CN105331812A

CN105331812A - Method for comprehensively recycling phosphorus and rare earth from rare earth phosphorite containing monazite

Info

Publication number: CN105331812A
Application number: CN201410375268.3A
Authority: CN
Inventors: 黄小卫; 王良士; 巫圣喜; 龙志奇; 冯宗玉; 崔大立; 董金诗; 黄莉
Original assignee: Grirem Advanced Materials Co Ltd
Current assignee: Grirem Advanced Materials Co Ltd
Priority date: 2014-07-31
Filing date: 2014-07-31
Publication date: 2016-02-17
Anticipated expiration: 2034-07-31
Also published as: CN105331812B

Abstract

The invention discloses a method for comprehensively recycling phosphorus and rare earth from rare earth phosphorite containing monazite. The method includes the following steps that rare earth phosphorite containing monazite is obtained from phosphoric acid in a leaching manner, and a monocalcium phosphate solution containing rare earth and slag containing monazite are obtained through filtration; the monocalcium phosphate solution containing rare earth is processed through a precipitation method, dissolved rare earth precipitates, a monocalcium phosphate solution and rare earth slag containing phosphoric acid are obtained through filtration, and the rare earth slag containing phosphoric acid and slag containing monazite are mixed to form mixed slag; and phosphorus in the monocalcium phosphate solution is recycled, and rare earth in the mixed slag is recycled. Acid leaching is conducted by adding phosphoric acid, phosphorus in rare earth phosphorite containing monazite forms monocalcium phosphate high in solubility, and therefore monazite existing in a precipitation manner and phosphorus can be separated. Then, the monocalcium phosphate solution containing rare earth is processed through the precipitation method, and rare earth and phosphorus elements in phosphorite can be effectively separated. Rare earth and phosphorus are effectively separated through two times of separation steps, and therefore the rare earth recycling rate is increased.

Description

From the method containing synthetical recovery phosphorus mengite rare-earth phosphorus ore and rare earth

Technical field

The present invention relates to rare earth and reclaim field, in particular to a kind of from the method containing synthetical recovery phosphorus mengite rare-earth phosphorus ore and rare earth.

Background technology

Rare-earth mineral at occurring in nature often together with the mineral paragenesis such as barite, calcite, phosphatic rock, silicate ore.Because the one-tenth ore deposit reason of mineral is different, the occurrence status of rare earth element in mineral is also different with content.In current the ores containing rare earths exploited out, the content of rare earth oxide only has percentum, even lower.In order to meet the needs that rare earth metallurgy is produced, must, first through beneficiation method, by rare earth and other ore separation, rare-earth mineral be made to obtain enrichment before smelting.The content of the mineral middle rare earth after beneficiation enrichment can reach more than 60% ~ 70%.Mineral after enrichment rare earth are commonly referred to rare earth ore concentrate, and the content of the rare earth oxide in concentrate is called the rare earth grade of concentrate.

The mineral of rare earth mainly contain hamartite, monazite, xenotime, ion adsorption type rare earth ore etc., and at present, the method reclaiming monazite middle-weight rare earths mainly contains following two kinds of modes:

(1) alkaline process disaggregating treatment monazite is applicable to high-grade solitary stone ore, in monazite and liquid caustic soda reaction process, rare earth generates water-fast oxyhydroxide, and phosphorus changes tertiary sodium phosphate into, and rare-earth hydroxide obtains mixed chlorinated rare earth through excellent molten, the removal of impurities of persalt again.If the foreign matter content such as iron, silicon is high in concentrate, easily form the colloidal materials such as water glass, ironic hydroxide, sedimentation and filtration separation circuit is difficult to carry out, and therefore this technique cannot normally be run.

(2) concentrated sulfuric acid roasting method decomposes solitary stone ore, monazite concentrate and the vitriol oil are blended in 200-220 DEG C and decompose 2-4 hour, vitriol oil consumption is 1.7-2 times of concentrate weight, after resolvent cooling with 7-10 doubly to the water extraction of concentrate weight, leach liquor middle-weight rare earths is about 55g/L (REO), 25g/LP ₂o ₅, 2.5g/LFe ₂o ₃, acidity is 2.5mol/L.This immersion liquid acidity is high, and foreign matter of phosphor, thorium are high, adopts sodium sulfate double salt precipitating rare earth and thorium, then transfers oxyhydroxide to through alkali, then adopt acid preferentially to leach rare earth, extracting and separating rear earth, thorium.The method complex process, solid-liquor separation step is many, 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 radioelement thorium is dispersed in slag and waste water and is difficult to reclaim.

Phosphorus ore is the main raw material producing phosphorus chemical product, and world phosphate resource reserve is large, normal association trace rare-earth.At present, the method reclaiming phosphorus ore middle-weight rare earths comprises: the phosphoric acid by wet process process rare earth of employing hydrochloric acid, nitrate method process phosphorus ore enters in solution, then adopts the mode recovering rare earths such as solvent extraction, ion-exchange, precipitation, crystallization; Adopt in the phosphoric acid by wet process process of sulfuric acid process process phosphorus ore, rare earth enters in solution and phosphogypsum respectively, adopt sulfuric acid to leach phosphogypsum to make rare earth enter solution again, the rare earth in solution can adopt the mode recovering rare earths such as solvent extraction, ion-exchange, precipitation, crystallization.Mixed with phosphoric acid solution by phosphorus concentrate containing rare earth in patent CN201110142415.0 and react, by Controlling Technology condition, phosphorus ore middle-weight rare earths is precipitated with fluoride form, rare earth more than 85% rare earth enters in slag.Adopt the rare earth in hydrochloric acid, nitric acid or sulfuric acid dissolution recovery slag again, but slag middle-weight rare earths grade is very low, about 1%, foreign matter of phosphor, calcium, aluminium, silicon equal size are high, and the very difficult acid dissolve of rare earth fluoride, and acid consumption is high, and the quantity of slag is large, and rare earth yield is low.The rare earth entering 15% in leach liquor in addition easily enters in gypsum tailings and is difficult to reclaim in deliming process.

Based on the existence of the problems referred to above, this area research staff, when recovering rare earth, chooses taste higher usually, and mineral or the solitary stone ore such as phosphatic rock, phosphorite that composition is relatively single.And researchist is when studying Rare earth recovery method, is usually also aimed at this taste higher, and the ore that composition is relatively single, to improve the rate of recovery of rare earth.At present, rare to be directed to quality lower, the scheme of the recovering rare earth that the composite ore that mineralogical composition is comparatively mixed proposes.And, existing higher to taste, and the recovery method of the relatively single middle-weight rare earths of composition, also and be not suitable for the rare earth reclaimed in composite ore.

To contain mengite rare-earth phosphorus ore, this mengite rare-earth phosphorus ore that contains contains various ingredients simultaneously, comprises monazite, rare earth and phosphorus ore etc.Because monazite and phosphorus ore belong to phosphate mineral, both mineralogy are comparatively close, and in the mineral of its symbiosis, often embedding cloth is in close relations for monazite and phosphorus ore.When reclaiming this composite ore rare earth elements and phosphoric, inlay due to material parcel each in composite ore and dissociate difficulty comparatively greatly, physical concentration is difficult to realize the effective sorting to ore.Particularly, need relative exacting terms owing to decomposing monazite, need higher temperature and potential of hydrogen etc., when adopting sulfuric acid process wet processing of the prior art to contain the phosphorus ore of monazite, monazite often cannot be made to decompose completely, fail to realize its effective recycling.

How to reclaim and be thisly similar to containing this kind of quality of mengite rare-earth phosphorus ore lower, the composite ore middle-weight rare earths that mineralogical composition is comparatively mixed, has become a new problem of research staff.

Summary of the invention

The present invention aims to provide a kind of from the method containing synthetical recovery phosphorus mengite rare-earth phosphorus ore and rare earth, to provide a kind of from the inferior novel method containing recovering rare earth mengite rare-earth phosphorus ore.

To achieve these goals, according to an aspect of the present invention, provide a kind of from the method containing synthetical recovery phosphorus mengite rare-earth phosphorus ore and rare earth, comprise the following steps: phosphoric acid leaches containing mengite rare-earth phosphorus ore, filter and obtain containing the mono-calcium phosphate solution of rare earth with containing solitary rock ballast; By the mono-calcium phosphate solution of precipitator method process containing rare earth, make the rare-earth precipitation of dissolving, filter and obtain mono-calcium phosphate solution and phosphoric acid rare earth slag, be mixed to form mixing slag by phosphoric acid rare earth slag with containing solitary rock ballast; Reclaim the phosphorus in mono-calcium phosphate solution, and reclaim the rare earth in mixing slag.

To achieve these goals, according to another aspect of the present invention, provide a kind of from the method containing synthetical recovery phosphorus mengite rare-earth phosphorus ore and rare earth, comprise the following steps: phosphoric acid leaches containing mengite rare-earth phosphorus ore, obtain the solidliquid mixture containing rare earth and mono-calcium phosphate solution; By precipitator method process solidliquid mixture, make the rare-earth precipitation of dissolving, filter the mixing slag obtaining mono-calcium phosphate solution and contain monazite and rare earth; Reclaim the phosphorus in mono-calcium phosphate solution, reclaim the rare earth in mixing slag.

Further, above-mentioned phosphoric acid leaches in step, and phosphoric acid mixes according to liquid-solid ratio 2-10L:1kg with containing mengite rare-earth phosphorus ore, P in preferably phosphoric acid ₂o ₅mass concentration is 15% ~ 50%, is preferably 20% ~ 35%.

Further, above-mentioned phosphoric acid leaches in step, and extraction temperature is 55 DEG C ~ 150 DEG C, and extraction time is 0.5 ~ 8 hour; Preferably, phosphoric acid extraction temperature is 60 ~ 90 DEG C, and extraction time is 2 ~ 5 hours.

Further, in above-mentioned precipitator method treatment step, add alkaline matter regulation system pH value to make the rare-earth precipitation of dissolving.

Further, in above-mentioned precipitator method treatment step, the alkaline matter added is magnesium oxide, magnesium hydroxide, magnesiumcarbonate, calcium oxide, calcium hydroxide, calcium carbonate or sodium hydroxide, sodium carbonate, preferential oxidation calcium, calcium hydroxide or calcium carbonate, preferred regulation system pH value is 0.5 ~ 2.5, and preferred system pH value is 0.5 ~ 1.5.

Further, in above-mentioned precipitator method treatment step, regulation system pH value, is less than 5% of calcium ion total content in system to make the calcium ion in the Si Liaodengji dicalcium phosphate feed grade that formed in system.

Further, in above-mentioned recovery mono-calcium phosphate solution, the step of phosphorus comprises: add sulfuric acid deliming, solid-liquid separation in mono-calcium phosphate solution after, obtains solution containing phosphate and calcium sulfate gypsum, reclaims the phosphorus in solution containing phosphate.

Further, in above-mentioned recovery mono-calcium phosphate solution, the step of phosphorus also comprises: prepare phosphoric acid by after solution containing phosphate removal of impurities, and prepared phosphoric acid is returned phosphoric acid leaching step recycling.

Further, the step of the rare earth in above-mentioned recovery mixing slag comprises: in mixing slag, add iron containing compounds, and after adding fluorochemicals, mix and carry out strengthening roasting, obtain fired slags with the vitriol oil; Fired slags adds water leaching, obtains containing rare earth infusion and water logging slag; Regulate the pH value containing rare earth infusion to be 3.5 ~ 5, filter and obtain phosphoric acid iron and thorium phosphate precipitation, and rare earth sulfate solution; In rare earth sulfate solution, add carbonate deposition rare earth, obtain rare earth carbonate product.

Further, in above-mentioned mixing slag, add iron containing compounds, and add in the process of fluorochemicals, fluorochemicals is 4.1 ~ 6:1 with mixing F:Si mol ratio in slag, preferred fluorochemicals is Calcium Fluoride (Fluorspan) or fluorite, and preferred iron containing compounds is iron content rare-earth tailing.

Further, above-mentioned mixing with the vitriol oil carries out in strengthening roasting process, and the vitriol oil mixes according to mass ratio 1-2:1 with containing solitary rock ballast and phosphoric acid rare earth slag, and preferably the maturing temperature of strengthening calcination steps is 250-500 DEG C.

Further, in the process of above-mentioned adjustment containing the pH value of rare earth infusion, adopt magnesium oxide and/or light dolomite to regulate the pH value containing rare earth infusion, preferably regulate pH value to 4 ~ 4.5 containing rare earth infusion.

Further, in above-mentioned water logging process, in immersion liquid, Fe/P mol ratio is greater than 2, is preferably greater than 3.。

Application the present invention is a kind of carries out acidleach from the method containing recovering rare earth mengite rare-earth phosphorus ore by adding phosphoric acid, makes to form solvability higher phosphorous acid one calcium containing the phosphorus in phosphorus ore, and then makes to there is monazite with precipitation forms and be separated with phosphorus ore.Again by precipitator method process containing the mono-calcium phosphate solution of rare earth, achieve being effectively separated the rare earth in phosphorus ore and phosphoric.Realize effectively being separated of rare earth and phosphorus by twice separating step, and then improve the rate of recovery of rare earth.Meanwhile, by phosphoric acid rare earth slag with containing common recovering rare earth after solitary rock ballast mixing, simplify recycling step, improve rare earth yield, realize the object of low cost synthetical recovery rare earth.

Accompanying drawing explanation

The Figure of description forming a application's part is used to provide a further understanding of the present invention, and schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:

Fig. 1 show according in one embodiment of the present invention from the flow chart of steps of the method containing recovering rare earth mengite rare-earth phosphorus ore; And

Fig. 2 show according in another embodiment of the present invention from the flow chart of steps of the method containing recovering rare earth mengite rare-earth phosphorus ore.

Embodiment

It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.Below with reference to the accompanying drawings and describe the present invention in detail in conjunction with the embodiments.

The English of monazite is called Monazite, and molecular formula is (Ln, Th) PO ₄, at least one in the rare earth element that in formula, Ln refers to except promethium.

As pointed by background technology, in the composite ore (the present invention is called for short containing mengite rare-earth phosphorus ore) of the multi mineral such as phosphatic rock and monazite, because monazite and phosphorus ore belong to phosphate mineral, both mineralogy are comparatively close, in the mineral of its symbiosis, often embedding cloth is in close relations for monazite and phosphorus ore, the comparatively difficulty that the phosphorus of composite ore of the multi mineral such as this phosphatic rock and monazite and the recovery operation of rare earth are carried out.

In order to solve above-mentioned technical barrier, in one embodiment of the invention, a kind of novel method from containing synthetical recovery phosphorus and rare earth mengite rare-earth phosphorus ore is proposed.As shown in Figure 1, the method comprises the following steps: phosphoric acid leaches containing mengite rare-earth phosphorus ore, filters the mono-calcium phosphate solution that obtains containing rare earth and contains solitary rock ballast; Contain mono-calcium phosphate solution by precipitator method process, make the rare-earth precipitation of dissolving, filter and obtain mono-calcium phosphate solution and phosphoric acid rare earth slag, be mixed to form mixing slag by phosphoric acid rare earth slag with containing solitary rock ballast; Reclaim the phosphorus in mono-calcium phosphate solution, and reclaim the rare earth in mixing slag.

Carry out acidleach at aforesaid method by adding phosphoric acid, phosphorus in phosphatic rock and rare earth are dissolved, and phosphorus forms the higher mono-calcium phosphate of solvability, and does not decompose containing rare earth monazite and stay in slag, and then monazite is separated with phosphorus.Again by precipitator method process containing the mono-calcium phosphate solution of rare earth, rare earth precipitate with the form of rare-earth phosphorate, and mono-calcium phosphate still stable existence is in solution, filtration, achieves being effectively separated the rare earth in phosphorus ore and phosphoric.Realize effectively being separated of rare earth and phosphorus by twice separating step, and then improve rare earth and the phosphorus rate of recovery separately.Meanwhile, by phosphoric acid rare earth slag and described containing recovering rare earth common after the mixing of solitary rock ballast, simplify recycling step, improve rare earth yield, realize the object of low cost synthetical recovery rare earth.

Same, in order to solve above-mentioned technical barrier, in another embodiment of the invention, propose another kind of from the novel method containing synthetical recovery phosphorus mengite rare-earth phosphorus ore and rare earth.As shown in Figure 2, the method comprises the following steps: phosphoric acid leaches containing mengite rare-earth phosphorus ore, obtains the solidliquid mixture containing rare earth and mono-calcium phosphate solution; By precipitator method process solidliquid mixture, make the rare-earth precipitation of dissolving, filter the mixing slag obtaining mono-calcium phosphate solution and contain monazite and rare earth; Reclaim the phosphorus in mono-calcium phosphate solution, reclaim the rare earth in mixing slag.

In the above-mentioned methods, acidleach is carried out by adding phosphoric acid, make to form solvability higher phosphorous acid one calcium containing the phosphorus in mengite rare-earth phosphorus ore, again by solidliquid mixture that precipitator method process step of acid dipping obtains, achieve the rare-earth precipitation being leached in step by phosphoric acid and dissolve in the solution, so with being effectively separated of phosphoric.The method is leached and the operate continuously of precipitator method process by phosphoric acid, while the flow process that simplifies the operation, realizes the high efficiency separation of rare earth and phosphorus, and then raising rare earth and the phosphorus rate of recovery separately.Meanwhile, the rare earth in phosphorus ore and monazite are all formed in mixing slag by the method, carry out rare earth recovery for this mixing slag, are conducive to simplifying recycling step, improve rare earth yield, realize the object of low cost synthetical recovery rare earth.

Adopt above-mentioned two kinds of methods, by adopting phosphoric acid to leach, forming solvability higher phosphorous acid one calcium, improving phosphorus ore resolution ratio and improve phosphrus reagent, reduce slag rate.Again by the rare earth in phosphorus ore and monazite are mixed to form mixing slag, to make in mineral the enrichment in mixing slag of more than 90% rare earth, be conducive to improving mixing slag middle-weight rare earths deposition rate and grade significantly improves, be conducive to the recovery of follow-up rare earth.

The object that phosphoric acid leaches in the present invention is will containing phosphoric stripping in mengite rare-earth phosphorus ore, and monazite does not decompose to stay in slag and makes rare-earth enrichment, reduces sour consumption.In the preferred embodiment of the present invention, above-mentioned phosphoric acid leaches in step, and phosphoric acid and ore deposit are that 2-10L:1kg mixes according to liquid-solid ratio.By controlling phosphoric acid consumption, being conducive to when reducing phosphoric acid consumption, making phosphorus and calcium generate soluble phosphoric acid one calcium (Ca (H ₂pO ₄) ₂) enter solution, now, insoluble monazite will be stayed in slag, which achieves effectively being separated of phosphorus ore and monazite.In actually operating, the rare earth in phosphatic rock inevitably also can be dissolved, and this part is precipitated in follow-up precipitator method treatment step by the rare earth dissolved, to realize effective enrichment of rare earth.

Preferably, P in the phosphoric acid used in step is leached at above-mentioned phosphoric acid ₂o ₅weight concentration is 15% ~ 50%, is preferably 20% ~ 35%.P in used phosphoric acid in the present invention ₂o ₅weight concentration is not limited to above-mentioned scope, at employing P ₂o ₅during the phosphoric acid of weight concentration in above-mentioned scope, higher acidity is conducive to the decomposition of phosphorus ore, thus improves the yield of phosphorus, but too high phosphorus acid content then exists the problems such as subsequent handling process energy consumption is high;

Preferably, leach in step at above-mentioned phosphoric acid, extraction temperature is 55 DEG C ~ 150 DEG C, and extraction time is 0.5 ~ 8 hour.Phosphoric acid of the present invention leaches extraction temperature and extraction time in step and is not limited to above-mentioned scope, and by adopting higher temperature, the decomposition of favourable phosphorus ore, and at high temperature rare-earth phosphorate solubility product is little, is conducive to forming RE phosphate precipitation and enters enrichment in slag.More preferably, the temperature that phosphoric acid leaches is 60 ~ 90 DEG C, and extraction time is 2 ~ 5 hours.

That the rare earth element dissolved in phosphoric acid leaching process in the solution and thorium element are precipitated in the object of above-mentioned precipitator method treatment step.In actually operating, select the suitable precipitator method to carry out precipitation process to the solidliquid mixture containing mono-calcium phosphate according to the application's above-mentioned purpose.In the preferred embodiment of the present invention, in above-mentioned precipitator method treatment step, form calcium phosphate precipitation by adding alkaline matter regulation system pH value enter enrichment in slag to make dissolving at phosphoric acid leaching process the rare earth, the thorium that.This method, by simply adjusting system pH, makes rare earth, thorium form calcium phosphate precipitation, and then is effectively separated with calcium with phosphorus, avoids rare earth in subsequent wet sulfur process, enter phosphogypsum loss.It is emphasized that in this precipitator method treatment step, add alkaline matter regulation system pH value, in method one, refer to the mono-calcium phosphate solution containing rare earth, in method two, refer to solidliquid mixture.

Preferably, in above-mentioned precipitator method treatment step, alkaline matter includes but not limited to magnesium oxide, magnesium hydroxide, magnesiumcarbonate, calcium oxide, calcium hydroxide, calcium carbonate, sodium hydroxide or sodium carbonate.Wherein be preferably calcium oxide, calcium hydroxide or calcium carbonate.Employing calcium oxide, calcium hydroxide or calcium carbonate while phosphorus and rare earth being carried out being separated, also have the advantage not introducing the impurity such as magnesium, sodium as alkaline matter.

Preferably, in above-mentioned precipitator method treatment step, be 0.5-2.5 by adding alkaline matter regulation system pH value, more preferably regulation system pH value is 0.5-1.5.PH value is controlled within the scope of this, be conducive to keeping calcium to exist with the form of mono-calcium phosphate, with by phosphoric and rare earths separation.More have preferably, in above-mentioned precipitator method treatment step, after regulation system pH value, the amount of the Si Liaodengji dicalcium phosphate feed grade formed in system is that wherein calcium ion is less than 5% of the total content of calcium ion in system.By controlling the amount of Si Liaodengji dicalcium phosphate feed grade, to make the form of phosphorus and calcium mono-calcium phosphate as much as possible in system exist, be conducive to making phosphoric and rare earths separation, and then increase the rate of recovery of phosphoric and rare earth element.

Before the step of the phosphorus in the present invention in above-mentioned recovery mono-calcium phosphate solution, phosphorus is separated with rare earth.Scheme Choice for the phosphorus reclaimed in mono-calcium phosphate solution is applicable to the method that phosphorus reclaims targetedly.In the preferred embodiment of the present invention, the step of the phosphorus in above-mentioned recovery mono-calcium phosphate solution comprises: add sulfuric acid deliming, solid-liquid separation in leach liquor after, forms solution containing phosphate and calcium sulfate gypsum, reclaims the phosphorus in solution containing phosphate.Reclaim phosphorus in phosphatic rock in the method and adopt ripe wet method sulfur process, this processing step is simple, and the rate of recovery is relatively high.

Preferably, the step of the phosphorus in above-mentioned recovery mono-calcium phosphate solution also comprises: prepare phosphoric acid by after solution containing phosphate removal of impurities, and prepared phosphoric acid is returned leaching phosphorus ore treatment step.In this approach, the phosphoric acid of recovery is used for the decomposition leaching of phosphatic rock and rare earth, whole Connection between Processes is reasonable, realizes rare earth and phosphorus high efficiente callback simultaneously, the low and low price of sulfuric acid consumption.In above-mentioned steps, the step of removal of impurities includes but not limited to solution containing phosphate deironing, silicon, aluminium, calcium, magnesium, thorium, uranium step.The step of these removal of impurities adopts common process of the prior art as required.

Same, before the step of the rare earth in the present invention in above-mentioned recovery mixing slag (comprise phosphoric acid rare earth slag and contain solitary rock ballast), phosphorus is separated with rare earth.For mixing slag Rare-Earth Content than phosphorus ore height 4-6 doubly, but content of rare earth is still lower, and the foreign matter content such as phosphorus, silicon, aluminium is high, adopts conventional sodium hydroxide decomposition method, sulfuric acid decomposition method is difficult to the efficient recovery realizing rare earth.In the preferred embodiment of the present invention, the step of above-mentioned recovery mixing slag middle-weight rare earths comprises: in mixing slag, add iron containing compounds, and after adding fluorochemicals, mix and carry out strengthening roasting, obtain fired slags with the vitriol oil; Fired slags is filtered in water logging, obtains containing rare earth infusion and water logging slag; Regulate the pH value containing rare earth infusion to be 3.5 ~ 5, make phosphorus form tertiary iron phosphate and thorium phosphate precipitation, and rare earth sulfate solution; And in rare earth sulfate solution, add carbonate deposition rare earth, obtain rare earth carbonate product.Now, further roasting rare earth carbonate can obtain earth oxide product.

The rare-earth phosphorate of monazite and precipitation is stayed in slag and is obtained enrichment by the present invention, and slag middle-weight rare earths grade can be made to improve, and significantly reduces subsequent disposal amount.Adopt unique simple process adding the solid phosphorus of iron, the vitriol intensified roasting of fluoridize silica removal again, eliminate the interference of phosphorus and silicon, thus effectively avoid leaching process middle-weight rare earths with the loss of rare-earth phosphorate precipitation; And avoid the formation of silica gel, affect subsequent filter separation circuit.The method acid and alkali consumption is few, and rare earth yield can reach more than 90%; Thorium is converted into thorium pyrophosphate is solidificated in slag simultaneously, avoids the dispersion of radiothorium in technical process to pollute.Meanwhile, solid phosphorus is carried out by adding iron containing compounds.

Preferably, above-mentioned added iron containing compounds is iron content rare-earth tailing.Add iron content rare-earth tailing to process, not only increase rare-earth yield, and achieve the comprehensive utilization of mine tailing iron resources, and achieve the recycling of this mine tailing middle-weight rare earths, significantly reduce running cost simultaneously.

Preferably, above-mentionedly in mixing slag, add iron containing compounds, and add in the process of fluorochemicals, fluorochemicals is 4.1 ~ 6:1 with mixing F:Si mol ratio in slag.Fluorochemicals is not limited to above-mentioned scope with the blending ratio mixing slag in the present invention, by by both being 4.1 ~ 6:1 mixing in molar ratio, be conducive under the prerequisite of the input amount reducing fluorochemicals, silicon in ore deposit can be formed the effusion of silicon fluoride gas at roasting process, avoid silicon in solution dedoping step, to form silica gel precipitate the filtering separation difficulty and the loss that causes of precipitation process absorption rare earth that cause, thus improve the yield of rare earth.Wherein operable fluorochemicals includes but not limited to Calcium Fluoride (Fluorspan) and fluorite.

Preferably, carry out in strengthening roasting process in above-mentioned to mix with the vitriol oil, the vitriol oil mixes than 1 ~ 2L:1kg according to liquid-solid ratio with containing solitary rock ballast and phosphoric acid rare earth slag, and maturing temperature is 250 ~ 500 DEG C.In this temperature range, carry out that roasting is conducive to that thorium, iron and phosphoric acid are formed phosphoric acid salt, pyrophosphate salt precipitates to be solidificated in slag and do not leached, radioelement thorium is also solidificated in slag simultaneously, avoids the dispersion of radiothorium in technical process to pollute.The concentration of the vitriol oil used in above-mentioned steps is more than or equal to the vitriol oil of 70%, is preferably the vitriol oil of concentration 98.3%.

Preferably, contain in the process of the pH value of rare earth infusion in above-mentioned adjustment, adopt magnesium oxide and/or light dolomite to regulate the pH value containing rare earth infusion, preferably adjustment is containing pH value to 4 ~ 4.5 of rare earth infusion.Adopt magnesium oxide and/or light dolomite to regulate the pH value containing rare earth infusion to have and make phosphorus as far as possible all form tertiary iron phosphate and thorium phosphate precipitation, the non-setting effect of rare earth.

Preferably, in above-mentioned water logging process, in immersion liquid, Fe/P mol ratio is greater than 2, is preferably greater than 3, and being more preferably Fe/P mol ratio is 3 ~ 6.Both ratio control are had within the scope of this and removes phosphorus in solution, improve the effect of rare-earth yield.And follow-up be in 3 ~ 5 dedoping step in adjust ph, control Fe/P mol ratio is greater than 2 effectively can form tertiary iron phosphate precipitation, and phosphor-removing effect is good, and excessive iron hydrolyzable under this pH value condition forms precipitation, avoid the formation of rare-earth phosphorate precipitation, thus avoid the loss of rare earth.

Beneficial effect of the present invention is further illustrated below with reference to embodiment 1-16.

Embodiment 1-1

With 50g containing monazite 23.6%, total amount of rare earth be the phosphorus ore of 15.5% for raw material, adopt mass concentration to be 15% (with P ₂o ₅meter) phosphoric acid solution leach, hierarchy of control liquid-solid ratio 2:1, adds the phosphoric acid solution of 100mL, at 55 DEG C, react 8h, obtains 124mL and contain the mono-calcium phosphate solution of rare earth and 12g containing solitary rock ballast after filtering.

Add sodium carbonate toward containing in mono-calcium phosphate solution, regulator solution pH is 0.5, makes the rare-earth precipitation in solution, obtains 130mL mono-calcium phosphate solution and 5.5g phosphoric acid rare earth slag after filtration.After adjust ph, in the Si Liaodengji dicalcium phosphate feed grade formed in system, calcium ion content accounts for 1.3% of calcium ion total content in system.

Add sulfuric acid deliming, solid-liquid separation in obtained mono-calcium phosphate solution after, form solution containing phosphate and gypsum, reclaim the phosphorus in solution containing phosphate.And prepare phosphoric acid after getting the removal of impurities of part solution containing phosphate, and prepared phosphoric acid is returned for phosphoric acid leaching process, the content of wherein obtained after tested mono-calcium phosphate solution middle-weight rare earths is 2.9g/L.

Obtained phosphoric acid rare earth slag and obtain are mixed to form mixing slag containing solitary rock ballast, and the gross weight of the mixing slag obtained is 17.5g, and it accounts for 35.0% of phosphorus ore raw material weight.

In the above-mentioned methods, except the rare earth contained in phosphoric acid one calcium solution, other rare earth all enter into obtain mixing slag, it is 95.1% of total rare earth (TRE) amount in phosphorus ore raw material that institute obtains mixing slag middle-weight rare earths amount.

Embodiment 1-2

Preparation technology is identical with embodiment 1-1, and difference is, after the step adding phosphoric acid leaching, does not filter, directly adds sodium carbonate, make the rare-earth precipitation in solution, obtains comprising phosphoric acid rare earth slag and the mixing slag containing solitary rock ballast.Wherein:

The weight of the mixing slag obtained is 17.7g, and it accounts for 35.4% of phosphorus ore raw material weight.

The amount calculated containing rare earth in the mono-calcium phosphate solution obtained is 0.37g after tested; Except the rare earth contained in phosphoric acid one calcium solution, other rare earth all enter into obtain mix slag, now, the rare earth content that obtains is 7.38g, and it is 95.2% of total rare earth (TRE) amount in phosphorus ore raw material.

Embodiment 2-1

With 50g containing monazite 10.0%, total amount of rare earth be the phosphorus ore of 6.2% for raw material, adopt mass concentration to be 18% (with P ₂o ₅meter) phosphoric acid solution leach, hierarchy of control liquid-solid ratio 4:1, reacts 0.5h at 60 DEG C, obtains mono-calcium phosphate solution containing rare earth and containing solitary rock ballast after filtering.

Add sodium hydroxide toward containing in mono-calcium phosphate solution, regulator solution pH is 1.0, makes the rare-earth precipitation in solution, obtains mono-calcium phosphate solution and phosphoric acid rare earth slag after filtration.After adjust ph, in the Si Liaodengji dicalcium phosphate feed grade formed in system, calcium ion content accounts for 2.2% of calcium ion total content in system.

Add sulfuric acid deliming, solid-liquid separation in obtained mono-calcium phosphate solution after, form solution containing phosphate and gypsum, reclaim the phosphorus in solution containing phosphate.And prepare phosphoric acid after getting the removal of impurities of part solution containing phosphate, and prepared phosphoric acid is returned for phosphoric acid leaching process., wherein calculate after tested, containing rare earth 0.13g in the mono-calcium phosphate solution obtained.

Obtained phosphoric acid rare earth slag and obtain are mixed to form mixing slag containing solitary rock ballast, and the gross weight of the mixing slag obtained is 15.6g, and it accounts for 31.2% of phosphorus ore raw material weight.

In the above-mentioned methods, except the rare earth contained in phosphoric acid one calcium solution, other rare earth all enter into obtain mixing slag, it is 95.9% of total rare earth (TRE) amount in phosphorus ore raw material that institute obtains mixing slag middle-weight rare earths amount.

Embodiment 2-2

Preparation technology is identical with embodiment 2-1, and difference is, after the step adding phosphoric acid leaching, does not filter, directly adds sodium carbonate, make the rare-earth precipitation in solution, obtains comprising phosphoric acid rare earth slag and the mixing slag containing solitary rock ballast.Wherein:

The weight of the mixing slag obtained is 15.7g, and it accounts for 31.4% of phosphorus ore raw material weight.

Calculate after tested, containing rare earth 0.12g in the mono-calcium phosphate solution obtained; Except the rare earth contained in phosphoric acid one calcium solution, other rare earth all enter into obtain mix slag, now, the rare earth content that obtains is 2.98g, and it is 96.2% of total rare earth (TRE) amount in phosphorus ore raw material.

Embodiment 3-1

With 100g containing monazite 5.8%, total amount of rare earth be the phosphorus ore of 3.9% for raw material, adopt mass concentration to be 35% (with P ₂o ₅meter) phosphoric acid solution leach, hierarchy of control liquid-solid ratio 10:1, reacts 1h at 70 DEG C, obtains mono-calcium phosphate solution containing rare earth and containing solitary rock ballast after filtering.

Add magnesium oxide toward containing in mono-calcium phosphate solution, regulator solution pH is 2, makes the rare-earth precipitation in solution, obtains mono-calcium phosphate solution and phosphoric acid rare earth slag after filtration.After adjust ph, in the Si Liaodengji dicalcium phosphate feed grade formed in system, calcium ion content accounts for the 4.1%. of calcium ion total content in system.

Add sulfuric acid deliming, solid-liquid separation in obtained mono-calcium phosphate solution after, form solution containing phosphate and gypsum, reclaim the phosphorus in solution containing phosphate.And prepare phosphoric acid after getting the removal of impurities of part solution containing phosphate, and prepared phosphoric acid is returned for phosphoric acid leaching process, wherein calculate after tested, containing rare earth 0.13g in the mono-calcium phosphate solution obtained.。

Obtained phosphoric acid rare earth slag and institute are obtained being mixed to form mixing slag containing solitary rock ballast, the gross weight that institute obtains mixing slag is 19.7g, and it accounts for 19.7% of phosphorus ore raw material weight.

In the above-mentioned methods, except the rare earth contained in phosphoric acid one calcium solution, other rare earth all enter into obtain mixing slag, it is 96.7% of total rare earth (TRE) amount in phosphorus ore raw material that institute obtains mixing slag middle-weight rare earths amount.

Embodiment 3-2

Preparation technology is identical with embodiment 3-1, and difference is, after the step adding phosphoric acid leaching, does not filter, directly adds sodium carbonate, make the rare-earth precipitation in solution, obtains comprising phosphoric acid rare earth slag and the mixing slag containing solitary rock ballast.Wherein:

The weight of the mixing slag obtained is 20.0g, and it accounts for 20.0% of phosphorus ore raw material weight.

Calculate after tested, containing rare earth 0.12g in the mono-calcium phosphate solution obtained; Except the rare earth contained in phosphoric acid one calcium solution, other rare earth all enter into obtain mix slag, now, the rare earth content that obtains is 3.78g, and it is 97.0% of total rare earth (TRE) amount in phosphorus ore raw material.

Embodiment 4-1

With 100g containing monazite 9.4%, total amount of rare earth be the phosphorus ore of 5.7% for raw material, adopt mass concentration to be 20% (with P ₂o ₅meter) phosphoric acid solution leach, hierarchy of control liquid-solid ratio 7:1, reacts 2h at 90 DEG C, obtains mono-calcium phosphate solution containing rare earth and containing solitary rock ballast after filtering;

Add calcium oxide toward containing in mono-calcium phosphate solution, regulator solution pH is 2.5, makes the rare-earth precipitation in solution, obtains mono-calcium phosphate solution and phosphoric acid rare earth slag after filtration.After adjust ph, in the Si Liaodengji dicalcium phosphate feed grade formed in system, calcium ion content accounts for 4.7% of calcium ion total content in system.

Add sulfuric acid deliming, solid-liquid separation in obtained mono-calcium phosphate solution after, form solution containing phosphate and gypsum, reclaim the phosphorus in solution containing phosphate.And prepare phosphoric acid after getting the removal of impurities of part solution containing phosphate, and prepared phosphoric acid is returned for phosphoric acid leaching process, calculate after tested, containing rare earth in the mono-calcium phosphate solution obtained is 0.17g.

Obtained phosphoric acid rare earth slag and institute are obtained being mixed to form mixing slag containing solitary rock ballast, the gross weight that institute obtains mixing slag is 23.7g, and it accounts for 23.7% of phosphorus ore raw material weight.

In the above-mentioned methods, except the rare earth contained in phosphoric acid one calcium solution, other rare earth all enter into obtain mixing slag, it is 97.0% of total rare earth (TRE) amount in phosphorus ore raw material that institute obtains mixing slag middle-weight rare earths amount.

Embodiment 4-2

Preparation technology is identical with embodiment 4-1, and difference is, after the step adding phosphoric acid leaching, does not filter, directly adds sodium carbonate, make the rare-earth precipitation in solution, obtains comprising phosphoric acid rare earth slag and the mixing slag containing solitary rock ballast.Wherein:

The weight of the mixing slag obtained is 23.8g, and it accounts for 23.8% of phosphorus ore raw material weight.

The content calculating the mono-calcium phosphate solution middle-weight rare earths obtained after tested is 0.17g; Except the rare earth contained in phosphoric acid one calcium solution, other rare earth all enter into obtain mix slag, now, the rare earth content that obtains is 5.53g, and it is 97.1% of total rare earth (TRE) amount in phosphorus ore raw material.

Embodiment 5-1

With 100g containing monazite 11.9%, total amount of rare earth be the phosphorus ore of 7.5% for raw material, adopt mass concentration to be 25% (with P ₂o ₅meter) phosphoric acid solution leach, hierarchy of control liquid-solid ratio 8:1, adds the phosphoric acid solution of 800mL, at 80 DEG C, react 3h, obtains about 820mL containing the mono-calcium phosphate solution of rare earth and about 12g containing solitary rock ballast after filtering;

Add calcium hydroxide toward containing in mono-calcium phosphate solution, regulator solution pH is 1.5, makes the rare-earth precipitation in solution, obtains the mono-calcium phosphate solution of about 835mL and the phosphoric acid rare earth slag of about 10g after filtration.After adjust ph, in the Si Liaodengji dicalcium phosphate feed grade formed in system, calcium ion content accounts for 2.1% of calcium ion total content in system.

Add sulfuric acid deliming, solid-liquid separation in obtained mono-calcium phosphate solution after, form solution containing phosphate and gypsum, reclaim the phosphorus in solution containing phosphate.And prepare phosphoric acid after getting the removal of impurities of part solution containing phosphate, and prepared phosphoric acid is returned for phosphoric acid leaching process, calculate after tested, containing rare earth in the mono-calcium phosphate solution obtained is 0.08g.。

Obtained phosphoric acid rare earth slag and obtain are mixed to form mixing slag containing solitary rock ballast, and the gross weight of the mixing slag obtained is 22g, and it accounts for 22.0% of phosphorus ore raw material weight.

In the above-mentioned methods, except the rare earth contained in phosphoric acid one calcium solution, other rare earth all enter into obtain mixing slag, it is 98.9% of total rare earth (TRE) amount in phosphorus ore raw material that institute obtains mixing slag middle-weight rare earths amount.

Embodiment 5-2

Preparation technology is identical with embodiment 5-1, and difference is, after the step adding phosphoric acid leaching, does not filter, directly adds sodium carbonate, make the rare-earth precipitation in solution, obtains comprising phosphoric acid rare earth slag and the mixing slag containing solitary rock ballast.Wherein:

The weight of the mixing slag obtained is 22.2g, and it accounts for 22.2% of phosphorus ore raw material weight.

The content calculating the mono-calcium phosphate solution middle-weight rare earths obtained after tested is 0.07g; Except the rare earth contained in phosphoric acid one calcium solution, other rare earth all enter into obtain mix slag, now, the rare earth content that obtains is 7.43g, and it is 99.1% of total rare earth (TRE) amount in phosphorus ore raw material.

Embodiment 6-1

With 100g containing monazite 10.6%, total amount of rare earth be the phosphorus ore of 6.8% for raw material, adopt mass concentration to be 22% (with P ₂o ₅meter) phosphoric acid solution leach, hierarchy of control liquid-solid ratio 6:1, reacts 4h at 90 DEG C, obtains mono-calcium phosphate solution containing rare earth and containing solitary rock ballast after filtering;

Add sodium hydroxide toward containing in mono-calcium phosphate solution, regulator solution pH is 1.2, makes the rare-earth precipitation in solution, obtains mono-calcium phosphate solution and phosphoric acid rare earth slag after filtration.After adjust ph, in the Si Liaodengji dicalcium phosphate feed grade formed in system, calcium ion content accounts for 2.0% of calcium ion total content in system.

Add sulfuric acid deliming, solid-liquid separation in obtained mono-calcium phosphate solution after, form solution containing phosphate and gypsum, reclaim the phosphorus in solution containing phosphate.And prepare phosphoric acid after getting the removal of impurities of part solution containing phosphate, and prepared phosphoric acid is returned for phosphoric acid leaching process, calculate after tested, containing rare earth in the mono-calcium phosphate solution obtained is 0.09g.

Obtained phosphoric acid rare earth slag and institute are obtained being mixed to form mixing slag containing solitary rock ballast, the gross weight that institute obtains mixing slag is 21.2g, and it accounts for 21.2% of phosphorus ore raw material weight.

In the above-mentioned methods, except the rare earth contained in phosphoric acid one calcium solution, other rare earth all enter into obtain mixing slag, it is 98.7% of total rare earth (TRE) amount in phosphorus ore raw material that institute obtains mixing slag middle-weight rare earths amount.

Embodiment 6-2

Preparation technology is identical with embodiment 6-1, and difference is, after the step adding phosphoric acid leaching, does not filter, directly adds sodium carbonate, make the rare-earth precipitation in solution, obtains comprising phosphoric acid rare earth slag and the mixing slag containing solitary rock ballast.

The weight of the mixing slag obtained is 21.3g, and it accounts for 21.3% of phosphorus ore raw material weight.

The content calculating the mono-calcium phosphate solution middle-weight rare earths obtained after tested is 0.08g; Except the rare earth contained in phosphoric acid one calcium solution, other rare earth all enter into obtain mix slag, now, the rare earth content that obtains is 6.72g, and it is 98.8% of total rare earth (TRE) amount in phosphorus ore raw material.

Embodiment 7-1

With 100g containing monazite 11.2%, total amount of rare earth be the phosphorus ore of 7.0% for raw material, adopt mass concentration to be 20% (with P ₂o ₅meter) phosphoric acid solution leach, hierarchy of control liquid-solid ratio 5:1, reacts 5h at 100 DEG C, obtains mono-calcium phosphate solution containing rare earth and containing solitary rock ballast after filtering;

Add sodium carbonate toward containing in mono-calcium phosphate solution, regulator solution pH is 0.8, makes the rare-earth precipitation in solution, obtains mono-calcium phosphate solution and phosphoric acid rare earth slag after filtration.After adjust ph, in the Si Liaodengji dicalcium phosphate feed grade formed in system, calcium ion content accounts for 1.7% of calcium ion total content in system.

Add sulfuric acid deliming, solid-liquid separation in obtained mono-calcium phosphate solution after, form solution containing phosphate and gypsum, reclaim the phosphorus in solution containing phosphate.And prepare phosphoric acid after getting the removal of impurities of part solution containing phosphate, and prepared phosphoric acid is returned for phosphoric acid leaching process, calculate after tested, containing rare earth in the mono-calcium phosphate solution obtained is 0.11g.

Obtained phosphoric acid rare earth slag and obtain are mixed to form mixing slag containing solitary rock ballast, and the gross weight of the mixing slag obtained is 22.4g, and it accounts for 22.4% of phosphorus ore raw material weight.

In the above-mentioned methods, except the rare earth contained in phosphoric acid one calcium solution, other rare earth all enter into obtain mixing slag, it is 98.5% of total rare earth (TRE) amount in phosphorus ore raw material that institute obtains mixing slag middle-weight rare earths amount.

Embodiment 7-2

Preparation technology is identical with embodiment 7-1, and difference is, after the step adding phosphoric acid leaching, does not filter, directly adds sodium carbonate, make the rare-earth precipitation in solution, obtains comprising phosphoric acid rare earth slag and the mixing slag containing solitary rock ballast.Wherein:

The weight of the mixing slag obtained is 22.6g, and it accounts for 22.6% of phosphorus ore raw material weight.

The content calculating the mono-calcium phosphate solution middle-weight rare earths obtained after tested is 0.1g.; Except the rare earth contained in phosphoric acid one calcium solution, other rare earth all enter into obtain mix slag, now, the rare earth content that obtains is 6.9g, and it is 98.6% of total rare earth (TRE) amount in phosphorus ore raw material.

Embodiment 8-1

With 100g containing monazite 32.5%, total amount of rare earth be the phosphorus ore of 20.3% for raw material, adopt mass concentration to be 50% (with P ₂o ₅meter) phosphoric acid solution leach, hierarchy of control liquid-solid ratio 7:1, reacts 3h at 150 DEG C, obtains mono-calcium phosphate solution containing rare earth and containing solitary rock ballast after filtering;

Add magnesiumcarbonate toward containing in mono-calcium phosphate solution, regulator solution pH is 0.5, makes the rare-earth precipitation in solution, obtains mono-calcium phosphate solution and phosphoric acid rare earth slag after filtration.After adjust ph, in the Si Liaodengji dicalcium phosphate feed grade formed in system, calcium ion content accounts for 2.3% of calcium ion total content in system.

Add sulfuric acid deliming, solid-liquid separation in obtained mono-calcium phosphate solution after, form solution containing phosphate and gypsum, reclaim the phosphorus in solution containing phosphate.And prepare phosphoric acid after getting the removal of impurities of part solution containing phosphate, and prepared phosphoric acid is returned for phosphoric acid leaching process, calculate after tested, containing rare earth in the mono-calcium phosphate solution obtained is 0.45g.

Obtained phosphoric acid rare earth slag and obtain are mixed to form mixing slag containing solitary rock ballast, and the weight of the mixing slag obtained is 41.9g, and it accounts for 41.9% of phosphorus ore raw material weight.

In the above-mentioned methods, except the rare earth contained in phosphoric acid one calcium solution, other rare earth all enter into obtain mixing slag, it is 97.8% of total rare earth (TRE) amount in phosphorus ore raw material that institute obtains mixing slag middle-weight rare earths amount.

Embodiment 8-2

Preparation technology is identical with embodiment 8-1, and difference is, after the step adding phosphoric acid leaching, does not filter, directly adds sodium carbonate, make the rare-earth precipitation in solution, obtains comprising phosphoric acid rare earth slag and the mixing slag containing solitary rock ballast.Wherein:

The weight of the mixing slag obtained is 42.1g, and it accounts for 42.1% of phosphorus ore raw material weight.

The content calculating the mono-calcium phosphate solution middle-weight rare earths obtained after tested is 0.41g; Except the rare earth contained in phosphoric acid one calcium solution, other rare earth all enter into obtain mix slag, now, the rare earth content that obtains is 19.89g, and it is 98.0% of total rare earth (TRE) amount in phosphorus ore raw material.

Embodiment 9-1

With 100g containing monazite 16.2%, total amount of rare earth be the phosphorus ore of 10.1% for raw material, adopt mass concentration to be 40% (with P ₂o ₅meter) phosphoric acid solution leach, hierarchy of control liquid-solid ratio 6:1, reacts 7h at 58 DEG C, obtains mono-calcium phosphate solution containing rare earth and containing solitary rock ballast after filtering;

Add calcium carbonate toward containing in mono-calcium phosphate solution, regulator solution pH is 1, makes the rare-earth precipitation in solution, obtains mono-calcium phosphate solution and phosphoric acid rare earth slag after filtration.After adjust ph, in the Si Liaodengji dicalcium phosphate feed grade formed in system, calcium ion content accounts for 1.5% of calcium ion total content in system.

Add sulfuric acid deliming, solid-liquid separation in obtained mono-calcium phosphate solution after, form solution containing phosphate and gypsum, reclaim the phosphorus in solution containing phosphate.And prepare phosphoric acid after getting the removal of impurities of part solution containing phosphate, and prepared phosphoric acid is returned for phosphoric acid leaching process, calculate after tested, containing rare earth in the mono-calcium phosphate solution obtained is 0.36g.

Obtained phosphoric acid rare earth slag and institute are obtained being mixed to form mixing slag containing solitary rock ballast, the gross weight that institute obtains mixing slag is 34.3g, and it accounts for 34.3% of phosphorus ore raw material weight.

In the above-mentioned methods, except the rare earth contained in phosphoric acid one calcium solution, other rare earth all enter into obtain mixing slag, to obtain rare earth content be phosphorus ore is 96.4% of total rare earth (TRE) amount in raw material.

Embodiment 9-2

Preparation technology is identical with embodiment 9-1, and difference is, after the step adding phosphoric acid leaching, does not filter, directly adds sodium carbonate, make the rare-earth precipitation in solution, obtains comprising phosphoric acid rare earth slag and the mixing slag containing solitary rock ballast.Wherein:

The weight of the mixing slag obtained is 34.5g, and it accounts for 34.5% of phosphorus ore raw material weight.

The content calculating the mono-calcium phosphate solution middle-weight rare earths obtained after tested is 0.34g; Except the rare earth contained in phosphoric acid one calcium solution, other rare earth all enter into obtain mixing slag, it is 9.76g that institute obtains mixing slag middle-weight rare earths amount, accounts for 96.6% of total rare earth (TRE) amount in phosphorus ore raw material.

Embodiment 10-1

With 100g containing monazite 10.0%, total amount of rare earth be the phosphorus ore of 6.2% for raw material, adopt mass concentration to be 60% (with P ₂o ₅meter) phosphoric acid solution leach, hierarchy of control liquid-solid ratio 7:1, reacts 10h at 50 DEG C, obtains mono-calcium phosphate solution containing rare earth and containing solitary rock ballast after filtering.

Add sodium hydroxide toward containing in mono-calcium phosphate solution, regulator solution pH is 3, makes the rare-earth precipitation in solution, obtains mono-calcium phosphate solution and phosphoric acid rare earth slag after filtration.After adjust ph, in the Si Liaodengji dicalcium phosphate feed grade formed in system, calcium ion content accounts for 16% of calcium ion total content in system.

Add sulfuric acid deliming, solid-liquid separation in obtained mono-calcium phosphate solution after, form solution containing phosphate and gypsum, reclaim the phosphorus in solution containing phosphate.And prepare phosphoric acid after getting the removal of impurities of part solution containing phosphate, and prepared phosphoric acid is returned for phosphoric acid leaching process, the content wherein calculating the mono-calcium phosphate solution middle-weight rare earths obtained after tested is 0.44g.

Obtained phosphoric acid rare earth slag and obtain are mixed to form mixing slag containing solitary rock ballast, and the gross weight obtained is 58.5g, and it accounts for 58.5% of phosphorus ore raw material weight.

In the above-mentioned methods, except the rare earth contained in phosphoric acid one calcium solution, other rare earth all enter into obtain mixing slag, it is 92.9% of total rare earth (TRE) amount in phosphorus ore raw material that institute obtains mixing slag middle-weight rare earths amount.

Embodiment 10-2

Preparation technology is identical with embodiment 10-1, and difference is, after the step adding phosphoric acid leaching, does not filter, directly adds sodium carbonate, make the rare-earth precipitation in solution, obtains comprising phosphoric acid rare earth slag and the mixing slag containing solitary rock ballast.Wherein:

The weight of the mixing slag obtained is 58.7g, and it accounts for 58.7% of phosphorus ore raw material weight.

The content calculating the mono-calcium phosphate solution middle-weight rare earths obtained after tested is 0.43g; Except the rare earth contained in phosphoric acid one calcium solution, other rare earth all enter into obtain mix slag, now, the rare earth content that obtains is 5.77g, and it is 93.0% of total rare earth (TRE) amount in phosphorus ore raw material.

Embodiment 11-1

With 500g containing the phosphorus ore of monazite 1.5%, rare earth 1% for raw material, adopt mass concentration to be 30% (with P ₂o ₅meter) phosphoric acid solution leach, hierarchy of control liquid-solid ratio 7:1, reacts 4h at 80 DEG C, obtains mono-calcium phosphate solution containing rare earth and containing solitary rock ballast after filtering;

Add calcium carbonate toward containing in mono-calcium phosphate solution, regulator solution pH is 0.5, makes the rare-earth precipitation in solution, obtains mono-calcium phosphate solution and phosphoric acid rare earth slag after filtration.After adjust ph, in the Si Liaodengji dicalcium phosphate feed grade formed in system, calcium ion content accounts for 1.2% of calcium ion total content in system.Calculate after tested, containing rare earth in the mono-calcium phosphate solution obtained is 0.13g.

Add sulfuric acid deliming, solid-liquid separation in mono-calcium phosphate solution after, form solution containing phosphate and gypsum, reclaim the phosphorus in solution containing phosphate.And prepare phosphoric acid after getting the removal of impurities of part solution containing phosphate, and prepared phosphoric acid is returned for phosphoric acid leaching process.

The gross weight comprised containing the mixing slag of solitary rock ballast and phosphoric acid rare earth slag obtained is 17.5g, accounts for 3.5% of phosphorus ore raw material weight, to obtain mixing slag middle-weight rare earths be phosphorus ore is 97.5% of total rare earth (TRE) amount in raw material.

Embodiment 11-2

Preparation technology is identical with embodiment 11-1, and difference is, after the step adding phosphoric acid leaching, does not filter, directly adds sodium carbonate, make the rare-earth precipitation in solution, obtains comprising phosphoric acid rare earth slag and the mixing slag containing solitary rock ballast.Wherein:

The weight of the mixing slag obtained is 17.7g, and it accounts for 3.5% of phosphorus ore raw material weight.

The content calculating the mono-calcium phosphate solution middle-weight rare earths obtained after tested is 0.12g; Except the rare earth contained in phosphoric acid one calcium solution, other rare earth all enter into obtain mix slag, now, the rare earth content that obtains is 4.88g, and it is 97.6% of total rare earth (TRE) amount in phosphorus ore raw material.

Embodiment 12-1

With 500g containing the phosphorus ore of monazite 0.8%, rare earth 0.2% for raw material, adopt mass concentration to be 35% (with P ₂o ₅meter) phosphoric acid solution leach, hierarchy of control liquid-solid ratio 6:1, reacts 5h at 80 DEG C, obtains mono-calcium phosphate solution containing rare earth and containing solitary rock ballast after filtering;

Add calcium carbonate toward containing in mono-calcium phosphate solution, regulator solution pH is 1, makes the rare-earth precipitation in solution, obtains mono-calcium phosphate solution and phosphoric acid rare earth slag after filtration.After adjust ph, in the Si Liaodengji dicalcium phosphate feed grade formed in system, calcium ion content accounts for 1.6% of calcium ion total content in system.Calculate after tested, containing rare earth in the mono-calcium phosphate solution obtained is 0.03g.

The gross weight comprised containing the mixing slag of solitary rock ballast and phosphoric acid rare earth slag obtained is 12g, accounts for 2.4% of phosphorus ore raw material weight, to obtain mixing slag middle-weight rare earths be phosphorus ore is 97.0% of total rare earth (TRE) amount in raw material.

Embodiment 12-2

Preparation technology is identical with embodiment 12-1, and difference is, after the step adding phosphoric acid leaching, does not filter, directly adds sodium carbonate, make the rare-earth precipitation in solution, obtains comprising phosphoric acid rare earth slag and the mixing slag containing solitary rock ballast.Wherein:

The weight of the mixing slag obtained is 12.3g, and it accounts for 2.5% of phosphorus ore raw material weight.

The content calculating the mono-calcium phosphate solution middle-weight rare earths obtained after tested is 0.028g; Except the rare earth contained in phosphoric acid one calcium solution, other rare earth all enter into obtain mix slag, now, the rare earth content that obtains is 0.972g, and it is 97.2% of total rare earth (TRE) amount in phosphorus ore raw material.

Embodiment 13-18 be with embodiment 5 comprising of obtaining containing the mixing slag of solitary rock ballast and phosphoric acid rare earth slag for raw material.

Embodiment 13

With embodiment 5-1 comprising of obtaining containing the mixing slag of solitary rock ballast and phosphoric acid rare earth slag for raw material, iron content rare-earth tailing is added according to phosphorus content in slag, control Fe/P mol ratio is 2.5, and add Calcium Fluoride (Fluorspan) according to silicone content in slag, control F/Si mol ratio is 4.1, then adds the vitriol oil (concentration is 98.3%) mixing, and vitriol oil add-on is 1 times containing solitary rock ballast and phosphoric acid rare earth slag weight, at 350 DEG C, carry out strengthening roasting, obtain fired slags.

Water logging fired slags, obtains containing rare earth infusion and water logging slag after filtering.

Adding light dolomite regulates the pH value containing rare earth infusion to be 3.5, filters and obtains phosphoric acid iron and thorium phosphate precipitation, and rare earth sulfate solution; In rare earth sulfate solution, add carbonate deposition rare earth, obtain rare earth carbonate product 10.2g, rare earth carbonate product purity is about 95.5%, and the rate of recovery of whole technological process middle-weight rare earths is 91.5%.

Comparative example 1

Adding light dolomite regulates the pH value containing rare earth infusion to be 2, filters and obtains phosphoric acid iron and thorium phosphate precipitation, and rare earth sulfate solution; In rare earth sulfate solution, add carbonate deposition rare earth, obtain rare earth carbonate product 21.5g, rare earth carbonate product purity is about 86.7%, and the foreign matter content such as phosphorus, iron is high.The rate of recovery of whole technological process middle-weight rare earths is 91.5%.

Embodiment 14

With embodiment 5-1 comprising of obtaining containing the mixing slag of solitary rock ballast and phosphoric acid rare earth slag for raw material, mixing slag weight is 22g, wherein phosphorus content is about 12%, silicone content is about 6%, iron content rare-earth tailing is added according to phosphorus content in slag, in iron content rare-earth tailing, iron level is about 8%, control Fe/P mol ratio is 2.8, and add fluorite according to silicone content in slag, control F/Si mol ratio is 4.5, then the vitriol oil (concentration is 98.3%) mixing is added, vitriol oil add-on is 1.8 times containing solitary rock ballast and phosphoric acid rare earth slag weight, strengthening roasting 4h is carried out at 500 DEG C, obtain fired slags.

Add 300mL water logging and go out fired slags, obtain containing rare earth infusion and water logging slag after filtering.

Adding light dolomite regulates the pH value containing rare earth infusion to be 4, filters and obtains phosphoric acid iron and thorium phosphate precipitation, and rare earth sulfate solution; In rare earth sulfate solution, add 20g sodium carbonate precipitating rare earth, obtain rare earth carbonate product 11.5g, rare earth carbonate product purity is about 96%, and the rate of recovery of whole technological process middle-weight rare earths is 93.3%.

Embodiment 15

With embodiment 5-2 comprising of obtaining containing the mixing slag of solitary rock ballast and phosphoric acid rare earth slag for raw material, iron content rare-earth tailing is added according to phosphorus content in slag, control Fe/P mol ratio is 3.1, and add Calcium Fluoride (Fluorspan) according to silicone content in slag, control F/Si mol ratio is 5, then adds the vitriol oil (concentration is 98.3%) mixing, and vitriol oil add-on is 1.5 times containing solitary rock ballast and phosphoric acid rare earth slag weight, at 400 DEG C, carry out strengthening roasting, obtain fired slags.

Adding magnesium oxide regulates the pH value containing rare earth infusion to be 4.2, filters and obtains phosphoric acid iron and thorium phosphate precipitation, and rare earth sulfate solution; In rare earth sulfate solution, add carbonate deposition rare earth, obtain rare earth carbonate product 13.1g, rare earth carbonate product purity is about 98%, and the rate of recovery of whole technological process middle-weight rare earths is 95.9%.

Embodiment 16

With embodiment 5-2 comprising of obtaining containing the mixing slag of solitary rock ballast and phosphoric acid rare earth slag for raw material, iron content rare-earth tailing is added according to phosphorus content in slag, control Fe/P mol ratio is 4, and add Calcium Fluoride (Fluorspan) according to silicone content in slag, control F/Si mol ratio is 5.5, then mixes with the vitriol oil (concentration is 98.3%), and vitriol oil add-on is 2 times containing solitary rock ballast and phosphoric acid rare earth slag weight, at 450 DEG C, carry out strengthening roasting, obtain fired slags.

Adding magnesium oxide regulates the pH value containing rare earth infusion to be 4.5, filters and obtains phosphoric acid iron and thorium phosphate precipitation, and rare earth sulfate solution; In rare earth sulfate solution, add carbonate deposition rare earth, obtain rare earth carbonate product 13.0g, rare earth carbonate product purity is about 98%, and the rate of recovery of whole technological process middle-weight rare earths is 96.6%.

Embodiment 17

With embodiment 5-2 comprising of obtaining containing the mixing slag of solitary rock ballast and phosphoric acid rare earth slag for raw material, iron content rare-earth tailing is added according to phosphorus content in slag, control Fe/P mol ratio is 1.3, and add fluorite according to silicone content in slag, control F/Si mol ratio is 6, then mixes with the vitriol oil (concentration is 98.3%), and vitriol oil add-on is 1.3 times containing solitary rock ballast and phosphoric acid rare earth slag weight, at 250 DEG C, carry out strengthening roasting, obtain fired slags.

Adding light dolomite regulates the pH value containing rare earth infusion to be 5, filters and obtains phosphoric acid iron and thorium phosphate precipitation, and rare earth sulfate solution; In rare earth sulfate solution, add carbonate deposition rare earth, obtain rare earth carbonate product 15.2g, rare earth carbonate product purity is about 97%, and the rate of recovery of whole technological process middle-weight rare earths is 92.7%.

Embodiment 18

With embodiment 5-2 comprising of obtaining containing the mixing slag of solitary rock ballast and phosphoric acid rare earth slag for raw material, iron content rare-earth tailing is added according to phosphorus content in slag, control Fe/P mol ratio is 2, and add Calcium Fluoride (Fluorspan) according to silicone content in slag, control F/Si mol ratio is 3.5, then adds the vitriol oil (concentration is 98.3%) mixing, and vitriol oil add-on is 3 times containing solitary rock ballast and phosphoric acid rare earth slag weight, at 200 DEG C, carry out strengthening roasting, obtain fired slags.

Adding light dolomite regulates the pH value containing rare earth infusion to be 2.5, filters and obtains phosphoric acid iron and thorium phosphate precipitation, and rare earth sulfate solution; In rare earth sulfate solution, add carbonate deposition rare earth, obtaining rare earth carbonate product rare earth carbonate product purity is about 96%, and the rate of recovery of whole technological process middle-weight rare earths is 90%.

The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims

1., from the method containing synthetical recovery phosphorus mengite rare-earth phosphorus ore and rare earth, it is characterized in that, comprise the following steps:

Phosphoric acid leaches described containing mengite rare-earth phosphorus ore, filters and obtains containing the mono-calcium phosphate solution of rare earth with containing solitary rock ballast;

By described in precipitator method process containing the mono-calcium phosphate solution of rare earth, make the rare-earth precipitation of dissolving, filter and obtain mono-calcium phosphate solution and phosphoric acid rare earth slag, by described phosphoric acid rare earth slag be describedly mixed to form mixing slag containing solitary rock ballast;

Reclaim the phosphorus in described mono-calcium phosphate solution, and reclaim the rare earth in described mixing slag.

2., from the method containing synthetical recovery phosphorus mengite rare-earth phosphorus ore and rare earth, it is characterized in that, comprise the following steps:

Phosphoric acid leaches described containing mengite rare-earth phosphorus ore, obtains the solidliquid mixture containing rare earth and mono-calcium phosphate solution;

By solidliquid mixture described in precipitator method process, make the rare-earth precipitation of dissolving, filter the mixing slag obtaining mono-calcium phosphate solution and contain monazite and rare earth;

Reclaim the phosphorus in described mono-calcium phosphate solution, reclaim the rare earth in described mixing slag.

3. method according to claim 1 and 2, is characterized in that, described phosphoric acid leaches in step, and described phosphoric acid mixes according to liquid-solid ratio 2-10L:1kg containing mengite rare-earth phosphorus ore with described, P in preferred described phosphoric acid ₂o ₅mass concentration is 15% ~ 50%, is preferably 20% ~ 35%.

4. method according to claim 1 and 2, is characterized in that, described phosphoric acid leaches in step, and extraction temperature is 55 DEG C ~ 150 DEG C, and extraction time is 0.5 ~ 8 hour; Preferably, described phosphoric acid extraction temperature is 60 ~ 90 DEG C, and extraction time is 2 ~ 5 hours.

5. method according to claim 1 and 2, is characterized in that, in described precipitator method treatment step, adds alkaline matter regulation system pH value to make the rare-earth precipitation of dissolving.

6. method according to claim 5, it is characterized in that, in described precipitator method treatment step, the alkaline matter added is magnesium oxide, magnesium hydroxide, magnesiumcarbonate, calcium oxide, calcium hydroxide, calcium carbonate or sodium hydroxide, sodium carbonate, preferential oxidation calcium, calcium hydroxide or calcium carbonate, the described system pH of preferred adjustment is 0.5 ~ 2.5, and preferred described system pH is 0.5 ~ 1.5.

7. method according to claim 4, is characterized in that, in described precipitator method treatment step, regulation system pH value, is less than 5% of calcium ion total content in system to make the calcium ion in the Si Liaodengji dicalcium phosphate feed grade that formed in system.

8. method according to claim 1 and 2, it is characterized in that, in described recovery mono-calcium phosphate solution, the step of phosphorus comprises: add sulfuric acid deliming, solid-liquid separation in described mono-calcium phosphate solution after, obtain solution containing phosphate and calcium sulfate gypsum, reclaim the phosphorus in described solution containing phosphate.

9. method according to claim 8, is characterized in that, in described recovery mono-calcium phosphate solution, the step of phosphorus also comprises: prepare phosphoric acid by after described solution containing phosphate removal of impurities, and prepared phosphoric acid is returned phosphoric acid leaching step recycling.

10. method according to claim 1 and 2, is characterized in that, the step of the described rare earth reclaimed in mixing slag comprises:

In described mixing slag, add iron containing compounds, and after adding fluorochemicals, mix with the vitriol oil and carry out strengthening roasting, obtain fired slags;

Described fired slags adds water leaching, obtains containing rare earth infusion and water logging slag;

Regulate the described pH value containing rare earth infusion to be 3.5 ~ 5, filter and obtain phosphoric acid iron and thorium phosphate precipitation, and rare earth sulfate solution;

In described rare earth sulfate solution, add carbonate deposition rare earth, obtain rare earth carbonate product.

11. methods according to claim 10, it is characterized in that, iron containing compounds is added in described mixing slag, and add in the process of fluorochemicals, described fluorochemicals is with described to mix F:Si mol ratio in slag be 4.1 ~ 6:1, preferred fluorochemicals is Calcium Fluoride (Fluorspan) or fluorite, and preferred described iron containing compounds is iron content rare-earth tailing.

12. methods according to claim 10, it is characterized in that, described mixing with the vitriol oil carries out in strengthening roasting process, and the described vitriol oil mixes according to mass ratio 1-2:1 with containing solitary rock ballast and phosphoric acid rare earth slag, and the maturing temperature of preferred described strengthening calcination steps is 250-500 DEG C.

13. methods according to claim 10, it is characterized in that, in the process of described adjustment containing the pH value of rare earth infusion, adopt magnesium oxide and/or light dolomite to regulate the described pH value containing rare earth infusion, preferably regulate described pH value to 4 ~ 4.5 containing rare earth infusion.

14. methods according to claim 10, is characterized in that, in described water logging process, in immersion liquid, Fe/P mol ratio is greater than 2, is preferably greater than 3.