CN105441674B - From the method for synthetical recovery phosphorus and rare earth in phosphorus ore containing monazite - Google Patents
From the method for synthetical recovery phosphorus and rare earth in phosphorus ore containing monazite Download PDFInfo
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- CN105441674B CN105441674B CN201410374916.3A CN201410374916A CN105441674B CN 105441674 B CN105441674 B CN 105441674B CN 201410374916 A CN201410374916 A CN 201410374916A CN 105441674 B CN105441674 B CN 105441674B
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Abstract
The invention discloses a kind of method from synthetical recovery phosphorus and rare earth in phosphorus ore containing monazite.This method comprises the following steps：Phosphoric acid leaches phosphorus ore containing monazite, and separation of solid and liquid obtains the solution of one-lime phosphate containing rare earth and containing solitary rock ballast；Extractant organic solution, extraction and recovery one-lime phosphate solution middle rare earth are added in the solution of one-lime phosphate containing rare earth, and obtains the raffinate of the calcium of phosphoric acid one；Reclaim containing the rare earth in solitary rock ballast, and reclaim the phosphorus in the raffinate of the calcium of phosphoric acid one.The characteristics of architectural feature for the rare-earth mineral that this method is decomposed using wherein monazite etc. hardly possible causes its decomposition condition harsh relative to phosphorus ore, leaching processing is carried out to phosphorus ore containing monazite using phosphoric acid, by phosphorus ore dissolving production one-lime phosphate (Ca (H2PO4)2) enter liquid phase, to cause apatite to be separated with monazite.The middle rare earth of solid slag containing monazite is neutralized to one-lime phosphate solution to reclaim, improve rare earth yield respectively.
Description
Technical field
The present invention relates to rare earth recovery field, in particular to one kind from synthetical recovery phosphorus in phosphorus ore containing monazite and
The method of rare earth.
Background technology
Rare-earth mineral is in nature often with the mineral intergrowth such as barite, calcite, apatite, silicate ore one
Rise.Because mineral are different into ore deposit reason, occurrence status and content of the rare earth element in mineral are also different.Currently produced
Ores containing rare earths in, the content of rare earth oxide only has a few percent, even lower.In order to meet the need of rare earth metallurgy production
Will, by rare earth and other ore separations, rare-earth mineral must be enriched with first through beneficiation method before smelting.It is rich through ore dressing
The content of mineral middle rare earth after collection can reach more than 60%~70%.The mineral being enriched with after rare earth are commonly referred to as dilute
The content of rare earth oxide in native concentrate, concentrate is referred to as the rare earth grade of concentrate.
The mineral of rare earth mainly have bastnaesite, monazite, xenotime, ion adsorption type rare earth ore etc., at present, reclaim only
Occupying the method for stone middle rare earth mainly has following two modes：
(1) alkaline process resolution process monazite is applied in high-grade solitary stone ore, monazite and liquid caustic soda course of reaction, dilute
Autochthonal into water insoluble hydroxide, phosphorus is changed into tertiary sodium phosphate, and rare-earth hydroxide is obtained through the excellent molten, removal of impurities of persalt again
Mixed chlorinated rare earth.If the impurity content such as iron, silicon is high in concentrate, the colloidal materials such as sodium metasilicate, iron hydroxide are easily formed, were precipitated
Filter separation circuit is difficult to, therefore the technique can not normally be run.
(2) concentrated sulfuric acid roasting method decomposes solitary stone ore, and monazite concentrate and the concentrated sulfuric acid are blended in into 200-230 DEG C of decomposition 2-
4 hours, concentrated sulfuric acid consumption was 1.7-2 times of concentrate weight, with the water extraction of 7-10 times of concentrate weight, leaching after analyte cooling
Go out liquid middle rare earth about 55g/L (REO), 25g/L P2O5, 2.5g/L Fe2O3, acidity is 2.5mol/L.The immersion liquid acidity is high, miscellaneous
Matter phosphorus, thorium are high, using sodium sulfate double salt precipitating rare earth and thorium, then switch to hydroxide by alkali, then leach using acid is preferential
Rare earth, 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；Soda acid
Cross-reference, industrial chemicals consuming cost is high, and phosphorus enters wastewater treatment difficulty greatly, and radioactive element thorium is dispersed in slag and waste water
In be difficult to reclaim.
Phosphorus ore is the primary raw material for producing phosphorus chemical product, and world phosphate resource reserve is big, normal association trace rare-earth.Mesh
Before, reclaiming the method for phosphorus ore middle rare earth includes：Phosphoric acid by wet process process rare earth using hydrochloric acid, nitrate method processing phosphorus ore enters solution
In, then using mode recovering rare earths such as solvent extraction, ion exchange, precipitation, crystallizations；The wet method phosphorus of phosphorus ore is handled using sulfuric acid process
During acid, rare earth is respectively enterd in solution and ardealite, then rare earth is entered in solution, solution using sulfuric acid to leach ardealite
Rare earth can be using the mode recovering rare earth such as solvent extraction, ion exchange, precipitation, crystallization.In patent CN 201110143415.0
Phosphorus concentrate containing rare earth is reacted with phosphoric acid solution mixing, by controlling process conditions to make phosphorus ore middle rare earth with fluoride shape
Formula is precipitated, and the rare earth of rare earth more than 85% enters in slag.The rare earth in slag is reclaimed using hydrochloric acid, nitric acid or sulfuric acid dissolution again, still
Slag middle rare earth grade is very low, and about 1%, foreign matter of phosphor, calcium, aluminium, silicon equal size are high, and rare earth fluoride is difficult with acid dissolving, acid consumption
Height, the quantity of slag is big, and rare earth yield is low.Enter 15% rare earth in leachate in addition during deliming easily to enter in gypsum tailings
It is difficult to reclaim.
Presence based on above mentioned problem, this area research staff is in recovering rare earth, and generally selection taste is higher, and composition
The mineral such as relatively single apatite, phosphorite or solitary stone ore.And researcher is when studying Rare earth recovery method, generally also
It is that to be directed to this taste higher, and composition single ore relatively, to improve the rate of recovery of rare earth.At present, it is rare to be directed to
Quality is relatively low, the scheme for the recovering rare earth that the more miscellaneous composite ore of mineralogical composition is proposed.Moreover, it is existing higher to sampling, and into
Split-phase is also not particularly suited for reclaiming the rare earth in composite ore to the recovery method of single middle rare earth.
By taking phosphorus ore containing monazite as an example, this phosphorus ore containing monazite contains various ingredients simultaneously, including monazite, rare earth,
And phosphorus ore etc..In the composite ore of the multi mineral such as this apatite and monazite, because monazite and phosphorus ore belong to phosphorus
Hydrochlorate mineral, both are closer to mineralogy, and often embedding cloth is in close relations with phosphorus ore for monazite in the mineral of its symbiosis.
When reclaiming this composite ore rare earth elements and P elements, due to each material parcel larger, thing of inlaying dissociation difficulty in composite ore
Manage ore dressing effective sorting difficult to realize to ore.Especially since decompose monazite need relatively harsh condition, it is necessary to compared with
High temperature and acid-base value etc., when containing the phosphorus ore of monazite using sulfuric acid process wet-treating of the prior art, often can not
Decompose monazite complete, fail to realize its effective recycling.
It is relatively low how this be similar to containing monazite phosphorus ore this kind of quality is reclaimed, it is dilute in the more miscellaneous composite ore of mineralogical composition
Soil, have become research staff has a new problem.
The content of the invention
The present invention is intended to provide a kind of method from synthetical recovery phosphorus and rare earth in phosphorus ore containing monazite, with provide it is a kind of from
The new method of recovering rare earth in low-quality phosphorus ore containing monazite.
To achieve these goals, according to an aspect of the invention, there is provided one kind is comprehensive from phosphorus ore containing monazite
The method for reclaiming phosphorus and rare earth, comprises the following steps：Phosphoric acid leaches the phosphorus ore containing monazite, and separation of solid and liquid obtains containing rare earth
One-lime phosphate solution and containing solitary rock ballast；Extractant organic solution is added in the solution of one-lime phosphate containing rare earth, is extracted back
The one-lime phosphate solution middle rare earth is received, and obtains the raffinate of the calcium of phosphoric acid one；The rare earth contained in solitary rock ballast is reclaimed,
And reclaim the phosphorus in the raffinate of the calcium of phosphoric acid one.
Further, in above-mentioned phosphoric acid leaches step, the phosphoric acid and the phosphorus ore containing monazite according to liquid-solid ratio 2~
10L:1kg is mixed, P in preferably described phosphoric acid2O5Mass concentration is 15%~50%, preferably 20%~35%.
Further, in above-mentioned phosphoric acid leaching process, extraction temperature is 25 DEG C~150 DEG C, and extraction time is that 0.5-8 is small
When；Preferably, the extraction temperature is 105~130 DEG C, and extraction time is 2~5 hours.
Further, add before extractant, first added in the one-lime phosphate solution in above-mentioned one-lime phosphate solution
Alkaline matter, using regulation system pH value as 0.1~0.5, preferable ph is 0.2~0.4.
Further, in the step of above-mentioned regulation system pH value, the calcium ion in Dicalcium Phosphate formed in system is small
The 5% of calcium ion total content in system.
Further, above-mentioned alkaline matter be magnesia, magnesium hydroxide, magnesium carbonate, calcium oxide, calcium hydroxide, calcium carbonate,
Sodium hydroxide or sodium carbonate, preferably described alkaline matter are calcium oxide, calcium hydroxide or calcium carbonate.
Further, in above-mentioned one-lime phosphate solution the step of extraction and recovery rare earth, extractant be P204, P507,
At least one of P215, DOPPA, DNPPA, preferably P204.
Further, in above-mentioned one-lime phosphate solution the step of extraction and recovery rare earth, extracted in extractant organic solution
Agent concentration is 0.1~1.5mol/L, and preferably described extractant organic solution compares 1 with one-lime phosphate solution specific volume：15~10：
1。
Further, reclaim it is above-mentioned contain solitary rock ballast middle rare earth the step of include：It is described contain add and contain in solitary rock ballast
Iron compound, and add after fluorochemical, progress reinforcing roasting is mixed with the concentrated sulfuric acid, fired slags are obtained；The fired slags are used
Water logging goes out, and is filtrated to get infusion containing rare earth and water logging slag；The pH value of the regulation infusion containing rare earth is 3.5~5, is filtered
Precipitated to phosphoric acid iron and thorium phosphate, and rare earth sulfate solution；Carbonate deposition is added in the rare earth sulfate solution dilute
Soil, obtains rare earth carbonate product.
Further, it is above-mentioned to add iron containing compoundses in containing solitary rock ballast, and during adding fluorochemical,
The fluorochemical contains solitary rock ballast by F with described:Si mol ratios are 4-6：1 mixing, preferably fluorochemical are calcirm-fluoride
Or fluorite, preferably described iron containing compoundses are iron content rare-earth tailing.
Further, it is above-mentioned to be mixed with the concentrated sulfuric acid in progress reinforcing roasting process, the concentrated sulfuric acid with containing solitary rock ballast and
Phosphoric acid rare earth slag is according to mass ratio 1-2：1 mixing, the sintering temperature of preferably described reinforcing calcination stepses is 250-500 DEG C.
Further, during the pH value of above-mentioned regulation infusion containing rare earth, using magnesia and/or light dolomite
The pH value of the regulation infusion containing rare earth, preferably adjusts the pH value of the infusion containing rare earth to 4.0~4.5.
Further, during above-mentioned water logging, Fe/P mol ratios are more than 2, preferably greater than 3 in immersion liquid.
Further, include in the raffinate of the above-mentioned recovery calcium of phosphoric acid one the step of phosphorus：To the phosphoric acid one
In the raffinate of calcium plus after sulfuric acid deliming, separation of solid and liquid, solution containing phosphate and calcium sulfate gypsum are obtained, is reclaimed in the solution containing phosphate
Phosphorus.
Further, the step of reclaiming phosphorus in the raffinate of the above-mentioned calcium of phosphoric acid one also includes：The solution containing phosphate is removed
Phosphoric acid is prepared after miscellaneous, and prepared phosphoric acid is returned into the phosphoric acid and leaches step recycling.
Apply the technical scheme of the present invention a kind of method from synthetical recovery phosphorus and rare earth in phosphorus ore containing monazite, is directed to
The special circumstances of the mineral of phosphorus ore containing monazite, the architectural feature of the rare-earth mineral decomposed using the hardly possible such as wherein monazite causes its point
The characteristics of solution condition is harsh relative to phosphorus ore, carries out leaching processing to phosphorus ore containing monazite using phosphoric acid, phosphorus ore is dissolved and produced
One-lime phosphate (Ca (H2PO4)2) enter liquid phase, to cause apatite to be separated with monazite.Meanwhile, distinguish in the present invention
The rare earth that one-lime phosphate solution neutralizes two kinds of different phases in solid slag containing monazite is reclaimed, rare earth recovery is being improved
While rate, the chemical industry consumptive material consumption such as acid, alkali is reduced.
Brief description of the drawings
The Figure of description for constituting the part of the application is used for providing a further understanding of the present invention, and of the invention shows
Meaning property embodiment and its illustrate be used for explain the present invention, do not constitute inappropriate limitation of the present invention.In the accompanying drawings：
Fig. 1 shows step flow chart of the present invention from the method for recovering rare earth in phosphorus ore containing monazite.
Embodiment
It should be noted that in the case where not conflicting, the feature in embodiment and embodiment in the application can phase
Mutually combination.Describe the present invention in detail below with reference to the accompanying drawings and in conjunction with the embodiments.
The English entitled Monazite of monazite, molecular formula is (Ln, Th) PO4, Ln refers to the rare earth in addition to promethium in formula
At least one of element.
As pointed by background technology, (the application is referred to as containing only for the composite ore of the multi mineral such as apatite and monazite
Occupy stone phosphorus ore) in, because monazite and phosphorus ore belong to phosphate mineral, both are closer to mineralogy, in its symbiosis
Mineral in monazite often embedding cloth is in close relations with phosphorus ore so that the composite ore of the multi mineral such as this apatite and monazite
Phosphorus and rare earth recovery operation carry out it is more difficult.In the present invention, precisely in order to based on this problem, it is proposed that a kind of
From the new method of synthetical recovery phosphorus and rare earth in phosphorus ore containing monazite.As shown in figure 1, this method comprises the following steps：Phosphoric acid soaks
Go out phosphorus ore containing monazite, separation of solid and liquid obtains the solution of one-lime phosphate containing rare earth and containing solitary rock ballast；It is molten in one-lime phosphate containing rare earth
Extractant organic solution, extraction and recovery leachate middle rare earth are added in liquid, and obtains the raffinate of the calcium of phosphoric acid one；Reclaim containing only
The rare earth in rock ballast is occupied, and reclaims the phosphorus in the raffinate of the calcium of phosphoric acid one.
The above method of the present invention is directed to the special circumstances of the mineral of phosphorus ore containing monazite, is decomposed using the hardly possible such as wherein monazite
The architectural feature of rare-earth mineral the characteristics of cause its decomposition condition harsh relative to phosphorus ore, using phosphoric acid to phosphorus ore containing monazite
Phosphoric acid leaching processing is carried out, phosphorus ore is dissolved, phosphorus and calcium is generated one-lime phosphate (Ca (H2PO4)2) enter liquid phase, and containing rare earth
Monazite is not decomposed and stayed in slag, and then make it that apatite mine is separated with monazite, so be conducive to phosphorus in phosphorus ore with
The independent recovery of rare earth in monazite.
Meanwhile, in the composite ore of multi mineral such as this apatite and monazite, rare earth is present in apatite and only simultaneously
Occupy in stone, in phosphoric acid leaches step, generate the calcium of soluble phosphoric acid one (Ca (H2PO4)2) when, the rare earth in apatite is dissolved
Into leachate, further reclaimed be dissolved into the solution of one-lime phosphate containing rare earth by the method for extraction and recovery in the present invention
Rare earth, rare earth is separated with phosphorus, and then improve the rate of recovery of rare earth, and avoids influenceing the production of phosphoric acid because of Extraction of rare earth
And phosphoric acid product quality.
In addition, the above method of the present invention has, technique is simple, matched with Wet Processes of Phosphoric Acid, and this method passes through to difference
The rare earth of form carries out substep recovery, makes full use of solitary stone ore and apatite mine mineralogical character difference, targetedly carries out area
Other places are managed, and are conducive to improving rare earth yield.
The purpose that phosphoric acid is leached in the present invention is that, by P elements dissolution in phosphorus ore containing monazite, and monazite is not decomposed and stayed
Make rare-earth enrichment in slag, reduce sour consumption.In practical operation, the amount of the phosphoric acid added is premised on realizing this purpose
It is added.In the preferred embodiment of the present invention, above-mentioned phosphoric acid is leached in step, phosphoric acid and phosphorus containing monazite
Ore deposit is according to liquid-solid ratio 2-10L:1kg is mixed.By controlling phosphoric acid consumption, be conducive to, in the case where reducing phosphoric acid consumption, making phosphorus
With the calcium generation calcium of soluble phosphoric acid one (Ca (H2PO4)2) enter solution, now, insoluble monazite will be left in slag, and this is just
Realize efficiently separating for phosphorus ore and monazite.In the process, the rare earth in apatite can be dissolved simultaneously, make its equally with
Monazite is realized and efficiently separated.And then can be formed for there is rare earth in phosphorus ore containing monazite with different compound forms
Different phase, and then the rare earth of different phase is carried out by targetedly reclaiming, and then improve the rate of recovery of rare earth..
Preferably, the P in the phosphoric acid that above-mentioned phosphoric acid leaches used in step2O5Mass concentration is 15%~50%, preferably
For 20%~35%.P in used phosphoric acid in the present invention2O5Weight concentration is not limited to above range, is using P2O5Weight
During concentration phosphoric acid within the above range, higher acidity is conducive to the decomposition of phosphorus ore, so that the yield of phosphorus is improved, but it is too high
Then there is subsequent handling process in phosphorus acid content；
Preferably, in above-mentioned phosphoric acid leaches step, extraction temperature is 30 DEG C~150 DEG C, and extraction time is 0.5~8 small
When.Phosphoric acid of the present invention leaches extraction temperature and extraction time in step and is not limited to above range, passes through the leaching of above range
Temperature, the decomposition of favourable phosphorus ore.It is highly preferred that extraction temperature is 105~130 DEG C, extraction time is 2~5 hours, higher leaching
Go out temperature, be more beneficial for the decomposition of phosphorus ore.
After the step of above-mentioned phosphoric acid is leached, extraction step is directly carried out.In order to improve the rate of recovery of rare earth, at this
Invention a kind of preferred embodiment in, before extraction step before, first add alkaline matter in one-lime phosphate solution, with adjust
It is 0.1~0.5 to save system pH, and preferably pH value is 0.2~0.4.It is to be directed to one-lime phosphate solution body based on the extraction step
It is extraction and recovery rare earth, the pH value of system is adjusted to above-mentioned scope, can effectively improve the extraction yield of rare earth, suppresses simultaneously
The extraction of calcium, realizes efficiently separating for rare earth and calcium ion, and then improve the rate of recovery of rare earth.
In the step of above-mentioned regulation one-lime phosphate solution system pH value, the alkaline matter that can be used includes but is not limited to
Magnesia, magnesium hydroxide, magnesium carbonate, calcium oxide, calcium hydroxide, calcium carbonate, sodium hydroxide or sodium carbonate, preferably calcium oxide, hydrogen
Calcium oxide or calcium carbonate.Calcium oxide, calcium hydroxide or calcium carbonate may advantageously facilitate the generation of one-lime phosphate as alkaline matter, enter
And be conducive to preferably being separated phosphorus with rare earth.The use of simultaneous oxidation calcium, calcium hydroxide or calcium carbonate, which also has, does not draw
Enter the advantage of the impurity such as magnesium, sodium.
It is highly preferred that in the step of above-mentioned regulation one-lime phosphate solution system pH value, making the di(2-ethylhexyl)phosphate formed in system
The amount of calcium is less than 5% of the total content of calcium ion in system for wherein calcium ion.By controlling the amount of Dicalcium Phosphate, so that system
The form of middle phosphorus and calcium one-lime phosphate as much as possible is present, and advantageously allows P elements and rare earths separation, and then increase
The rate of recovery of P elements and rare earth element.
In the above-mentioned solution from one-lime phosphate of the present invention the step of extraction and recovery rare earth in, in extractant organic solution, extraction
It is at least one of P204, P507, P215, DOPPA, DNPPA to take agent, wherein preferably P204.Organic solution uses rare earth
Extractant diluent is often used in extraction field, and such as sulfonated kerosene, kerosene, n-hexane, normal heptane, alcohol are more highly preferred to extraction
Extractant concentration is 0.1~1.5mol/L in agent organic solution, extractant organic solution and one-lime phosphate solution than volume
Than 1：15~10：1.Extractant concentration in extractant organic solution, and extractant organic solution and phosphoric acid one in the present invention
Calcium solution is compared to above range is not limited to, by within the above range, being conducive to the two state modulators to extract in reduction
In the case that agent organic solution is strong, optimize the effect of extracting of rare earth.
In the present invention before the step of rare earth in above-mentioned recovery leached mud containing monazite, the hardly possible such as monazite is decomposed
Rare-earth mineral stay in slag and be enriched with.For higher than phosphorus ore 4-6 times containing solitary rock ballast Rare-Earth Content, but content of rare earth is also
It is that than relatively low, and the impurity content such as phosphorus, silicon, aluminium is high, is difficult to using conventional sodium hydroxide decomposition method, sulfuric acid decomposition method
Effective recovery of rare earth.In the preferred embodiment of the present invention, the step of above-mentioned recovery contains solitary rock ballast middle rare earth wraps
Include：Iron containing compoundses are added in containing solitary rock ballast, and are added after fluorochemical, progress reinforcing roasting is mixed with the concentrated sulfuric acid,
The vitriol intensified roasting of fired slags is obtained to be formed in fired slags；Fired slags are filtered in water logging, are filtrated to get infusion containing rare earth and water logging
Slag；The pH value for adjusting the infusion containing rare earth is 3.5~5, is filtrated to get phosphoric acid iron and thorium phosphate is precipitated, and sulfuric acid rare earth is molten
Liquid；Carbonate deposition rare earth is added in rare earth sulfate solution, rare earth carbonate product is obtained.Now, further roasting rare earth
Carbonate can obtain earth oxide product.
The rare-earth mineral that the hardly possible such as monazite is decomposed is stayed in slag and is enriched with by the present invention, and content of rare earth in raw ore than improving
4~20 times；Slag middle rare earth grade is high, and up to 15%-50%, subsequent handling treating capacity is greatly reduced.Iron is added using unique
Gu phosphorus plus fluorine remove the simple process of the vitriol intensified roasting of silicon, it is prevented effectively from leaching process middle rare earth and is lost with phosphoric acid rare-earth precipitation,
And form the loss for being separated by filtration that difficulty and precipitation process absorption rare earth are caused caused by silica gel is precipitated；Eliminate phosphorus interference, it is dilute
The native rate of recovery is high, acid and alkali consumption is few, good product quality；Thorium is converted into thorium pyrophosphate simultaneously to be solidificated in slag, it is to avoid radioactivity
Scattered pollution of the thorium in technological process.By adjusting pH value for 3~5, form ferric phosphate precipitation, it is to avoid phosphoric acid rare-earth precipitation
Formation, so as to avoid the loss of rare earth.Wherein preferably sulfuric acid earth solution use carbonate deposition obtain purity 95% with
On rare earth carbonate product.
Preferably, above-mentioned added iron containing compoundses are iron content rare-earth tailing.Addition iron content rare-earth tailing is handled,
Rare-earth yield is not only increased, and realizes the comprehensive utilization of mine tailing iron resource, and realizes the recovery profit of the mine tailing middle rare earth
With while significantly reducing operating cost.
Preferably, it is above-mentioned to add iron containing compoundses in containing solitary rock ballast, and during adding fluorochemical, it is fluorine-containing
Compound is with pressing F in mixing slag:Si mol ratios are 4.1~6：1 mixing.Fluorochemical is with containing solitary rock ballast in the present invention
Mixed proportion is not limited to above range, by being 4.1~6 in molar ratio by both：1 mixing, is conducive in reduction containing fluorination
On the premise of the input amount of compound, silicon in ore deposit can be escaped in roasting process formation silicon fluoride gas, it is to avoid silicon is removed in solution
Formed during miscellaneous and the loss that difficult and precipitation process absorption rare earth is caused is separated by filtration caused by silica gel is precipitated, so as to improve
The yield of rare earth.The fluorochemical that can wherein use includes but is not limited to calcirm-fluoride and fluorite.
Preferably, above-mentioned to be mixed with the concentrated sulfuric acid in progress reinforcing roasting process, sintering temperature is 250-500 DEG C.In the temperature
Roasting is carried out in the range of degree to be conducive to that thorium, iron and phosphoric acid formation phosphate, pyrophosphate precipitation are solidificated in slag and be not leached,
Radioactive element thorium is also solidificated in slag simultaneously, it is to avoid scattered pollution of the radiothorium in technological process.In above-mentioned steps
The used concentrated sulfuric acid is the concentrated sulfuric acid of concentration 70% and the above, and preferably concentration is 98.3% concentrated sulfuric acid.
Preferably, during the pH value of above-mentioned regulation infusion containing rare earth, using magnesia and/or light dolomite
The pH value of the infusion containing rare earth is adjusted, the pH value of the infusion containing rare earth is preferably adjusted to 4~4.5.Using magnesia and/or light-burned
The pH value of dolomite regulation infusion containing rare earth, which has, makes phosphorus be completely formed ferric phosphate and thorium phosphate precipitation as far as possible, and rare earth does not sink
The effect in shallow lake.
Preferably, during water logging, Fe/P mol ratios are more than 2, preferably greater than 3 in immersion liquid, and more preferably Fe/P rubs
You are than being 3~6..Both ratio controls are had into phosphorus in removal solution within the range, the effect of rare-earth yield is improved, is adjusting
PH value is saved in 3.5~5 dedoping steps, control Fe/P mol ratios, which are more than 2, can be effectively formed ferric phosphate precipitation, and phosphor-removing effect is good,
And excessive iron hydrolyzable formation precipitation under the pH value condition, it is to avoid the formation of phosphoric acid rare-earth precipitation, so as to avoid dilute
The loss of soil.
Before in the present invention in the raffinate of the above-mentioned calcium of recovery phosphoric acid one the step of phosphorus, phosphorus and rare earth are carried out
Separation.Targetedly it is applied to the method that phosphorus is reclaimed for the Scheme Choice for reclaiming phosphorus in raffinate.The present invention's
In a kind of preferred embodiment, include in the raffinate of the above-mentioned calcium of recovery phosphoric acid one the step of phosphorus：Add sulfuric acid into leachate
After deliming, separation of solid and liquid, solution containing phosphate and calcium sulfate gypsum are formed, the phosphorus in solution containing phosphate is reclaimed.Phosphorus is reclaimed in the method
Phosphorus is using ripe wet method sulfur process in lime stone, and the processing step is simple, and the rate of recovery is of a relatively high.
Preferably, also include the step of phosphorus in the raffinate of the above-mentioned calcium of recovery phosphoric acid one：It will be made after solution containing phosphate removal of impurities
Standby phosphoric acid, and prepared phosphoric acid is returned into phosphoric acid leaching phosphorus ore step recycling.In this approach, the phosphoric acid of recovery is used
Leached in the decomposition of apatite and rare earth, whole flow process linking is reasonable, realize rare earth and phosphorus high efficiente callback, sulfuric acid consumption simultaneously
It is low and cheap.Include but is not limited in above-mentioned steps the step of removal of impurities solution containing phosphate except iron, silicon, aluminium, calcium, magnesium,
Thorium, uranium step.The step of these removal of impurities, uses common process of the prior art as needed.
Beneficial effects of the present invention are further illustrated below with reference to embodiment 1-12.
Embodiment 1
(1) it is raw material as 15.5% phosphorus ore containing monazite (containing rare earth 60%) 23.6%, rare earth total content using 500g, adopts
Leached with mass concentration for 15% (in terms of P2O5) phosphoric acid solution, control system liquid-solid ratio 2L：1kg, adds 100mL phosphoric acid
Solution, reacts at 25 DEG C and the one-lime phosphate solution containing rare earth is obtained after 8h, filtering and containing solitary rock ballast, is obtained after filtering
The one-lime phosphate solution and 12g that 124mL contains rare earth contain solitary rock ballast, and resulting accounts for phosphorus ore raw material containing solitary rock ballast gross weight
The 36.3% of weight.
(2) using resulting one-lime phosphate solution as raw material, sodium carbonate is added wherein, and regulation system pH value is 0.1, is adjusted
Save after pH value, calcium ion content accounts for 2.2% of calcium ion total content in system in the Dicalcium Phosphate formed in system.Then to
Extractant organic solution is added in one-lime phosphate solution, and (extractant P507, organic solvent is sulfonated kerosene, and extractant concentration is
0.1mol/L), the extractant organic solution is in a ratio of 10 with one-lime phosphate solution:1, it is dilute in extraction and recovery one-lime phosphate solution
Soil, extraction series is 15 grades, hydrochloric acid back extraction recovering rare earth, and back extraction series is 15 grades, obtains rare earth 2g, the rate of recovery of rare earth is
95.2%, and obtain the raffinate of the calcium of phosphoric acid one；
Into the raffinate of one-lime phosphate plus after sulfuric acid deliming, separation of solid and liquid, solution containing phosphate and gypsum are formed, is reclaimed phosphorous
Phosphorus in solution.And take phosphoric acid is prepared after the solution containing phosphate removal of impurities of part, and prepared phosphoric acid is returned at phosphoric acid leaching
Reason.
(3) solitary rock ballast is contained as raw material using resulting, iron content rare-earth tailing is added according to phosphorus content in slag, Fe/P is controlled
Mol ratio is 2.5, and adds calcirm-fluoride according to silicone content in slag, and it is 4.1 to control F/Si mol ratios, then adds the concentrated sulfuric acid (dense
98.3%) degree mixes, and concentrated sulfuric acid addition is 1 times containing solitary rock ballast and phosphoric acid rare earth slag weight, is carried out at 350 DEG C strong
Change roasting, obtain fired slags.Infusion containing rare earth and water logging slag are obtained after water logging fired slags, filtering.
The pH value for adding light dolomite regulation infusion containing rare earth is 3, is filtrated to get phosphoric acid iron and thorium phosphate precipitation,
And rare earth sulfate solution；Carbonate deposition rare earth is added in rare earth sulfate solution, rare earth carbonate product 32g, carbon is obtained
Hydrochlorate product purity is 96.1%, and the rate of recovery of monazite middle rare earth is 92.2%.
The rare earth reclaimed with reference to the rare earth and vitriol intensified calcining monazite of extraction and recovery, whole technical process middle rare earth
The rate of recovery be 92.5%.
Embodiment 2
(1) it is raw material as 6.2% phosphorus ore containing monazite (containing rare earth 55%) 10%, rare earth total content using 500g, uses
Mass concentration leaches for 18% (in terms of P2O5) phosphoric acid solution, control system liquid-solid ratio 4L：1kg, 18h is reacted at 105 DEG C,
The one-lime phosphate solution containing rare earth is obtained after filtering and containing solitary rock ballast, the one-lime phosphate solution containing rare earth is obtained after filtering
With containing solitary rock ballast, resulting accounts for the 15.2% of phosphorus ore raw material weight containing solitary rock ballast gross weight.
(2) using resulting one-lime phosphate solution as raw material, sodium carbonate is added wherein, and regulation system pH value is 0.1, is adjusted
Save after pH value, calcium ion content accounts for 2.2% of calcium ion total content in system in the Dicalcium Phosphate formed in system.Then to
Extractant organic solution is added in one-lime phosphate solution, and (extractant P507, organic solvent is n-hexane, and extractant concentration is
0.1mol/L), the extractant organic solution is in a ratio of 8 with one-lime phosphate solution:1, extraction and recovery one-lime phosphate solution middle rare earth,
It is 20 grades to extract series, hydrochloric acid back extraction recovering rare earth, and back extraction series is 15 grades, obtains rare earth 4.3g, the rate of recovery of rare earth is
95.6g, and obtain the raffinate of the calcium of phosphoric acid one；
Into the raffinate of one-lime phosphate plus after sulfuric acid deliming, separation of solid and liquid, solution containing phosphate and gypsum are formed, is reclaimed phosphorous
Phosphorus in solution.And take phosphoric acid is prepared after the solution containing phosphate removal of impurities of part, and prepared phosphoric acid is returned at phosphoric acid leaching
Reason.
(3) solitary rock ballast is contained as raw material using resulting, iron content rare-earth tailing is added according to phosphorus content in slag, Fe/P is controlled
Mol ratio is 2.5, and adds calcirm-fluoride according to silicone content in slag, and it is 4.1 to control F/Si mol ratios, then adds the concentrated sulfuric acid (dense
98.3%) degree mixes, and concentrated sulfuric acid addition is 1 times containing solitary rock ballast and phosphoric acid rare earth slag weight, is carried out at 350 DEG C strong
Change roasting, obtain fired slags.Infusion containing rare earth and water logging slag are obtained after water logging fired slags, filtering.Light dolomite is added to adjust
The pH value for saving the infusion containing rare earth is 3, is filtrated to get phosphoric acid iron and thorium phosphate precipitation, and rare earth sulfate solution；In sulfuric acid
Carbonate deposition rare earth is added in earth solution, rare earth carbonate product 46g is obtained, carbonate products purity is 96.3, solitary
The rate of recovery of stone middle rare earth is 92.5.
The rare earth reclaimed with reference to the rare earth and vitriol intensified calcining monazite of extraction and recovery, whole technical process middle rare earth
The rate of recovery be 93.5%.
Embodiment 3
(1) using containing monazite 5.8%, rare earth 3.9% phosphorus ore as raw material, use mass concentration be 35% (in terms of P2O5)
Phosphoric acid solution leach, control system liquid-solid ratio 10L：1kg, reacts at 110 DEG C and the phosphoric acid containing rare earth is obtained after 1h, filtering
One calcium solution and containing solitary rock ballast, obtains the one-lime phosphate solution containing rare earth and containing solitary rock ballast, resulting contains after filtering
Solitary rock ballast gross weight accounts for the 9.5% of phosphorus ore raw material weight.
(2) using resulting one-lime phosphate solution as raw material, sodium hydroxide is added wherein, and regulation system pH value is
0.15, adjust after pH value, calcium ion content accounts for calcium ion total content in system in the Dicalcium Phosphate formed in system
2.1%.Then extractant organic solution is added into one-lime phosphate solution, and (extractant P204, organic solvent is sulfonated kerosene, extraction
It is 0.5mol/L to take agent concentration), the extractant organic solution is in a ratio of 5 with one-lime phosphate solution:1, extraction and recovery one-lime phosphate
Solution middle rare earth, extraction series is 15 grades, hydrochloric acid back extraction recovering rare earth, and back extraction series is 10 grades, and obtains the calcium of phosphoric acid one
Raffinate；
Into the raffinate of one-lime phosphate plus after sulfuric acid deliming, separation of solid and liquid, solution containing phosphate and gypsum are formed, is reclaimed phosphorous
Phosphorus in solution.And take phosphoric acid is prepared after the solution containing phosphate removal of impurities of part, and prepared phosphoric acid is returned at phosphoric acid leaching
Reason.
(3) solitary rock ballast is contained as raw material using resulting, iron content rare-earth tailing is added according to phosphorus content in slag, Fe/P is controlled
Mol ratio is 2.8, and adds fluorite according to silicone content in slag, and it is 4.5 to control F/Si mol ratios, then adds the concentrated sulfuric acid (concentration
98.3%) mix, concentrated sulfuric acid addition is 1.8 times containing solitary rock ballast and phosphoric acid rare earth slag weight, carried out at 500 DEG C strong
Change roasting, obtain fired slags.Water logging fired slags, obtain infusion containing rare earth and water logging slag after filtering.Light dolomite is added to adjust
The pH value for saving the infusion containing rare earth is 4, is filtrated to get phosphoric acid iron and thorium phosphate precipitation, and rare earth sulfate solution；In sulfuric acid
Carbonate deposition rare earth is added in earth solution, rare earth carbonate product is obtained.
The rare earth reclaimed with reference to the rare earth and vitriol intensified calcining monazite of extraction and recovery, whole technical process middle rare earth
The rate of recovery be 93.3%
Embodiment 4
(1) using containing monazite 9.5%, rare earth 5.7% phosphorus ore as raw material, use mass concentration be 20% (in terms of P2O5)
Phosphoric acid solution leach, control system liquid-solid ratio 7L：1kg, reacts at 120 DEG C and the phosphoric acid containing rare earth is obtained after 2h, filtering
One calcium solution and containing solitary rock ballast, obtains the one-lime phosphate solution containing rare earth and containing solitary rock ballast, resulting contains after filtering
Solitary rock ballast gross weight accounts for the 11.7% of phosphorus ore raw material weight.
(2) using resulting one-lime phosphate solution as raw material, sodium hydroxide is added wherein, and regulation system pH value is
0.15, adjust after pH value, calcium ion content accounts for calcium ion total content in system in the Dicalcium Phosphate formed in system
2.1%.Then extractant organic solution is added into one-lime phosphate solution, and (extractant P204, organic solvent is sulfonated kerosene, extraction
It is 0.5mol/L to take agent concentration), the extractant organic solution is in a ratio of 1 with one-lime phosphate solution：5, extraction and recovery one-lime phosphate
Solution middle rare earth, extraction series is 10 grades, hydrochloric acid back extraction recovering rare earth, and back extraction series is 10 grades, and obtains the calcium of phosphoric acid one
Raffinate；
Into the raffinate of one-lime phosphate plus after sulfuric acid deliming, separation of solid and liquid, solution containing phosphate and gypsum are formed, is reclaimed phosphorous
Phosphorus in solution.And take phosphoric acid is prepared after the solution containing phosphate removal of impurities of part, and prepared phosphoric acid is returned at phosphoric acid leaching
Reason.
(3) solitary rock ballast is contained as raw material using resulting, iron content rare-earth tailing is added according to phosphorus content in slag, Fe/P is controlled
Mol ratio is 2.8, and adds fluorite according to silicone content in slag, and it is 4.5 to control F/Si mol ratios, then adds the concentrated sulfuric acid (concentration
98.3%) mix, concentrated sulfuric acid addition is 1.8 times containing solitary rock ballast and phosphoric acid rare earth slag weight, carried out at 500 DEG C strong
Change roasting, obtain fired slags.Water logging fired slags, obtain infusion containing rare earth and water logging slag after filtering.Light dolomite is added to adjust
The pH value for saving the infusion containing rare earth is 4, is filtrated to get phosphoric acid iron and thorium phosphate precipitation, and rare earth sulfate solution；In sulfuric acid
Carbonate deposition rare earth is added in earth solution, rare earth carbonate product is obtained.
The rare earth reclaimed with reference to the rare earth and vitriol intensified calcining monazite of extraction and recovery, whole technical process middle rare earth
The rate of recovery be 93.3%.
Embodiment 5
(1) using containing monazite 11.9%, rare earth 7.5% phosphorus ore as raw material, use mass concentration for 25% (with P2O5
Meter) phosphoric acid solution leach, control system liquid-solid ratio 8L：1kg, reacts at 105 DEG C and the phosphorus containing rare earth is obtained after 3h, filtering
A sour calcium solution and containing solitary rock ballast, obtains the one-lime phosphate solution containing rare earth and containing solitary rock ballast after filtering, resulting
The 11.9% of phosphorus ore raw material weight is accounted for containing solitary rock ballast gross weight.
(2) using resulting one-lime phosphate solution as raw material, magnesia is added wherein, and regulation system pH value is 0.4, is adjusted
Save after pH value, calcium ion content accounts for 1.4% of calcium ion total content in system in the Dicalcium Phosphate formed in system.Then to
Extractant organic solution is added in one-lime phosphate solution, and (extractant P215, organic solvent is normal heptane, and extractant concentration is
1mol/L), the extractant organic solution is in a ratio of 1 with one-lime phosphate solution：5, extraction and recovery one-lime phosphate solution middle rare earth, extraction
It is 5 grades to take series, hydrochloric acid back extraction recovering rare earth, and back extraction series is 6 grades, and obtains the raffinate of the calcium of phosphoric acid one；
Into the raffinate of one-lime phosphate plus after sulfuric acid deliming, separation of solid and liquid, solution containing phosphate and gypsum are formed, is reclaimed phosphorous
Phosphorus in solution.And take phosphoric acid is prepared after the solution containing phosphate removal of impurities of part, and prepared phosphoric acid is returned at phosphoric acid leaching
Reason.
(3) solitary rock ballast is contained as raw material using resulting, iron content rare-earth tailing is added according to phosphorus content in slag, Fe/P is controlled
Mol ratio is 3.1, and adds calcirm-fluoride according to silicone content in slag, and it is 5 to control F/Si mol ratios, then adds concentrated sulfuric acid mixing,
The concentrated sulfuric acid (concentration 98.3%) addition is 1.5 times containing solitary rock ballast and phosphoric acid rare earth slag weight, is carried out at 400 DEG C strong
Change roasting, obtain fired slags.Water logging fired slags, obtain infusion containing rare earth and water logging slag after filtering.Magnesia regulation is added to contain
The pH value of rare earth infusion is 4.2, is filtrated to get phosphoric acid iron and thorium phosphate precipitation, and rare earth sulfate solution；It is dilute in sulfuric acid
Carbonate deposition rare earth is added in native solution.
The rare earth reclaimed with reference to the rare earth and vitriol intensified calcining monazite of extraction and recovery, whole technical process middle rare earth
The rate of recovery be 95.9%.
Embodiment 6
(1) using containing monazite 10.6%, rare earth 6.8% phosphorus ore as raw material, use mass concentration for 22% (with P2O5
Meter) phosphoric acid solution leach, control system liquid-solid ratio 6L：1kg, reacts at 130 DEG C and the phosphorus containing rare earth is obtained after 4h, filtering
A sour calcium solution and containing solitary rock ballast, obtains the one-lime phosphate solution containing rare earth and containing solitary rock ballast after filtering, resulting
The 10.9% of phosphorus ore raw material weight is accounted for containing solitary rock ballast gross weight.
(2) using resulting one-lime phosphate solution as raw material, magnesia is added wherein, and regulation system pH value is 0.4, is adjusted
Save after pH value, calcium ion content accounts for 1.4% of calcium ion total content in system in the Dicalcium Phosphate formed in system.Then to
Extractant organic solution is added in one-lime phosphate solution, and (extractant P215, organic solvent is kerosene, and extractant concentration is 1mol/
L), the extractant organic solution is in a ratio of 1 with one-lime phosphate solution：5, extraction and recovery one-lime phosphate solution middle rare earth extracts level
Number is 5 grades, hydrochloric acid back extraction recovering rare earth, and back extraction series is 5 grades, and obtains the raffinate of the calcium of phosphoric acid one；
Into the raffinate of one-lime phosphate plus after sulfuric acid deliming, separation of solid and liquid, solution containing phosphate and gypsum are formed, is reclaimed phosphorous
Phosphorus in solution.And take phosphoric acid is prepared after the solution containing phosphate removal of impurities of part, and prepared phosphoric acid is returned at phosphoric acid leaching
Reason.
(3) solitary rock ballast is contained as raw material using resulting, iron content rare-earth tailing is added according to phosphorus content in slag, Fe/P is controlled
Mol ratio is 3.1, and adds calcirm-fluoride according to silicone content in slag, and it is 5 to control F/Si mol ratios, then adds the concentrated sulfuric acid (concentration
98.3%) mix, concentrated sulfuric acid addition is 1.5 times containing solitary rock ballast and phosphoric acid rare earth slag weight, carried out at 400 DEG C strong
Change roasting, obtain fired slags.Water logging fired slags, obtain infusion containing rare earth and water logging slag after filtering.Magnesia regulation is added to contain
The pH value of rare earth infusion is 4.2, is filtrated to get phosphoric acid iron and thorium phosphate precipitation, and rare earth sulfate solution；It is dilute in sulfuric acid
Carbonate deposition rare earth is added in native solution, rare earth carbonate product is obtained.
The rare earth reclaimed with reference to the rare earth and vitriol intensified calcining monazite of extraction and recovery, whole technical process middle rare earth
The rate of recovery be 95.9%.
Embodiment 7
(1) using containing monazite 11.2%, rare earth 7% phosphorus ore as raw material, use mass concentration be 20% (in terms of P2O5)
Phosphoric acid solution leach, control system liquid-solid ratio 5L：1kg, reacts the phosphoric acid one obtained after 5h, filtering containing rare earth at 80 DEG C
Calcium solution and containing solitary rock ballast, obtains the one-lime phosphate solution containing rare earth and containing solitary rock ballast after filtering, resulting containing only
Occupy rock ballast gross weight accounts for phosphorus ore raw material weight 11.8%.
(2) using resulting one-lime phosphate solution as raw material, calcium oxide is added wherein, and regulation system pH value is 0.5, is adjusted
Save after pH value, calcium ion content accounts for 1.7% of calcium ion total content in system in the Dicalcium Phosphate formed in system.Then to
Extractant organic solution is added in one-lime phosphate solution, and (extractant P204, organic solvent is kerosene, and extractant concentration is 1mol/
L), the extractant organic solution is in a ratio of 5 with one-lime phosphate solution：1, extraction and recovery one-lime phosphate solution middle rare earth extracts base
Number is 10 grades, hydrochloric acid back extraction recovering rare earth, and back extraction series is 8 grades, and obtains the raffinate of the calcium of phosphoric acid one；
Into the raffinate of one-lime phosphate plus after sulfuric acid deliming, separation of solid and liquid, solution containing phosphate and gypsum are formed, is reclaimed phosphorous
Phosphorus in solution.And take phosphoric acid is prepared after the solution containing phosphate removal of impurities of part, and prepared phosphoric acid is returned at phosphoric acid leaching
Reason.
(3) solitary rock ballast is contained as raw material using resulting, iron content rare-earth tailing is added according to phosphorus content in slag, Fe/P is controlled
Mol ratio is 4, and adds calcirm-fluoride according to silicone content in slag, and it is 5.5 to control F/Si mol ratios, is then mixed with the concentrated sulfuric acid, dense
Sulphuric acid is 2 times containing solitary rock ballast and phosphoric acid rare earth slag weight, and reinforcing roasting is carried out at 450 DEG C, is calcined
Slag.Water logging fired slags, obtain infusion containing rare earth and water logging slag after filtering.Add the pH value that magnesia adjusts the infusion containing rare earth
For 4.5, phosphoric acid iron and thorium phosphate precipitation, and rare earth sulfate solution are filtrated to get；Carbonic acid is added in rare earth sulfate solution
Salt precipitating rare earth, obtains rare earth carbonate product.
The rare earth reclaimed with reference to the rare earth and vitriol intensified calcining monazite of extraction and recovery, whole technical process middle rare earth
The rate of recovery be 96.6%.
Embodiment 8
(1) using containing monazite 32.5%, rare earth 20.3% phosphorus ore as raw material, use mass concentration for 50% (with P2O5
Meter) phosphoric acid solution leach, control system liquid-solid ratio 7L：1kg, reacts at 150 DEG C and the phosphorus containing rare earth is obtained after 3h, filtering
A sour calcium solution and containing solitary rock ballast, obtains the one-lime phosphate solution containing rare earth and containing solitary rock ballast after filtering, resulting
The 34.6% of phosphorus ore raw material weight is accounted for containing solitary rock ballast gross weight.
(2) using resulting one-lime phosphate solution as raw material, calcium oxide is added wherein, and regulation system pH value is 0.5, is adjusted
Save after pH value, calcium ion content accounts for 1.7% of calcium ion total content in system in the Dicalcium Phosphate formed in system.Then to
Extractant organic solution is added in one-lime phosphate solution, and (extractant P204, organic solvent is kerosene, and extractant concentration is 1mol/
L), the extractant organic solution is in a ratio of 5 with one-lime phosphate solution：1, extraction and recovery one-lime phosphate solution middle rare earth extracts level
Number is 10 grades, hydrochloric acid back extraction recovering rare earth, and back extraction series is 10 grades, and obtains the raffinate of the calcium of phosphoric acid one；
Into the raffinate of one-lime phosphate plus after sulfuric acid deliming, separation of solid and liquid, solution containing phosphate and gypsum are formed, is reclaimed phosphorous
Phosphorus in solution.And take phosphoric acid is prepared after the solution containing phosphate removal of impurities of part, and prepared phosphoric acid is returned at phosphoric acid leaching
Reason.
(3) solitary rock ballast is contained as raw material using resulting, iron content rare-earth tailing is added according to phosphorus content in slag, Fe/P is controlled
Mol ratio is 4, and adds calcirm-fluoride according to silicone content in slag, and it is 5.5 to control F/Si mol ratios, then with the concentrated sulfuric acid (concentration
98.3%) mix, concentrated sulfuric acid addition is 2 times containing solitary rock ballast and phosphoric acid rare earth slag weight, is strengthened at 450 DEG C
Roasting, obtains fired slags.Water logging fired slags, obtain infusion containing rare earth and water logging slag after filtering.Magnesia regulation is added containing dilute
The pH value of native infusion is 4.5, is filtrated to get phosphoric acid iron and thorium phosphate precipitation, and rare earth sulfate solution；In sulfuric acid rare earth
Carbonate deposition rare earth is added in solution, rare earth carbonate product is obtained.
The rare earth reclaimed with reference to the rare earth and vitriol intensified calcining monazite of extraction and recovery, whole technical process middle rare earth
The rate of recovery be 96.6%.
Embodiment 9
(1) using containing monazite 16.2%, rare earth 10.1% phosphorus ore as raw material, use mass concentration for 40% (with P2O5
Meter) phosphoric acid solution leach, control system liquid-solid ratio 6L：1kg, reacts at 50 DEG C and the phosphorus containing rare earth is obtained after 7h, filtering
A sour calcium solution and containing solitary rock ballast, obtains the one-lime phosphate solution containing rare earth and containing solitary rock ballast after filtering, resulting
The 20.3% of phosphorus ore raw material weight is accounted for containing solitary rock ballast gross weight.
(2) using resulting one-lime phosphate solution as raw material, calcium hydroxide is added wherein, and regulation system pH value is 0.2,
Adjust after pH value, calcium ion content accounts for 1.1% of calcium ion total content in system in the Dicalcium Phosphate formed in system.Then
Extractant organic solution is added into one-lime phosphate solution, and (extractant DOPPA, organic solvent is kerosene, and extractant concentration is
1.5mol/L), the extractant organic solution is in a ratio of 1 with one-lime phosphate solution:15, it is dilute in extraction and recovery one-lime phosphate solution
Soil, extraction series is 3 grades, hydrochloric acid back extraction recovering rare earth, and back extraction series is 3 grades and obtains the raffinate of the calcium of phosphoric acid one；
Into the raffinate of one-lime phosphate plus after sulfuric acid deliming, separation of solid and liquid, solution containing phosphate and gypsum are formed, is reclaimed phosphorous
Phosphorus in solution.And take phosphoric acid is prepared after the solution containing phosphate removal of impurities of part, and prepared phosphoric acid is returned at phosphoric acid leaching
Reason.
(3) solitary rock ballast is contained as raw material using resulting, iron content rare-earth tailing is added according to phosphorus content in slag, Fe/P is controlled
Mol ratio is 1.3, and adds fluorite according to silicone content in slag, and it is 6 to control F/Si mol ratios, is then mixed with the concentrated sulfuric acid, dense sulphur
Sour addition is 1.3 times containing solitary rock ballast and phosphoric acid rare earth slag weight, and reinforcing roasting is carried out at 250 DEG C, is calcined
Slag.Water logging fired slags, obtain infusion containing rare earth and water logging slag after filtering.Add light dolomite regulation infusion containing rare earth
PH value is 5, is filtrated to get phosphoric acid iron and thorium phosphate precipitation, and rare earth sulfate solution；Carbon is added in rare earth sulfate solution
Hydrochlorate precipitating rare earth, obtains rare earth carbonate product.
The rare earth reclaimed with reference to the rare earth and vitriol intensified calcining monazite of extraction and recovery, whole technical process middle rare earth
The rate of recovery be 92.7%.
Embodiment 10
(1) using containing monazite 16.2%, rare earth 10.1% phosphorus ore as raw material, use mass concentration for 60% (with P2O5
Meter) phosphoric acid solution leach, control system liquid-solid ratio 6L：1kg, reacts at 20 DEG C and the phosphorus containing rare earth is obtained after 10h, filtering
A sour calcium solution and containing solitary rock ballast, obtains the one-lime phosphate solution containing rare earth and containing solitary rock ballast after filtering, resulting
The 30% of phosphorus ore raw material weight is accounted for containing solitary rock ballast gross weight.
(2) using resulting one-lime phosphate solution as raw material, alkaline matter is added wherein, and regulation system pH value is 1, is adjusted
Save after pH value, calcium ion content accounts for 2.3% of calcium ion total content in system in the Dicalcium Phosphate formed in system.Then to
Extractant organic solution is added in one-lime phosphate solution, and (extractant P204, organic solvent is kerosene, and extractant concentration is
0.2mol/L), the extractant organic solution is in a ratio of 12 with one-lime phosphate solution：1, it is dilute in extraction and recovery one-lime phosphate solution
Soil, extraction series is 15 grades, hydrochloric acid back extraction recovering rare earth, and back extraction series is 10 grades, and obtains the raffinate of the calcium of phosphoric acid one；
Into the raffinate of one-lime phosphate plus after sulfuric acid deliming, separation of solid and liquid, solution containing phosphate and gypsum are formed, is reclaimed phosphorous
Phosphorus in solution.And take phosphoric acid is prepared after the solution containing phosphate removal of impurities of part, and prepared phosphoric acid is returned at phosphoric acid leaching
Reason.
(3) mixing slag containing solitary rock ballast and phosphoric acid rare earth slag is included as raw material using resulting, contained according to phosphorus in slag
Amount addition iron content rare-earth tailing, it is 1 to control Fe/P mol ratios, and adds calcirm-fluoride according to silicone content in slag, controls F/Si moles
Than for 3.5, then adding the concentrated sulfuric acid (concentration 98.3%) mixing, concentrated sulfuric acid addition is containing solitary rock ballast and phosphoric acid rare earth slag
3 times of weight, reinforcing roasting is carried out at 200 DEG C, fired slags are obtained.Water logging fired slags, obtain infusion containing rare earth after filtering
With water logging slag.The pH value for adding light dolomite regulation infusion containing rare earth is 2.5, is filtrated to get phosphoric acid iron and thorium phosphate is heavy
Form sediment, and rare earth sulfate solution；Carbonate deposition rare earth is added in rare earth sulfate solution, rare earth carbonate product is obtained.
The rare earth reclaimed with reference to the rare earth and vitriol intensified calcining monazite of extraction and recovery, whole technical process middle rare earth
The rate of recovery be 84.5%.
Embodiment 11
(1) using containing monazite 1%, rare earth 1.5% phosphorus ore as raw material, use mass concentration for 60% (with P2O5Meter)
Phosphoric acid solution is leached, control system liquid-solid ratio 7L：1kg, reacts the phosphoric acid one obtained after 5h, filtering containing rare earth at 100 DEG C
Calcium solution and containing solitary rock ballast, obtains the one-lime phosphate solution containing rare earth and containing solitary rock ballast after filtering, resulting containing only
Occupy rock ballast gross weight accounts for phosphorus ore raw material weight 3.3%.
(2) using resulting one-lime phosphate solution as raw material, alkaline matter is added wherein, and regulation system pH value is 0.2,
Adjust after pH value, calcium ion content accounts for 2.3% of calcium ion total content in system in the Dicalcium Phosphate formed in system.Then
Extractant organic solution is added into one-lime phosphate solution, and (extractant P204, organic solvent is kerosene, and extractant concentration is
1mol/L), the extractant organic solution is in a ratio of 1 with one-lime phosphate solution：5, extraction and recovery one-lime phosphate solution middle rare earth, extraction
It is 10 grades to take series, hydrochloric acid back extraction recovering rare earth, and back extraction series is 8 grades, and obtains the raffinate of the calcium of phosphoric acid one；
Into the raffinate of one-lime phosphate plus after sulfuric acid deliming, separation of solid and liquid, solution containing phosphate and gypsum are formed, is reclaimed phosphorous
Phosphorus in solution.And take phosphoric acid is prepared after the solution containing phosphate removal of impurities of part, and prepared phosphoric acid is returned at phosphoric acid leaching
Reason.
(3) mixing slag containing solitary rock ballast and phosphoric acid rare earth slag is included as raw material using resulting, contained according to phosphorus in slag
Amount addition iron content rare-earth tailing, it is 3 to control Fe/P mol ratios, and adds calcirm-fluoride according to silicone content in slag, controls F/Si moles
Than for 4, then adding the concentrated sulfuric acid (concentration 98.3%) mixing, concentrated sulfuric acid addition is containing solitary rock ballast and phosphoric acid rare earth slag weight
3 times of amount, reinforcing roasting is carried out at 300 DEG C, fired slags are obtained.Water logging fired slags, after filtering obtain infusion containing rare earth with
Water logging slag.The pH value for adding light dolomite regulation infusion containing rare earth is 4, is filtrated to get phosphoric acid iron and thorium phosphate precipitation,
And rare earth sulfate solution；Carbonate deposition rare earth is added in rare earth sulfate solution, rare earth carbonate product is obtained.
The rare earth reclaimed with reference to the rare earth and vitriol intensified calcining monazite of extraction and recovery, whole technical process middle rare earth
The rate of recovery be 93.5%.
Embodiment 12
(1) using containing monazite 0.8%, rare earth 0.2% phosphorus ore as raw material, use mass concentration for 60% (with P2O5Meter)
Phosphoric acid solution leach, control system liquid-solid ratio 7L：1kg, reacts at 105 DEG C and the phosphoric acid containing rare earth is obtained after 5h, filtering
One calcium solution and containing solitary rock ballast, obtains the one-lime phosphate solution containing rare earth and containing solitary rock ballast, resulting contains after filtering
Solitary rock ballast gross weight accounts for the 2.2% of phosphorus ore raw material weight.
(2) using resulting one-lime phosphate solution as raw material, alkaline matter is added wherein, and regulation system pH value is 0.3,
Adjust after pH value, calcium ion content accounts for 2.3% of calcium ion total content in system in the Dicalcium Phosphate formed in system.Then
Extractant organic solution is added into one-lime phosphate solution, and (extractant P204, organic solvent is kerosene, and extractant concentration is
1mol/L), the extractant organic solution is in a ratio of 1 with one-lime phosphate solution：5, extraction and recovery one-lime phosphate solution middle rare earth, extraction
It is 10 grades to take series, hydrochloric acid back extraction recovering rare earth, and back extraction series is 8 grades, and obtains the raffinate of the calcium of phosphoric acid one；
Into the raffinate of one-lime phosphate plus after sulfuric acid deliming, separation of solid and liquid, solution containing phosphate and gypsum are formed, is reclaimed phosphorous
Phosphorus in solution.And take phosphoric acid is prepared after the solution containing phosphate removal of impurities of part, and prepared phosphoric acid is returned at phosphoric acid leaching
Reason.
(3) mixing slag containing solitary rock ballast and phosphoric acid rare earth slag is included as raw material using resulting, contained according to phosphorus in slag
Amount addition iron content rare-earth tailing, it is 3.5 to control Fe/P mol ratios, and adds calcirm-fluoride according to silicone content in slag, and control F/Si rubs
You add the concentrated sulfuric acid (concentration 98.3%) mixing than being 5, then, and concentrated sulfuric acid addition is containing solitary rock ballast and phosphoric acid rare earth slag
3 times of weight, reinforcing roasting is carried out at 300 DEG C, fired slags are obtained.Water logging fired slags, obtain infusion containing rare earth after filtering
With water logging slag.The pH value for adding light dolomite regulation infusion containing rare earth is 4.5, is filtrated to get phosphoric acid iron and thorium phosphate is heavy
Form sediment, and rare earth sulfate solution；Carbonate deposition rare earth is added in rare earth sulfate solution, rare earth carbonate product is obtained.
The rare earth reclaimed with reference to the rare earth and vitriol intensified calcining monazite of extraction and recovery, whole technical process middle rare earth
The rate of recovery be 92.5%.
The preferred embodiments of the present invention are these are only, are not intended to limit the invention, for those skilled in the art
For member, the present invention can have various modifications and variations.Any modification within the spirit and principles of the invention, being made,
Equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (24)
1. from the method for synthetical recovery phosphorus and rare earth in phosphorus ore containing monazite, it is characterised in that comprise the following steps：
Phosphoric acid leaches the phosphorus ore containing monazite, and separation of solid and liquid obtains the solution of one-lime phosphate containing rare earth and containing solitary rock ballast；
Added in the solution of one-lime phosphate containing rare earth dilute in extractant organic solution, one-lime phosphate solution described in extraction and recovery
Soil, and obtain the raffinate of the calcium of phosphoric acid one；
The rare earth contained in solitary rock ballast is reclaimed, and reclaims the phosphorus in the raffinate of the calcium of phosphoric acid one；
The step of containing solitary rock ballast middle rare earth described in reclaiming includes：
It is described contain add iron containing compoundses in solitary rock ballast, and add after fluorochemical, strengthened with concentrated sulfuric acid mixing
Roasting, obtains fired slags；
The fired slags are gone out with water logging, are filtrated to get infusion containing rare earth and water logging slag；
The pH value of the regulation infusion containing rare earth is 3.5~5, is filtrated to get phosphoric acid iron and thorium phosphate precipitation, and sulfuric acid
Earth solution；
Carbonate deposition rare earth is added in the rare earth sulfate solution, rare earth carbonate product is obtained.
2. according to the method described in claim 1, it is characterised in that in the phosphoric acid leaches step, the phosphoric acid with it is described
Phosphorus ore containing monazite is according to 2~10L of liquid-solid ratio:1kg is mixed.
3. according to the method described in claim 1, it is characterised in that P in the phosphoric acid2O5Mass concentration is 15%~50%.
4. according to the method described in claim 1, it is characterised in that P in the phosphoric acid2O5Mass concentration is 20%~35%.
5. method according to any one of claim 1 to 4, it is characterised in that in the phosphoric acid leaching process, is leached
Temperature is 25 DEG C~150 DEG C, and extraction time is 0.5-8 hours.
6. method according to any one of claim 1 to 4, it is characterised in that described in the phosphoric acid leaching process
Extraction temperature is 105~130 DEG C, and extraction time is 2~5 hours.
7. according to the method described in claim 1, it is characterised in that added in the one-lime phosphate solution before extractant, first
Alkaline matter is added in the one-lime phosphate solution, using regulation system pH value as 0.1~0.5.
8. according to the method described in claim 1, it is characterised in that added in the one-lime phosphate solution before extractant, first
Alkaline matter is added in the one-lime phosphate solution, using regulation system pH value as 0.2~0.4.
9. method according to claim 7, it is characterised in that in the step of the regulation system pH value, institute's shape in system
Into Dicalcium Phosphate in calcium ion be less than system in calcium ion total content 5%.
10. method according to claim 7, it is characterised in that the alkaline matter is magnesia, magnesium hydroxide, carbonic acid
Magnesium, calcium oxide, calcium hydroxide, calcium carbonate, sodium hydroxide or sodium carbonate.
11. according to the method described in claim 1, it is characterised in that the step of extraction and recovery rare earth in the one-lime phosphate solution
In rapid, extractant is at least one of P204, P507, P215, DOPPA, DNPPA.
12. according to the method described in claim 1, it is characterised in that the step of extraction and recovery rare earth in the one-lime phosphate solution
In rapid, extractant concentration is 0.1~1.5mol/L in extractant organic solution.
13. according to the method described in claim 1, it is characterised in that the extractant organic solution and one-lime phosphate solution
Specific volume compares 1：15~10：1.
14. according to the method described in claim 1, it is characterised in that iron containing compoundses are added in containing solitary rock ballast, and are added
During fluorochemical, the fluorochemical contains solitary rock ballast by F with described:Si mol ratios are 4-6：1 mixing.
15. according to the method described in claim 1, it is characterised in that the fluorochemical is calcirm-fluoride or fluorite.
16. according to the method described in claim 1, it is characterised in that the iron containing compoundses are iron content rare-earth tailing.
17. according to the method described in claim 1, it is characterised in that described to be mixed with the concentrated sulfuric acid in progress reinforcing roasting process,
The concentrated sulfuric acid is with containing solitary rock ballast and phosphoric acid rare earth slag according to mass ratio 1-2：1 mixing.
18. according to the method described in claim 1, it is characterised in that the sintering temperature of the reinforcing calcination stepses is 250-500
℃。
19. according to the method described in claim 1, it is characterised in that during the pH value of regulation infusion containing rare earth,
Using the pH value of magnesia and/or the light dolomite regulation infusion containing rare earth.
20. according to the method described in claim 1, it is characterised in that the pH value of the regulation infusion containing rare earth to 4.0~
4.5。
21. according to the method described in claim 1, it is characterised in that during the water logging, Fe/P mol ratios are more than in immersion liquid
2。
22. according to the method described in claim 1, it is characterised in that during the water logging, Fe/P mol ratios are big in immersion liquid
In 3.
23. according to the method described in claim 1, it is characterised in that phosphorus in the raffinate for reclaiming the calcium of phosphoric acid one
The step of include：Into the raffinate of the calcium of phosphoric acid one plus after sulfuric acid deliming, separation of solid and liquid, solution containing phosphate and sulfuric acid are obtained
Calcium gypsum, reclaims the phosphorus in the solution containing phosphate.
24. method according to claim 23, it is characterised in that reclaim the step of phosphorus in the raffinate of the calcium of phosphoric acid one
Suddenly also include：Phosphoric acid will be prepared after the solution containing phosphate removal of impurities, and prepared phosphoric acid is returned into the phosphoric acid and leaches step again
Utilize.
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| CN106391293A (en) * | 2016-08-30 | 2017-02-15 | 北京矿冶研究总院 | Method for separating and enriching rare earth in phosphorite through mineral separation |
| CN106755995A (en) * | 2016-12-06 | 2017-05-31 | 贵州大学 | A kind of process for separating and recovering of rare earth containing rare earth phosphate rock and phosphorus |
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