~150 DEG C, preferably 80~120 DEG C to the first solution
Change processing 0.5~24 hour, preferably 1~8 hour, separation of solid and liquid obtained phosphoric acid rare-earth precipitation and one-lime phosphate solution.
It further, also include hydrochloric acid and/or nitric acid in the solution of phosphoric acid；Preferably, in terms of the molal quantity of anion,
Ratio shared by hydrochloric acid and/or nitric acid is less than 30% in the solution of phosphoric acid, and more preferably 2~15%.
Further, with P2O5It counts, the mass concentration of phosphoric acid is 15%~50%, preferably 15% in the solution of phosphoric acid
~30%.
Further, before step S1, method further includes by the solution of phosphoric acid and containing monazite and/or xenotime
The step of phosphorus ore is mixed according to the ratio that liquid-solid ratio is 2~10L:1kg, preferably liquid-solid ratio are 3~6L:1kg.
It applies the technical scheme of the present invention, is studied in detail by the separation method of the phosphorus ore to alloy containing mixed rare earth,
And a kind of therefrom isolated higher substance containing RE phosphate of rare earth grade, the RE phosphate in the substance is at least
Contain the 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 substance containing RE phosphate is rich in the rare earth of a variety of phase structures, and rare-earth enrichment degree is high, grade
Height, convenient for carrying out comprehensive reutilization to rare earth.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 shows a kind of preferred embodiment according to the present invention and separates from the phosphorus ore containing monazite and/or xenotime
Obtain the flow diagram containing RE phosphate；And
Fig. 2 shows the X-ray diffraction spectrograms for the substance containing RE phosphate that embodiment according to the present invention 3 obtains.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
In the following description, the molecular formula of monazite (the entitled Monazite of English) is (Ln, Th) PO4, Ln refers in formula
At least one of rare earth element in addition to promethium.
As pointed by background technique, rare earth phosphate rock is as containing apatite, monazite and xenotime multi mineral
Composite ore using existing separation method when being separated, it is difficult to efficiently separate rare earth element and P elements in this kind of composite ore
Obtain the higher substance of content of rare earth.In order to improve drawbacks described above in the prior art, inventor mixes above-mentioned relatively special
The separation method for closing mine is studied in detail, and a kind of therefrom isolated phosphoric acid containing rare earth that content of rare earth is relatively high
The substance of salt.What the present invention exactly proposed on this basis.
In a kind of typical embodiment of the invention, a kind of substance containing RE phosphate is provided, in the substance
RE phosphate at least contain the first phase structure and the second phase structure, wherein the first phase structure be amorphous phase, the second phase knot
Structure includes monazite phase or/and xenotime phase.The above-mentioned substance containing RE phosphate is rich in the rare earth of a variety of phase structures, and rare earth is rich
Intensity is high, and grade is high, convenient for carrying out comprehensive reutilization to rare earth.
Amorphous phase is that phosphoric acid rare-earth precipitation is formed by phase in the substance containing RE phosphate comprising above-mentioned phase structure
The control of structure, the height of content and rare earth occurrence patterns in rare earth phosphate rock and content and rare earth phosphate rock in leaching step
Condition is related.But the height that the rare earth of the height of its content and the obtained substance containing RE phosphate is sampled is closely related,
And determining the comprehensive reutilization rate of rare earth, the substance containing RE phosphate with above-mentioned a variety of phase structures has had phase
It is in a preferred embodiment of the invention, above-mentioned to contain RE phosphate in order to further increase its grade to higher grade
Substance in, content of the amorphous phase in RE phosphate be greater than 1wt%, preferably 5~40wt%.Amorphous phase content is big
When 1wt%, be conducive to the recycling of rare earth in the subsequent substance containing RE phosphate.And amorphous phase content is 5~40wt%
When, rare earth grade is relatively higher, is more advantageous to the comprehensive reutilization of rare earth element.
Phosphoric acid containing rare earth in above preferred embodiment, when amorphous phase accounts for the content of RE phosphate within the above range
The substance rare earth grade of salt be it is relatively high, in order to further increase the utility value of the substance, of the invention another
In preferred embodiment, in the above-mentioned substance containing RE phosphate, the weight ratio of the first phase structure and the second phase structure be 1:1~
20.The weight ratio of the first phase structure and the second phase structure in the above-mentioned substance containing RE phosphate is controlled in above range
It is interior, so that the substance for containing RE phosphate is provided simultaneously with above two phase structure, thus the advantage high with rare earth grade.Contain
The substance rare earth grade of RE phosphate is high, convenient for carrying out comprehensive reutilization, and rare-earth yield with higher to rare earth.
In the above-mentioned substance containing RE phosphate, due to association iron and/or aluminium mineral in rare earth phosphate rock, thus separation process
In still inevitably contain the impurity of above-mentioned element species, thus further comprise the impurity of iron content and/or aluminium.This partial impurities
The height of content it is related with the content and acidleach process control of the iron of rare earth phosphate rock institute association and/or aluminium.In the present invention one
In kind preferred embodiment, in terms of oxide, content of the impurity of above-mentioned iron content and/or aluminium in the substance containing RE phosphate
For 1~50wt%, preferably 3~25wt%.By the impurity content control of iron content in the above-mentioned substance containing RE phosphate and/or aluminium
System has content of rare earth relatively high within the scope of 1~50wt%, is convenient for rare earth recovery；By impurity enriched in solid phase, reduce
Impurity element enters in leachate, reduce subsequent phosphoric acid purification removal of impurities burden, and iron aluminium is deposited in the substance containing RE phosphate
Be conducive to play the role of solid phosphorus in subsequent rare earth recovery process, and then be conducive to improve rare-earth yield and realize iron aluminium
Comprehensive utilization；And the content of the impurity of iron content and/or aluminium in the above-mentioned substance containing RE phosphate is controlled in 3~25wt%
In the range of, with the high advantage of content of rare earth, the substance rare earth grade containing RE phosphate with above-mentioned impurity content is high,
Convenient for rare earth recovery, and realize the comprehensive utilization of impurity iron aluminium.
Equally, control impurity content enable within the above range the substance of the invention containing RE phosphate have compared with
High rare earth grade, in order to further increase rare earth grade, in another preferred embodiment of the present invention, above-mentioned phosphorus containing rare earth
In the substance of hydrochlorate, in terms of oxide, rare earth is 2~20:1 with the weight ratio of iron and/or aluminium.By rare earth and iron and/or aluminium
Weight ratio controls within the above range, can make the content of rare earth with higher of the substance containing RE phosphate of the invention.Have
Conducive to subsequent sulfuric acid baking processing recovering rare earth technique processing, it can be achieved that iron bauxite resource comprehensive utilization, and by impurity
Iron aluminium is enriched in solid phase, is reduced impurity element and is entered in leachate, and subsequent phosphoric acid purification removal of impurities burden is reduced.
It, can be from containing monazite and/or xenotime according to the difference in rare earth source in the above-mentioned substance containing RE phosphate
Phosphorus ore in it is isolated.In a preferred embodiment of the invention, contain from the phosphate mineral containing monazite is isolated
The method of the substance of RE phosphate includes: step S1, with the solution of phosphoric acid to the phosphorus ore containing monazite and/or xenotime into
Row leaches, and obtains the leachate and rare earth acid leaching residue containing rare earth ion, calcium ion and dihydrogen phosphate ions；Step S2, to leaching
Liquid carries out ripening out, and separation of solid and liquid obtains phosphoric acid rare-earth precipitation and one-lime phosphate solution；And step S3, by rare earth acidleach
Slag is mixed with phosphoric acid rare-earth precipitation, obtains the substance containing RE phosphate；The reaction temperature of step S2 is higher than the reaction of step S1
Temperature.
It is above-mentioned from phosphorus ore the step of the isolated substance containing RE phosphate, in relatively low reaction temperature
Under, the rare earth phosphate rock containing monazite and/or xenotime is leached by using the solution of phosphoric acid, utilizes the hydrogen in phosphorous acid solution
Phosphorus in ion-solubility phosphorus ore forms one-lime phosphate solution, while rare earth element is also dissolved and enters in solution, is formed containing dilute
Native ion, Ca2+And H2PO4 -Leachate；And monazite during acidleach do not dissolve be retained in slag, realize phosphorus with it is solitary
The separation of stone.Ripening is carried out to leachate, is conducive to that rare earth element is formed phosphoric acid rare-earth precipitation and further realized dilute
The separation of earth elements and P elements.Reaction temperature is smaller to the influence of extraction of P elements during acidleach, and at a lower temperature
Phosphoric acid rare earth solubility is relatively large, is conducive to the leaching of rare earth element, while can effectively inhibit iron in phosphorus ore, aluminium etc. under low temperature
The leaching of impurity element, so that leaching rate < 5% of ferro element and aluminium element, significantly reduces subsequent phosphoric acid purification removal of impurities burden.
Thus, the temperature by controlling ripening is higher than the temperature of step of acid dipping, at a relatively high temperature phosphoric acid rare earth solubility
Product it is small, be conducive to make the rare earth element in leachate to precipitate in the form of RE phosphate, further realize rare earth element with
P elements efficiently separate.From the phosphorus ore containing rare earth to phosphoric acid rare-earth precipitation, rare-earth enrichment multiple be up to tens times even it is up to a hundred
Times, for rare earth grade up to 45% or more, even up to 55% or more, rare-earth yield reaches 80% or more in phosphoric acid rare-earth precipitation,
Even up to 90% or more, Rare Earth Separation efficiency is improved, the purpose of low-cost separation rare earth is realized, convenient for subsequent to rare earth member
It is plain further to recycle.
It is that will contain P elements and rare earth member in the phosphorus ore of rare earth with the purpose that the solution of phosphoric acid leaches in above-mentioned steps S1
Element dissolution, and by impurity element and the phosphoric acid insoluble matter (xenotime in the rare earth and/or xenotime of the monazite phase in monazite
The rare earth of phase) it is retained in acid leaching residue of the formation containing rare earth in slag.It is thus any to make soluble rare earth in P elements and phosphorus ore
The extract technology condition that element dissolves out as much as possible is adapted to the present invention.In the preferred embodiment of the present invention, exist
At a temperature of 10 DEG C~60 DEG C, the phosphorus ore containing monazite and/or xenotime is leached 0.5~8 hour with the solution of phosphoric acid, it is excellent
It selects 2~5 hours, obtains above-mentioned leachate and rare earth acid leaching residue.
In the above-mentioned solution leaching step using phosphoric acid, through control reaction temperature within the scope of 10 DEG C~60 DEG C, compared with
Low reaction temperature enables in the phosphorus ore containing monazite and/or xenotime P elements and soluble rare earth element as much as possible
Dissolution completely, and can effectively inhibit the leaching of the impurity elements such as iron and/or aluminium in phosphorus ore, so that ferro element and/or aluminium element
Leaching rate < 5% can significantly reduce subsequent removal of impurities burden.It is highly preferred that extraction time is 2~5 hours.Select the model
The extraction time enclosed, can make P elements and can dissolved rare earth dissolve out completely and leaching cycle.
In the step of above-mentioned ripening, the specific time of ripening and temperature can be according to the phosphorus ore types containing rare earth
Difference is adjusted.In a kind of preferred embodiment of the present invention, to leachate at 60 DEG C~150 DEG C, preferably 80~120 DEG C
At a temperature of ripening 0.5~24 hour, preferably 1~8 hour, separation of solid and liquid obtains phosphoric acid rare-earth precipitation and one-lime phosphate is molten
Liquid.Phosphoric acid rare earth solubility product is small at high temperature, by using above-mentioned higher temperature, is conducive to make to be dissolved in the rare earth in leachate
Ion is precipitated in the form of RE phosphate, to further realize efficiently separating for rare earth element and P elements.In above-mentioned ageing
In time range, the rare earth element in leachate is enabled to precipitate more thorough, thus more effectively realize rare earth element with
The separation of P elements, in the substance obtained from containing RE phosphate, content of rare earth is relatively higher, is more advantageous to subsequent rare earth
The recycling of element.It is easily understood that one-lime phosphate solution herein be not 100% by calcium ion and dihydrogen phosphate from
Molecular solution, but main body is one-lime phosphate solution, simultaneously containing the impurity such as micro one hydrogen radical ion of phosphoric acid, iron or aluminium from
The solution of son.
During the solution of above-mentioned phosphoric acid leaches the phosphorus ore containing monazite and/or xenotime, the solution of phosphoric acid
In include phosphoric acid, hydrochloric acid and/or nitric acid can also be suitably added according to the actual situation.In one preferred embodiment of the invention,
The solution of above-mentioned phosphoric acid also includes hydrochloric acid and/or nitric acid.Hydrochloric acid or nitric acid in mixed acid solution are conducive to point of apatite
Solution, to improve the leaching rate of phosphorus.And hydrochloric acid or nitric acid can provide hydrogen ion H+, under the conditions of same acids amount, phosphorus can be reduced
The content of acid group, reduces system viscosity, is conducive to the leaching of phosphorus；Meanwhile the presence of chloride ion or nitrate ion, be conducive to
The solubility of calcium ion in the solution is improved, the decomposition of apatite is conducive to.In a kind of more preferred embodiment of the invention, with
The molal quantity meter of anion, ratio shared by hydrochloric acid and/or nitric acid is not less than 30% (including 0), and preferably 2~15%.The present invention
Used in hydrochloric acid or the content of nitric acid be not limited to above range.But the hydrochloric acid or nitric acid according to too high amount will simultaneously
Increase solubility of the phosphoric acid rare earth in the system, makes rare earth more difficult Precipitation during above-mentioned ripening, cause dilute
Soil can not be enriched in phosphoric acid rare-earth precipitation, cause rare-earth yield relatively low.
In the solution of above-mentioned phosphoric acid, the mass concentration of phosphoric acid can contain monazite and/or xenotime according to leaching
The difference of phosphorus ore ingredient reasonably selected.In one preferred embodiment of the invention, in the solution of above-mentioned phosphoric acid, with
P2O5Meter, the mass concentration of phosphoric acid are 15%~50%, preferably 15%~30%.Used phosphoric acid is molten in the present invention
P in liquid2O5Mass concentration is not limited to above range, is using P2O5Mass concentration within the above range when, higher acidity has
Conducive to the decomposition of phosphorus ore, to improve the yield of phosphorus, but then there is viscosity height and cause mass-transfer efficiency low etc. in excessively high phosphorus acid content
Problem.
Before the solution of above-mentioned phosphoric acid leaches the phosphorus ore containing monazite and/or xenotime, the solution and phosphorus ore of phosphoric acid
Rational proportion can be carried out according to the solution phosphoric acid concentration and phosphorus ore ingredient difference of phosphoric acid, so that phosphorus and rare earth element dissolve out.
In a preferred embodiment of the present invention, it is 2 that the solution of phosphoric acid, which mixes liquid-solid ratio with the phosphorus ore containing monazite and/or xenotime,
~10L:1kg, preferably 3~6L:1kg.By controlling sour dosage, be conducive to make phosphorus and calcium in the case where reducing sour dosage
Generate one calcium Ca (H of soluble phosphoric acid2PO4)2Into solution, the solubility of phosphoric acid rare earth is big under the conditions of highly acidity, is conducive to phosphorus ash
Rare earth is leached into solution in stone, and above range proportion is conducive to being fully dissolved out for P elements and rare earth element, is conducive to subsequent
Ripening forms phosphoric acid rare-earth precipitation and is enriched with rare earth.Insoluble monazite and/or xenotime will be left in slag.To real
Existing rare earth element and P elements efficiently separate.
Beneficial effects of the present invention are further illustrated below with reference to embodiment.
It should be noted that the detection method of phase structure and its content is by X-ray diffraction (XRD) in the following example
It is detected, and the detection mode of constituent content is obtained by the method detection of ICP or XRF.XRD diagram in the following example
The peak figure of spectrum is all closely similar, referring specifically to the peak figure result of embodiment 3 as shown in Figure 2.
Embodiment 1
It is 23wt% with 1000g monazite content, the phosphorus ore that rare earth total content is 16.4wt% is raw material, dense using quality
The phosphoric acid solution that degree is 15% is (with P2O5Meter) rare earth phosphate rock containing monazite is leached, control system liquid-solid ratio is 10:
1,8h is reacted at 10 DEG C, and the one-lime phosphate solution containing rare earth and 330g rare earth acid leaching residue are obtained after filtering.
One-lime phosphate solution containing rare earth is placed at 60 DEG C and carries out ripening for 24 hours, keeps rare earth element dilute with phosphoric acid
The form of soil precipitating is separated with one-lime phosphate solution, thus is separated by solid-liquid separation, and one-lime phosphate solution and 13.6g phosphoric acid are obtained
Rare-earth precipitation.
Rare earth acid leaching residue is mixed with phosphoric acid rare-earth precipitation, obtains the substance containing RE phosphate.
Through detecting, in the substance containing RE phosphate, the content of amorphous phase is 4.27wt%, iron and aluminium impurity content
(in terms of oxide) is 9.2wt%, and the first phase structure and the second phase structure weight ratio are 0.045, in terms of oxide, rare earth and iron
Weight ratio with aluminium impurity is 5.04.
Embodiment 2
Be 15wt% with 1000g monazite content, the phosphorus ore that rare earth total content is 11.1wt% is raw material, using phosphoric acid and
The mixed acid solution of hydrochloric acid leaches, and the mass concentration of phosphoric acid is 50% (with P in mixed acid2O5Content meter), with mole of anion
The ratio that number meter hydrochloric acid accounts for mixed acid solution is 2%, and control system liquid-solid ratio is 2:1, and 0.5h is reacted at 60 DEG C, is obtained after filtering
Obtain one-lime phosphate solution and 267g acid leaching residue containing rare earth.
Progress ripening 0.5h at 150 DEG C is placed in the one-lime phosphate solution containing rare earth, makes rare earth element with phosphoric acid
The form of rare-earth precipitation is separated with one-lime phosphate solution, thus is separated by solid-liquid separation, and one-lime phosphate solution and 18.9g phosphorus are obtained
Acid rare earth precipitating.
Rare earth acid leaching residue is mixed with phosphoric acid rare-earth precipitation, obtains the substance containing RE phosphate.
Through detecting, in the substance containing RE phosphate, iron and aluminium impurity content (in terms of oxide) are 1.9wt%, without fixed
The content of shape phase is 8.82wt%；First phase structure and the second phase structure weight ratio are 0.097.In terms of oxide, rare earth and iron
Weight ratio with aluminium impurity is 19.73.
Embodiment 3
Be 9.5wt with 1000g monazite content, rare earth total content is that the phosphorus ore of 7.4wt% sum is raw material, using phosphoric acid and
The mixed acid solution of hydrochloric acid leaches, and the mass concentration of phosphoric acid is 30% (with P in mixed acid2O5Content meter), with mole of anion
Number meter, the ratio that hydrochloric acid accounts for mixed acid solution is 25%, and control system liquid-solid ratio is 8:1, and 1h is reacted at 20 DEG C, is obtained after filtering
Obtain one-lime phosphate solution and 205g acid leaching residue containing rare earth.
Progress ripening 8h at 80 DEG C is placed in the one-lime phosphate solution containing rare earth, makes rare earth element with phosphoric acid rare earth
The form of precipitating is separated with one-lime phosphate solution, thus is separated by solid-liquid separation, and obtains one-lime phosphate solution and 15.6g phosphoric acid is dilute
Soil precipitating.
Rare earth acid leaching residue is mixed with phosphoric acid rare-earth precipitation, obtains the substance containing RE phosphate.
Through detecting, the X-ray diffraction spectrogram of the substance containing RE phosphate of the embodiment is as shown in Figure 2.It can be with from Fig. 2
It is calculated, this contains in the substance of RE phosphate, and iron and aluminium impurity content (in terms of oxide) are 5.2wt%, amorphous phase
Content be 10.92wt%；First phase structure and the second phase structure weight ratio are 0.123.In terms of oxide, rare earth and iron and aluminium
The weight ratio of impurity is 6.23.
Embodiment 4
It is 28wt% with 1000g monazite content, rare earth total content is that the phosphorus ore of 19.8wt% sum is raw material, using phosphorus
The mixed acid solution of acid, hydrochloric acid and nitric acid leaches, and the mass concentration of phosphoric acid is 15% (with P in mixed acid2O5Content meter), with yin
The ratio that the molal quantity meter of ion, hydrochloric acid and nitric acid account for mixed acid solution is 15%, and control system liquid-solid ratio is 6:1,20
4h is reacted at DEG C, and one-lime phosphate solution and 375g acid leaching residue containing rare earth are obtained after filtering.
Progress ripening 1h at 100 DEG C is placed in the one-lime phosphate solution containing rare earth, keeps rare earth element dilute with phosphoric acid
The form of soil precipitating is separated with one-lime phosphate solution, thus is separated by solid-liquid separation, and one-lime phosphate solution and 21.7g phosphoric acid are obtained
Rare-earth precipitation.
Rare earth acid leaching residue is mixed with phosphoric acid rare-earth precipitation, obtains the substance containing RE phosphate.
Through detecting, in the substance containing RE phosphate, iron and aluminium impurity content (in terms of oxide) are 23wt%, amorphous
The content of phase is 5.66wt%；First phase structure and the second phase structure weight ratio are 0.060.In terms of oxide, rare earth and iron and
The weight ratio of aluminium impurity is 2.10.
Embodiment 5
It is 35.0wt with 1000g xenotime content, rare earth total content is that the phosphorus ore of 24.5wt% sum is raw material, using phosphoric acid
It is leached with the mixed acid solution of hydrochloric acid, the mass concentration of phosphoric acid is 25% (with P in mixed acid2O5Content meter), with rubbing for anion
That number meter, the ratio that hydrochloric acid accounts for mixed acid solution is 20% (in terms of the molal quantity of anion), and control system liquid-solid ratio is 2:1,
0.5h is reacted at 15 DEG C, and one-lime phosphate solution and 463g acid leaching residue containing rare earth are obtained after filtering.
Progress ripening 2h at 75 DEG C is placed in the one-lime phosphate solution containing rare earth, makes rare earth element with phosphoric acid rare earth
The form of precipitating is separated with one-lime phosphate solution, thus is separated by solid-liquid separation, and obtains one-lime phosphate solution and 19.3g phosphoric acid is dilute
Soil precipitating.
Rare earth acid leaching residue is mixed with phosphoric acid rare-earth precipitation, obtains the substance containing RE phosphate.
Through detecting, in the substance containing RE phosphate, iron and aluminium impurity content (in terms of oxide) are 23wt%, amorphous
The content of phase is 4.07wt%；First phase structure and the second phase structure weight ratio are 0.042.
Embodiment 6
It is 3.5wt% with 1000g xenotime content, rare earth total content is that the phosphorus ore of 3.3wt% sum is raw material, using phosphoric acid
It is leached with the mixed acid solution of hydrochloric acid, the mass concentration of phosphoric acid is 25% (with P in mixed acid2O5Content meter), with rubbing for anion
That number meter, the ratio that hydrochloric acid accounts for mixed acid solution is 10% (in terms of the molal quantity of anion), and control system liquid-solid ratio is 3:1,
2h is reacted at 15 DEG C, and one-lime phosphate solution and 143g acid leaching residue containing rare earth are obtained after filtering.
Progress ripening 2h at 120 DEG C is placed in the one-lime phosphate solution containing rare earth, keeps rare earth element dilute with phosphoric acid
The form of soil precipitating is separated with one-lime phosphate solution, thus is separated by solid-liquid separation, and one-lime phosphate solution and 18.6g phosphoric acid are obtained
Rare-earth precipitation.
Rare earth acid leaching residue is mixed with phosphoric acid rare-earth precipitation, obtains the substance containing RE phosphate.
Through detecting, in the substance containing RE phosphate, iron and aluminium impurity content (in terms of oxide) are 5.8wt%, without fixed
The content of shape phase is 28.66wt%；First phase structure and the second phase structure weight ratio are 0.402.In terms of oxide, rare earth and iron
Weight ratio with aluminium impurity is 3.46.
Embodiment 7
With 1000g 2.0wt% containing monazite, the phosphorus ore that rare earth total content is 2.3wt% is raw material, using phosphoric acid and hydrochloric acid
Mixed acid solution leach, the mass concentration of phosphoric acid is 30% (with P in mixed acid2O5Content meter), with the molal quantity of anion
Meter, the ratio that hydrochloric acid accounts for mixed acid solution is 25% (in terms of the molal quantity of anion), control system liquid-solid ratio 6:1, at 15 DEG C
Lower reaction 2h obtains the one-lime phosphate solution containing rare earth and 124g phosphoric acid rare earth slag after filtering.
Progress ripening 2h at 120 DEG C is placed in the one-lime phosphate solution containing rare earth, keeps rare earth element dilute with phosphoric acid
The form of soil precipitating is separated with one-lime phosphate solution, thus is separated by solid-liquid separation, and one-lime phosphate solution and 22.5g phosphoric acid are obtained
Rare-earth precipitation.
Rare earth acid leaching residue is mixed with phosphoric acid rare-earth precipitation, obtains the substance containing RE phosphate.
Through detecting, in the substance containing RE phosphate, iron and aluminium impurity content (in terms of oxide) are 5.6wt%, without fixed
The content of shape phase is 49.56wt%；First phase structure and the second phase structure weight ratio are 0.983.In terms of oxide, rare earth and iron
Weight ratio with aluminium impurity is 2.77.
Embodiment 8
With 1000g 35wt% containing monazite, the phosphorus ore that rare earth total content is 24.5wt% is raw material, using phosphoric acid and hydrochloric acid
Mixed acid solution leach, the mass concentration of phosphoric acid is 25% (with P in mixed acid2O5Content meter), with the molal quantity of anion
Meter, the ratio that hydrochloric acid accounts for mixed acid solution is 10% (in terms of the molal quantity of anion), control system liquid-solid ratio 3:1, at 90 DEG C
Lower reaction 10h obtains one-lime phosphate solution and 483g phosphoric acid rare earth slag after filtering.
It is detected, in the slag of phosphoric acid containing rare earth, iron and aluminium impurity content (in terms of oxide) are 31wt%, and amorphous phase contains
Amount is 3.6wt%；First phase structure and the second phase structure weight ratio are 0.037.In terms of oxide, rare earth and iron and aluminium impurity
Weight ratio is 2.20.
Embodiment 9
With 1000g 3.5wt% containing monazite, the phosphorus ore that rare earth total content is 3.3wt% is raw material, using phosphoric acid and hydrochloric acid
Mixed acid solution leach, the mass concentration of phosphoric acid is 10% (with P in mixed acid2O5Content meter), with the molal quantity of anion
Meter, hydrochloric acid account for mixed acid solution ratio be 30% (in terms of the molal quantity of anion), control system liquid-solid ratio 3:1, at 5 DEG C
2h is reacted, the one-lime phosphate solution containing rare earth and 123g phosphoric acid rare earth slag are obtained after filtering.
Progress ripening 2h at 55 DEG C is placed in the one-lime phosphate solution containing rare earth, makes rare earth element with phosphoric acid rare earth
The form of precipitating is separated with one-lime phosphate solution, thus is separated by solid-liquid separation, and obtains one-lime phosphate solution and 2.4g phosphoric acid is dilute
Soil precipitating.
Rare earth acid leaching residue is mixed with phosphoric acid rare-earth precipitation, obtains the substance containing RE phosphate.
Through detecting, in the substance containing RE phosphate, iron and aluminium impurity content (in terms of oxide) are 1.3wt%, without fixed
The content of shape phase is 3.7wt%；First phase structure and the second phase structure weight ratio are 0.038.In terms of oxide, rare earth and iron and
The weight ratio of aluminium impurity is 19.90.
In the various embodiments described above, leached according to rare earth occurrence patterns in rare earth phosphate rock and content and by rare earth phosphate rock
The process control of journey, content of the amorphous phase in RE phosphate are 5~40wt%, are more advantageous to subsequent containing RE phosphate
Substance in rare earth recycling；By the impurity content of iron content and/or aluminium control in the above-mentioned substance containing RE phosphate 3~
Within the scope of 25wt%, have content of rare earth relatively higher, be convenient for rare earth recovery, by impurity enriched in solid phase, reduces impurity member
Element enters in leachate, reduces subsequent phosphoric acid purification removal of impurities burden, and in the substance containing RE phosphate iron aluminium presence, favorably
In playing the role of solid phosphorus in subsequent rare earth recovery process, and then is conducive to improve rare-earth yield and realizes the comprehensive benefit of iron aluminium
With.
After obtaining the substance containing RE phosphate of the various embodiments described above, can further to rare earth element therein into
Row recycles, and specific the step of recycling is as shown in Figure 1.Into the substance containing RE phosphate add iron compound or
Simultaneously the substance of calcic and magnesium is added, and be added mass concentration greater than 90% the concentrated sulfuric acid carry out it is acidizing fired, then with water pair
Product of roasting is leached, and rare earth infusion and water logging slag are obtained；The pH value of the infusion containing rare earth is adjusted to 3.8~5, is filtered
To rare earth sulfate solution and filter residue, ferro element, P elements and thorium element are contained in the filter residue；Using acidic phosphorus extractant to sulfuric acid
Earth solution finally using extraction and separation are carried out, is mixed or single rare earth chloride；Alternatively, being added into rare earth sulfate solution
Carbonate or oxalate precipitation rare earth obtain rare earth carbonate or rare-earth oxalate；Further to rare earth carbonate or rare earth grass
Hydrochlorate is calcined, available rare earth oxide.
Similarly, one-lime phosphate solution obtained in above-described embodiment is sulfuric acid-treated obtains calcium sulfate and solution containing phosphate, sulphur
Sour calcium can be used to prepare commercially available gypsum product, and the purified removal of impurities of solution containing phosphate obtains phosphoric acid solution and can be further used for phosphorus
The step of acid dipping of mine, to realize recycling for material.
It can be seen from the above description that the application the above embodiments realize following technical effect: of the invention
Embodiment is leached dilute containing monazite and/or xenotime using the solution of phosphoric acid by under relatively low reaction temperature
Native phosphorus ore forms one-lime phosphate solution, while rare earth element using the phosphorus in the hydrogen ion dissolution phosphorus ore in phosphorous acid solution
It is dissolved and enters in solution, formed and contain rare earth ion, Ca2+And H2PO4 -Leachate；And monazite is insoluble during acidleach
Solution be retained in slag from.Ripening is carried out to leachate, is conducive to rare earth element formation phosphoric acid rare-earth precipitation is further
Realize the separation of rare earth element and P elements.Reaction temperature is smaller to the influence of extraction of P elements during acidleach, and lower
At a temperature of phosphoric acid rare earth solubility it is relatively large, be conducive to the leaching of rare earth element, while can effectively inhibit in phosphorus ore under low temperature
The leaching of the impurity elements such as iron, aluminium, so that leaching rate < 5% of ferro element and aluminium element, significantly reduces subsequent phosphoric acid purification and remove
Miscellaneous burden.Thus, the temperature by controlling ripening is higher than the temperature of step of acid dipping, and phosphoric acid is dilute at a relatively high temperature
Native solubility product is small, is conducive to make the rare earth element in leachate to precipitate in the form of RE phosphate, further realizes rare earth
Element and P elements efficiently separate.Thus, the substance rare earth prepared by the above embodiment of the present invention containing RE phosphate
Grade is high, greatly facilitates the subsequent recycling to rare earth.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (11)
1. a kind of substance containing RE phosphate, which is characterized in that the substance containing RE phosphate be from containing monazite and/
Or it is isolated in the phosphorus ore of xenotime, which includes:
Step S1,10 DEG C~60 DEG C at a temperature of, with the solution of phosphoric acid to the phosphorus ore containing monazite and/or xenotime
It leaches 0.5~8 hour, obtains leachate and rare earth acid leaching residue；The leachate contains rare earth ion, calcium ion and biphosphate
Radical ion；
Step S2, carries out ripening to the leachate, obtains phosphoric acid rare-earth precipitation and one-lime phosphate solution through being separated by solid-liquid separation；
The reaction temperature of step S2 is higher than the reaction temperature of the step S1；
Step S3 mixes the rare earth acid leaching residue with the phosphoric acid rare-earth precipitation, obtains the substance containing RE phosphate；
RE phosphate at least contains the first phase structure and the second phase structure in the substance containing RE phosphate, and described first
Phase structure is amorphous phase, which is the phase structure that the phosphoric acid rare-earth precipitation is formed；Second phase structure includes
Monazite phase and/or xenotime phase；In terms of weight content, content of the amorphous phase in the RE phosphate is greater than
1%；It further include the impurity of iron content and/or aluminium in the substance containing RE phosphate, in terms of oxide, iron and/or aluminium content
For 3~25wt%；In the substance containing RE phosphate, in terms of oxide, the weight ratio of rare earth and the iron and/or aluminium
For 2~20:1.
2. the substance according to claim 1 containing RE phosphate, which is characterized in that in terms of weight content, the nothing is fixed
Mutually the content in the RE phosphate is 5~40% to shape.
3. the substance according to claim 1 containing RE phosphate, which is characterized in that the substance containing RE phosphate
Described in the weight ratio of the first phase structure and second phase structure be 1:1~20.
4. the substance according to claim 1 containing RE phosphate, which is characterized in that with the solution of the phosphoric acid to institute
It states and is leached 1~4 hour containing the phosphorus ore of monazite and/or xenotime.
5. the substance according to claim 1 containing RE phosphate, which is characterized in that the step S2 includes:
To the leachate 60 DEG C~150 DEG C at a temperature of ripening 0.5~24 hour, separation of solid and liquid obtain the phosphoric acid
Rare-earth precipitation and the one-lime phosphate solution.
6. the substance according to claim 5 containing RE phosphate, which is characterized in that the leachate 80~120
Ripening 1~8 hour at a temperature of DEG C, separation of solid and liquid obtain the phosphoric acid rare-earth precipitation and the one-lime phosphate solution.
7. the substance according to claim 1 containing RE phosphate, which is characterized in that also wrapped in the solution of the phosphoric acid
Hydrochloric and/or nitric acid.
8. the substance according to claim 7 containing RE phosphate, which is characterized in that in terms of the molal quantity of anion, institute
Ratio shared by hydrochloric acid and/or nitric acid is stated in the solution of phosphoric acid less than 30%.
9. the substance according to claim 8 containing RE phosphate, which is characterized in that in terms of the molal quantity of anion, institute
Stating in the solution of phosphoric acid ratio shared by hydrochloric acid and/or nitric acid is 2~15%.
10. the substance according to any one of claim 1 to 9 containing RE phosphate, which is characterized in that with P2O5Meter, institute
The mass concentration for stating phosphoric acid in the solution of phosphoric acid is 15%~50%；The solution of the phosphoric acid and it is described containing monazite and/
Or the phosphorus ore of xenotime is mixed according to the ratio that liquid-solid ratio is 2~10L:1kg.
11. the substance according to claim 10 containing RE phosphate, which is characterized in that with P2O5Meter, the phosphoric acid
The mass concentration of phosphoric acid is 15%~30% in solution；The solution of the phosphoric acid and described containing monazite and/or xenotime
Phosphorus ore is 3~6L:1kg according to liquid-solid ratio.
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| CN201510347681.3A CN106319248B (en) | 2015-06-19 | 2015-06-19 | Substance containing RE 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 |
| 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 |
| 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 |
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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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