CN103274377A - Method for enriching P2O5 and rare earth elements in low grade phosphorite - Google Patents

Method for enriching P2O5 and rare earth elements in low grade phosphorite Download PDF

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CN103274377A
CN103274377A CN2013102124837A CN201310212483A CN103274377A CN 103274377 A CN103274377 A CN 103274377A CN 2013102124837 A CN2013102124837 A CN 2013102124837A CN 201310212483 A CN201310212483 A CN 201310212483A CN 103274377 A CN103274377 A CN 103274377A
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phosphorite
acid
rare earth
content
reaction
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张�杰
宋春玉
王建蕊
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Guizhou University
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Abstract

The invention discloses a method for enriching P2O5 and rare earth elements in low grade phosphorite. The method is characterized by comprising the following steps of: adding 10-20 parts of low-medium grade rare earth-containing phosphorite into 400-800 parts of organic acid with concentration of 1.5-10% for a reaction, under the condition that the reaction temperature is 40 DEG C, continuously reacting for 30-40 minutes while stirring, washing the filter residue for several times with the distilled water, drying the filter residue and preparing a sample. Since the organic acid is used for reaction, the reaction time of a leaching agent is shorter, generally, reaction is finished within 40 minutes. The P2O5-containing rock phosphate is leached out by using the organic acid, and the calcium ions in the rock phosphate are migrated out more completely. The leacheate is purer. Moreover, due to addition of the organic acid, a treatment effect is triple of that of the inorganic acid, thus, the method is more efficient and can be used more widely.

Description

P in the low-grade phosphorite of enrichment 2O 5And the method for rare earth element
Technical field
The present invention relates to the method that a kind of phosphorite is recycled, particularly relate to P in the low-grade phosphorite of a kind of enrichment 2O 5And the method for rare earth element.
Background technology
In the main valuable mineral of low-grade phosphorite be collophanite.China's phosphate rock resource reserves are abundant, but the few lean ore of rich ore is many, and are comparatively difficult in industrial utilization.Therefore, exploitation mid low grade phosphate rock rock, and effectively fully utilize valuable element in the mid low grade phosphate rock rock, be the guarantee of China's phosphor resource industry Sustainable development.But low-grade phosphorite resource in will effectively utilizing just must make P wherein 2O 5And the rare earth element enrichment, to make namely that carbonate minerals separates with phosphate mineral in the phosphate ores.For a long time, people have spent the separation problem that very big energy solves carbonate minerals in the phosphate ores, particularly to appositional pattern phosphorite ore, lack at present and can effectively it be carried out separation processes.Low-grade phosphorite ore grade is low, foreign matter content is high, disseminated grain size is thin, the charcoal shale is many, it is the ore of difficult choosing in the domestic Rock Phosphate (72Min BPL), but because this kind mineral deposit standing stock are big, the mineral resources abundance is the important reserve phosphate rock resource mineral deposit that one in China demands urgently developing.
Discover low-grade phosphorite P 2O 5Content, generally about 20%-25%, ree content is generally 0.01%～0.1%.The phosphorite of this part occupies very big ratio in the phosphorus ore rock is overall, therefore, the value of excavating this part phosphorite seems very important.In in the low-grade phosphorite, the main tax deposited P 2O 5Mineral be collophanite, its essential mineral composition is fluorapatite, molecular formula Ca 5(PO 4) 3(F, Cl, OH).Wherein, rhombspar (composition: CaMg[CO3] 2, average content 49.35%), calcite (composition: CaCO 3, average content 4.38%), be contained main carbonate gangue mineralogical composition in the phosphorite, other gangue mineral composition is a small amount of, pyrite (content 5%), barite (on a small quantity) and clay mineral (content 8.84%).Rare earth element is composed in the isomorph mode and is stored in the collophanite, then rare earth element enrichment of collophanite enrichment.
Summary of the invention
The objective of the invention is for P in the low-grade phosphorite of a kind of enrichment is provided 2O 5And the method for rare earth element, can significantly improve P in the phosphorite 2O 5And the accumulation rate of rare earth element, and the material choice of ore dressing is wider, can also increase speed of response, and it is more thorough that calcium ion is moved out, and the product of leaching is also purer, to overcome the deficiencies in the prior art.
The sample that the present patent application experimental technique adopts is for containing rare earth biological chip white clouds matter phosphorite, its P 2O 5Content is 21.141% or lower, the low-grade rare earth Rock Phosphate (72Min BPL) that contains in the genus.
Scholars such as (2008) such as Lian Bin thinks that microorganism-mineral facies mutual effect can promote many hypergene biogeochemical reaction processes, is the important content of hypergene geochemical investigation.Especially the CO that discharges of the organic acid of microorganism secretion and microbial respiratory 2Acidization to rock table moisture is also accelerated the decomposition of rock forming mineral.Be subjected to the inspiration of this result of study, select the sequence organic acid that white clouds matter phosphorite is carried out acidleach and go out test, mainly contain following sequence acids: oxalic acid, tartrate, C acid, D acid, E acid and F acid.
Certain acidolysis reaction can take place in white clouds matter phosphorite under acidic conditions, make to move out P after the carbonate minerals acidleach 2O 5Grade is improved.In the phosphorite efflorescence, the complex process that its contained various migration of elements are organic and inorganic mixing effects, along with the carrying out of weathering, various mineral tend to stable because of different separately stability condition under the hypergene environment.The different types of organic acid that exists in the nature weathering condition should be the major influence factors of weathering.This test is adopted and different types ofly organicly phosphorite to be carried out acidleach is gone out enrichment experiment, its objective is to explain in the physical environment P after the phosphorite weathering 2O 5The universal phenomenon that grade is improved, in the low-grade phosphorite utilization of resources seek effective operational path.As utilize grade be about 21% or lower phosphorite as raw material, then can increase selected phosphorus ore scope greatly, make this technology higher in industrial utility value, thereby bring huge industrial output value.
Therefore the method for P2O5 and rare earth element is such in the low-grade phosphorite of enrichment of the present invention: with the fragmentation of middle low-grade primary phosphorite, make-sample of 0.074mm carries out acidleach and goes out test, and test conditions is that temperature is that 30 ℃～60 ℃, leaching time are 24h.Wherein, to go out the solution that test adopts be organic acid in acidleach.
Further, P in the low-grade phosphorite of enrichment of the present invention 2O 5And the method for rare earth element is carried out as follows: calculate by weight, contain the rare earth phosphorite to add 400 parts～800 parts concentration be that 1.5%～10% organic acid reacts low-grade in 10～20 parts, be under 30 ℃～60 ℃ the condition in temperature of reaction, continue stirring reaction 30～40min, after finishing, reaction with the distilled water wash filter residue for several times, filter residue is dried sample preparation.
Because adopted organic acid to participate in reaction, the leach liquor reaction times is very fast, 40min～60 min(minutes usually) internal reaction can finish.Organic acid leaches and contains the P2O5 Rock Phosphate (72Min BPL), and calcium ion is moved out more thorough in the Rock Phosphate (72Min BPL).It is purer to leach product.And after organic acid added, treatment effect was that mineral acid is more than 3 times.
When adopting method of the present invention to promote technology, its enter this technical process to contain the rare earth phosphorite at first dry and broken, particle size distribution 0.04～0.2mm.
The present invention analysis contain the major element of rare earth phosphorite and trace element variation characteristic, find out that the material of each mineral forms on the basis, the occurrence status of research rare earth element, and analyzed and contain rare earth phosphorite weathering mechanism.Adopt diluted acid (nitration mixture) to make leaching liquid by using for reference the chemical mineral processing method, by setting up chemical reaction system, obtain P 2O 5With the new mode of the enrichment of rare earth element.
(1) is experiment basis with carbonate rock weathering dissolving-karst theory, carries out P 2O 5And rare earth element enrichment experiment.Draw corresponding rare earth element enrichment experiment scheme and corresponding enrichment parameter, and study this mineral deposit at efflorescence middle-weight rare earths element and P 2O 5The enrichment mode.Prove carbonate weathering loss by experiment, collophanite-fluorapatite is concentrated relatively, causes P in the weathering phosphorite 2O 5Grade and ree content increase enrichment.
(2) this area's phosphorite weathering mechanism is carried out systematic research, conclusion summary nitration mixture soaks phosphorite makes its P 2O 5And regularity and the practicality of ree content increase, carry out the exploration of application prospect, for suitability for industrialized production is in the future laid good experiment basis.
Test sample ore of the present invention be in the low-grade rare earth biological chip white clouds matter phosphorite that contains, the main chemical compositions of this sample is CaO, P2O5, MgO and SiO2, CaO content is 41.28%, P2O5 content is 21.141% or lower, Mg content is that 8.68%, SiO2 content is 6.04%, and rare earth element total content ∑ REE is more than the 1172.95ppm, be typical in the low-grade rare earth biological chip white clouds matter phosphorite that contains, so just provide strong condition for its acidolysis.
Dissolve carbonate minerals (rhombspar, calcite) with organic acid and make its stripping, reduce the content of gangue mineral in the phosphorite, to improve P 2O 5And the grade of rare earth element.
Organic acid (nitration mixture) decomposes the relevant chemical reaction of phosphorite:
For this phosphorus deposit, because its composition is mainly collophanite, principal reaction is as follows:
Organic acid leaches chemical reaction:
4HA+CaMg(CO 3) 2=CaA 2+MgA 2+2CO 2↑+2H 2O
2HA+CaCO3=CaA2+CO2↑+H2O
The present invention adopts the organic acid system that mid low grade phosphate rock is leached, and the enrichment grade can be brought up to 30%-34% from 21%, shows that the selected grade of ore is 21% or lower, and the accumulation rate that reaches is higher, is more than 40%～65%, and accumulation rate is higher more effective.The utilization of the low-grade phosphorite of centering is more meaningful.
Because adopted organic acid to participate in reaction, the leach liquor reaction times is very fast, 30min(minute usually)～60 min(minute) internal reaction can finish.Organic acid leaches and contains the P2O5 Rock Phosphate (72Min BPL), and calcium ion is moved out more thorough in the Rock Phosphate (72Min BPL).It is purer to leach product.And after organic acid added, treatment effect was mineral acid more than 3 times, so better effects if, and range of application is wider.
Embodiment
Be described in further detail below in conjunction with the present invention of embodiment.
Verify that at first concentration of oxalic acid per-cent is to the influence of phosphorite test :
To fetch the primary phosphorite fragmentation that comes from Guizhou Zhijin dagger-axe second month in a season 5, make-sample of 0.074mm carries out acidleach to be gone out to test, test conditions is that temperature is 40 ℃, the oxalic acid organic acid soln of 400ml, leaching time is 24h, consider different concentration of oxalic acid to its influence of leaching the result, the result is as shown in table 1.
Figure 2013102124837100002DEST_PATH_IMAGE002
2H 2C 2O 4+?CaMg(CO 3) 2=CaC 2O 4↓+MgC 2O 4·2H 2O↓+2CO 2↑
H 2C 2O 4+?CaCO 3=?CaC 2O 4↓+?CO 2↑+H 2O
As can be seen from Table 1, when concentration of oxalic acid is 1.5%, P 2O 5Content high, and when concentration of oxalic acid is 5%, P 2O 5Content reduced a lot, this is because oxalic acid and rhombspar, calcite reaction have generated water-fast caoxalate and magnesium oxalate, has increased slag content, makes the total mass rising, and P 2O 5Quality constant again, so cause P 2O 5Content reduces, but when concentration of oxalic acid is 10%, P 2O 5Content begin again to increase, but amount of increase is little, this is because magnesium oxalate can be dissolved in diluted acid, so slag content has reduced some, and P 2O 5Content just increase.
The influence that checking tartaric acid concentration per-cent is tested phosphorite:
Will be from the secondary 5 primary phosphorite fragmentations of Guizhou Zhijin dagger-axe, make-sample of 0.074mm carries out acidleach to be gone out to test, test conditions is that temperature is 40 ℃, the tartrate organic acid soln of 400ml, leaching time is 24h, consider different tartaric acid concentration to its influence of leaching the result, the result is as shown in table 2.
Figure 1
2H 6C 6O 6+?Ca?Mg(CO 3) 2=CaH 4C 6O 6↓+?MgH 4C 6O 6↓+?2CO 2↑+H 2O
H 6C 6O 6+?CaCO 3=?CaH 4C 6O 6↓+?CO 2↑+H 2O
As can be seen from Table 2, when tartaric acid concentration is 1.5%, P 2O 5Content high, and when tartaric acid concentration is 5%, P 2O 5Content reduced a lot, this is because tartrate and rhombspar, calcite reaction have generated water-fast calcium tartrate and magnesium tartrate, has increased slag content, makes the total mass rising, and P 2O 5Quality constant again, so cause P 2O 5Content reduces, but when tartaric acid concentration is 10%, P 2O 5Content still continue to reduce, this is because be exactly all water insoluble and diluted acids of calcium tartrate and magnesium tartrate, thus slag content further increase, thereby cause P2O5 content to continue to reduce.
The influence that checking C acid concentration per-cent is tested phosphorite:
With primary phosphorite fragmentation, to make-sample of 0.074mm carries out acidleach and goes out test, test conditions is that temperature is 40 ℃, the C acid organic acid soln of 400ml, and leaching time is 24h, considers different C acid concentrations to its leaching result's influence, and the result is as shown in table 3.
Figure 2
4γH+CaMg(CO 3) 2=Caγ 2+?Mgγ 2+?2CO 2↑+2H 2O
2γH+CaCO 3=Caγ 2+?CO 2↑+H 2O
As can be seen from Table 3, when the C acid concentration is 1.5%, P 2O 5Content low, and when the C acid concentration is 5%, P 2O 5Content fall and continue to increase, this is because C acid and rhombspar, calcite reaction have generated water-soluble C acid calcium and C acid magnesium, has reduced slag content, makes total mass descend, and P 2O 5Quality constant again, so cause P 2O 5Content rises, when the C acid concentration is 10%, and P 2O 5Content still continue to increase, but amount of increase is little, this is because the reaction of C acid and rhombspar, calcite reacts completely substantially, so P 2O 5The content increase be not clearly.
The influence that checking D acid concentration per-cent is tested phosphorite:
Primary phosphorite fragmentation with Guizhou Zhijin dagger-axe second month in a season 5, make granularity and goes out test for the sample of-0.074mm carries out acidleach, test conditions is that temperature is 40 ℃, the D of 400ml acid organic acid soln, leaching time is 24h, consider different D acid concentrations to its influence of leaching the result, the result is as shown in table 4 below.
Figure DEST_PATH_IMAGE008
4δH 3+?3CaMg(CO 3) 2=δ 2Ca 3·4H 2O↓+δ 2Mg 3·2H 2O↓+?6CO 2↑4δH 3+?3CaCO 3=δ 2Ca 3·4H 2O↓+?3CO 2↑
As can be seen from Table 4, when the D acid concentration is 1.5%, P 2O 5Content low, this is because D acid and rhombspar, calcite reaction have generated water-fast D acid calcium and water insoluble, as the to dissolve in diluted acid sour magnesium of D, and when the D acid concentration is 5%, P 2O 5Content fall and continue to increase, this is because after D acid and rhombspar, the calcite reaction, water insoluble, the D acid magnesium that dissolves in diluted acid of generation have reduced slag content, make total mass descend, and P 2O 5Quality constant again, so cause P 2O 5Content rises, when the D acid concentration is 10%, and P 2O 5Content reduce to some extent, but amount of decrease is little, this is because the reaction of D acid and rhombspar, calcite reacts completely substantially, and the also dissolving substantially of the D that reaction generates acid magnesium, so P 2O 5The content amount of decrease be not clearly.
The influence that checking E acid concentration per-cent is tested phosphorite:
With making granularity after the primary phosphorite fragmentation be-sample of 0.074mm carries out acidleach to be gone out to test, test conditions is that temperature is 40 ℃, the E of 400ml acid organic acid soln, leaching time is 24h, considers different E acid concentrations to its influence of leaching the result, and the result is as shown in table 5.
Figure 3
H 2O+4εH+CaMg(CO 3) 2=2ε·Ca↓+2ε·Mg·3H 2O↓+2CO 2↑
2εH?+CaCO 3=2ε·Ca↓+CO 2↑+H 2O
As can be seen from Table 5, E acid can with its reaction, generate E acid calcium and E acid magnesium, E acid calcium free from extraneous odour is soluble in hot water, is insoluble to ethanol etc., has advantages such as the high and dissolution rate of solubleness is fast.E acid magnesium odorless is soluble in hot water.When the E acid concentration increases, P 2O 5Content also constantly increase, this is because material and E acid in the primary phosphorite are reacted, having generated can hot water soluble E acid calcium and the sour magnesium of E, has so just reduced total mass, enrichment P 2O 5, make P 2O 5Content increase.
The influence that checking F acid concentration per-cent is tested phosphorite:
With primary phosphorite fragmentation, make granularity and goes out test for the sample of-0.074mm carries out acidleach, test conditions is that temperature is 40 ℃, the F acid organic acid soln of 400ml, and leaching time is 24h, consider different F acid concentrations to its influence of leaching the result, the result is as shown in table 6.
Figure 4
3ζH 2+CaMg(CO 3) 2=ζCa+2ζMg+2CO 2↑+2H 2O
ζH 2+CaCO 3=ζCa+CO 2↑+H 2O
From table 6 as can be seen, F acid can react with phosphorite, generates F acid calcium and F acid magnesium, and all water-soluble, so along with the increase of the concentration of F acid, P 2O 5Content also increase, but when material in the phosphorite dissolves fully, when acid concentration increases again, P 2O 5Content also no longer increase.
Test-results shows:
C acid is played important effect to the weathering of primary phosphorite, and can very fast enrichment P 2O 5, when the concentration of acid is 5%, P 2O 5Content can reach 35.11%, when the concentration of acid is 10%, P 2O 5Content can reach 35.61%.Be between the 5%-10% in acid concentration, P 2O 5The variation of content be not very big, this just illustrates that the material in the phosphorite is dissolved by acid substantially, reaction reaches balance.
D acid plays a role to the weathering of primary phosphorite, can enrichment P 2O 5, when the concentration of acid is 5%, P 2O 5Content can reach 35.43%, when the concentration of acid is 10%, P 2O 5Content can reach 35.20%.Be between the 5%-10% in acid concentration, P 2O 5The variation of content be not very big, but also lower to some extent, Here it is because generated water-fast D acid magnesium, causes P 2O 5Content lower to some extent.
E acid also plays a role to the weathering of primary phosphorite, can enrichment P 2O 5, when the concentration of acid is 5%, P 2O 5Content can reach 28.89%, when the concentration of acid is 10%, P 2O 5Content can reach 32.82%.Be between the 5%-10% in acid concentration, P 2O 5Content change to some extent, this is because the E that generates acid calcium and E acid magnesium dissolve in hot water, has reduced overall quality, so P 2O 5Content increase to some extent.
F acid also plays a role to the weathering of primary phosphorite, can enrichment P 2O 5, when the concentration of acid is 5%, P 2O 5Content can reach 27.59%, when the concentration of acid is 10%, P 2O 5Content can reach 30.06%.Be between the 5%-10% in acid concentration, P 2O 5Content change to some extent, this is because the F that generates acid calcium and F acid magnesium water soluble have reduced overall quality, so P 2O 5Content increase to some extent.
Tartrate plays certain restraining effect to the weathering of primary phosphorite, when the concentration of acid is 5%, and P 2O 5Content only reach 6.83%, when the concentration of acid is 10%, P 2O 5Content have only 4.49%.This is because the calcium tartrate that generates is water insoluble, has increased overall quality, so reduced P 2O 5Content.
Oxalic acid also plays certain restraining effect to the weathering of primary phosphorite, when the concentration of acid is 5%, and P 2O 5Content only reach 2.74%, when the concentration of acid is 10%, P 2O 5Content also have only 3.26%.This is because the caoxalate and the magnesium oxalate that generate are all water insoluble, has increased overall quality, so reduced P 2O 5Content.
Certainly, be the concrete exemplary applications of invention more than, the present invention also has other embodiment, and all employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop within the protection domain of the presently claimed invention.

Claims (3)

1. P in the low-grade phosphorite of enrichment 2O 5And the method for rare earth element, it is characterized in that: with the fragmentation of middle low-grade primary phosphorite, make-sample of 0.074mm carries out acidleach and goes out test, test conditions is that temperature is that 30 ℃～60 ℃, leaching time are 24h.
2. the method for P2O5 and rare earth element in the low-grade phosphorite of enrichment according to claim 1 is characterized in that: it is organic acid that described acidleach goes out the solution that test adopts.
3. the method for P2O5 and rare earth element in the low-grade phosphorite of enrichment according to claim 2, it is characterized in that carrying out as follows: calculate by weight, contain the rare earth phosphorite to add 400 parts～800 parts concentration be that 1.5%～10% organic acid reacts low-grade in 10～20 parts, be under 30 ℃～60 ℃ the condition in temperature of reaction, continue stirring reaction 30～40min, after finishing, reaction with the distilled water wash filter residue for several times, filter residue is dried sample preparation.
CN2013102124837A 2013-05-31 2013-05-31 Method for enriching P2O5 and rare earth elements in low grade phosphorite Pending CN103274377A (en)

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CN104445112A (en) * 2014-09-30 2015-03-25 贵州大学 Method for recycling phosphate ores by using acid leaching method

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CN101824536A (en) * 2009-03-03 2010-09-08 北京有色金属研究总院 Process for extracting rare-earth from sulfuric acid treating phosphorite process
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Application publication date: 20130904