CN102676853A - Rare earth separation method with material linkage cyclic utilization function - Google Patents
Rare earth separation method with material linkage cyclic utilization function Download PDFInfo
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Abstract
The invention relates to a rare earth separation method with the material linkage cyclic utilization function. The rare earth separation method comprises the following steps: the organic phase of loaded rare earth prepared by extractant A and rare earth soap stock through mixing is used for the follow-up linkage extraction separation, and inorganic acid in the residual water phase is extracted and concentrated by extractant C and is then reused for material dissolving or recovering rare earth with oxalic acid precipitated therein; purified rare earth solution is subjected to extraction separation, the rare earth is precipitated through oxalic acid, sediment mother solution containing oxalic acid and inorganic acid is mixed with extractant B, the oxalic acid is extracted to be reused for precipitating rare earth, and the residual inorganic acid is directly used for washing and back extraction processes or is used for material dissolving after being concentrated by the extractant C. With the rare earth separation method provided by the invention, intermediate materials generated in the rare earth separation process can be recycled in process sections in a linkage manner, the alkali saponification process is avoided, and the material dissolving, washing and back extraction processes can be finished only by the recycled inorganic acid, so that the rare earth separation and purification process disclosed by the invention does not consume alkaline and inorganic acid, the cost is low, and the rare earth separation method is green and environmental-friendly.
Description
Technical field
The invention belongs to the Rare Earth Separation technical field, be specifically related to the Rare Earth Separation method of material interlock recycle.
Background technology
Rare earth is the general name of whole 15 lanthanon of scandium, yttrium, because chemical property is very close, and association coexistence in mineral, and excellent light, electricity, magnetic, the catalytic intrinsic property of each element often needs single high-purity rare-earth just can demonstrate fully.Therefore, separate the significant process that purification becomes rare earth material industry.
The separation of rare earth is purified and is adopted solvent extraction and separation method, this method to have that treatment capacity is big, speed of response fast, the advantage of good separating effect usually, is the main working method of domestic and international Rare Earth Separation.Rare earth extraction separates used extraction agent and is mainly acidic phosphorus extractant; As: P204 (2-ethylhexyl phosphoric acid), P507 (di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester) and Cyanex272 (two (2; 4,4-tri-methyl-amyl) P229 (two (2-ethylhexyl) phosphonic acids) etc. phosphonic acids)).
Rare earth extraction separates purification process and has mainly comprised independent process such as molten material, extracting and separating, deposition.
Molten material process refers to mainly that with rare earth oxide or carbonate with sour dissolved process, available following equation is represented:
RE
2O
3+ 6HCl=2RECl
3+ 3H
2O (rare earth oxide dissolving) (1)
RE
2(CO
3)
3+ 6HCl=2RECl
3+ 3H
2O+3CO
2↑ (rare earth carbonate dissolving) (2)
For improving separation efficiency, acidic phosphorus extractant needs through alkaline matter saponification such as ammoniacal liquor or sodium hydroxide or bicarbonate of ammonia, and the organic phase after the saponification is a rare earth soap.Saponification reaction can be represented (wherein HA representes acidic extractant) with following equation:
HA+NaOH=NaA+H
2O (soda soapization) (3)
Or HA+NH
4OH=NH
4A+H
2O (ammonia saponification) (4)
3NaA+RECl
3=REA
3+ 3NaCl (rare earth saponification) (5)
Usually make the easy collection component of organic phase in extraction section extraction feed liquid of the difficult collection of load component; Obtain the difficulty collection component aqueous solution of purification; Load is prone to the organic phase of collection component and uses acid again or be prone to the countercurrent washing of collection component at washing section; Obtain the organic phase of load purify easy collection component, after sour back extraction, obtain the pure easy collection component aqueous solution, organic phase obtains recycling utilization simultaneously.
REA
3+ 3HCl=RECl
3+ 3HA (washing, reextraction) (6)
Single rare earth is behind oxalic acid precipitation (pressing equation (7)), and calcination is a rare earth oxide again.
2RECl
3+3H
2C
2O
4=RE
2(C
2O
4)
3+6HCl (7)
Dissolving needs to consume inorganic acid solution rare earth oxide or carbonate in the material process, adopt the saponification process of the rare earth extraction sepn process of acidic phosphorus extractant system need consume alkali, produces corresponding saliferous saponification waste-water discharging thus; The deposition operation consumes oxalic acid, produces the high acidity mother liquor of precipitation of ammonium that contains oxalic acid and mineral acid, need in a large amount of alkali with after with the form of salinity with discharge of wastewater.To separate 120,000 tons of rare earth oxides year, wastewater discharge is up to more than 1,200 ten thousand tons, and the salt quantity discharged surpasses 500,000 tons, and a large amount of uses of industrial chemicals have not only increased production cost, and environmental protection pressure is huge.Therefore, the rare earth worker of China has developed multinomial rare earth cleaning technology of preparing.
Dissolve the material step except directly dissolving with mineral acid, can also adopt the method for the direct dissolved carbon hydrochlorate of acid organic extractant, the hydrogen ion that consumes in the extraction agent with carbonate makes rare earth get in the organic extractant.Like one Chinese patent application " a kind of rare earth carbonate solvent extraction and separation technology " (application number: 200810155328.5; October 27 2008 applying date; Open day on March 18th, 2009), " a kind of pretreatment process of organic extractant and application thereof " (application number: 200710163930.9; October 11 2007 applying date; Open day on September 10th, 2008), " a kind of method for saponification of organic extractant " (application number: 200610001858.5, January 24 2006 applying date, open day on August 16th, 200).Above method is directly dissolved rare earth with acidic extractant; The preparation load has the organic phase replacement aqueous phase liquid of mishmetal to advance groove; Can utilize the acid in the organic phase; Reduce the acid consumption of material dissolution, be used for the saponification of the blank organic phase of sepn process and washing, the back extraction regeneration of load organic phases but still need to consume soda acid, and the discharging of corresponding generation salt.
Saponifiable extraction can produce a large amount of brine wastes, when increasing production cost environment is caused bigger pollution.Organic phase is directly carried out the rare earth saponification reaction without alkali soapization, and this reaction can be expressed as:
RECl
3+3HA=REA
3+3HCl (8)
One Chinese patent application " a kind of high concentration rare earth solution non-saponifiable extraction full-separating process " (application number 200610076405.9; April 25 2006 applying date; Open day on December 20th, 2006), " a kind of technology of extracting and separating rare earth elements from non-saponification system " (application number 200610072668.2; April 7 2006 applying date; Open day on October 10th, 2007), " a kind of full separating technique of non-saponification organic phase extracting rare-earth " (application number 200610057908.1, February 27 2006 applying date, open day on August 30th, 2006), " a kind of technology of extracting rare earth element by non-saponifiable phosphorous mixing extractant " (application number 200510137231.8; December 31 2005 applying date, open day on July 19th, 2006) be the rare earth extraction method under the non-saponification system.In order to reduce the acidity of aqueous phase after the non-saponification, in this process, add neutralizations such as alkaline matter MgO, CaO again to improve loading capacity.Like one Chinese patent application " process method of solvent extraction separation purification of rare earth element " (application number 200710100026.3; June 4 2007 applying date; Open day December 10 in 2008), " a kind of method for saponification of extraction agent " (application number 200610078830.1; May 10 2006 applying date, open day on December 6th, 2006).The acid that non-saponification system comes out from the organic phase displace is not recycled, and finally still need neutralize, and discharging brine waste amount is suitable with saponification process.
Oxalic acid precipitation waste water contains oxalic acid and a large amount of mineral acids, and conventional treatment method is a lime neutralization precipitation facture.One Chinese patent application " a kind of washing methods of oxalic acid precipitation " (application number: 201110095141.2 applyings date: 2011-04-15; Open day on October 26th, 2011) with the method reuse water of organic solvent extraction; Do not consider the recycle of hydrochloric acid and oxalic acid; Acid still need neutralize, and produces the discharging of brine waste.
Above method is all to single process; Only can reduce the reagent consumption or the discharge of wastewater of certain single link; As a whole consideration is not done in sepn process; Generation and the utilization to different operation reagent do not link, and finally still can produce a large amount of brine wastes, can't eliminate the environmental stress that Rare Earth Separation is brought.
Summary of the invention
To the defective that exists in the prior art; The Rare Earth Separation method that the purpose of this invention is to provide two kinds of material interlock recycles; The Rare Earth Separation whole process that adopts this method to make to comprise material dissolution, extracting and separating and oxalic acid precipitation can both be carried out the material interlock recycle of acid; Extraction agent alkali soap process can be avoided, only material dissolution and processes such as washing, back extraction can be accomplished with the mineral acid of recycling.The Rare Earth Separation purification process does not consume alkali and mineral acid, does not produce brine waste, and production cost is low, environmental protection.
For reaching above purpose, the technical scheme that the present invention adopts is: the Rare Earth Separation method of material interlock recycle may further comprise the steps:
(I) is dissolved in mishmetal infusion that mix sulphur acid rare earth infusion that mixed rare earth solution that inorganic acid solution obtains or sulfuric acid roasting method obtain or the IX of southern ore deposit obtains as treating extraction feed with rare earth carbonate or oxide compound;
(II) is 0.1-20 with the rare earth soap stock with using the blank extraction agent A behind the organic solvent diluting by volume: 1 ratio thorough mixing, directly carry out the rare earth saponification reaction, and obtain the organic phase of supported rare earth and contain acid rare earth solution;
The organic phase of treating the supported rare earth that extraction feed and step (II) obtain that (III) obtains step (I) is mixed in the cascade extraction groove and is carried out the rare earth exchanged purification reaction; Through repeatedly the washing, the back extraction organic phase; Obtain single rare earth solution and blank extraction agent A respectively, blank extraction agent A returns step (II) and utilizes again;
Single rare earth solution and oxalic acid solution or solid oxalic acid mixed precipitation rare earth ion that (IV) obtains step (III) separate, wash the rare earth oxalate throw out, obtain containing the oxalic acid precipitation waste water of oxalic acid and mineral acid;
The oxalic acid precipitation waste water that (V) obtains step (IV) with the 0.1-20 by volume of the extraction agent B behind the organic solvent diluting: 1 ratio thorough mixing; The balance water that obtains the organic phase of load oxalic acid and contain mineral acid, the oxalic acid in organic phase precipitating rare earth ion again after reclaiming;
The balance water that contains mineral acid that (VI) step (V) obtains returns step (I) dissolving rare earth carbonate or oxide compound, perhaps returns step (III) washing, back extraction organic phase;
The acid rare earth solution that contains that obtains after (VII) step (II) middle-weight rare earths saponification reaction adopts the method precipitating rare earth ion in the step (IV), and adopts the method for step (V)-(VI) to handle oxalic acid precipitation waste water.
Further; In the step (II); The rare earth soap stock is 1-5 with the volume ratio of using the blank extraction agent A behind the organic solvent diluting: 1; Said extraction agent A is selected from one or more in 2-ethylhexyl phosphoric acid (P204), di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (P507), two (2,4, the 4-tri-methyl-amyl) phosphonic acids (Cyanex272) and two (2-ethylhexyl) phosphonic acid ester (P229); Said organic solvent is selected from one or more in industrial kerosene, sulfonated kerosene, solvent oil, isooctyl alcohol, the secondary octanol, and the concentration of extraction agent A is 0.5-1.8mol/L.
Further, the rare earth soap stock in the step (II) is single rare earth solution or the earth solution that after extraction is divided into groups, obtains, and its content of rare earth is counted 0.1-2.5mol/L with REO.Here, the earth solution that after extraction is divided into groups, obtains is preferably the solution that contains difficult collection rare earth component that after extraction is divided into groups, obtains.
Further again; When the rare earth soap stock in the step (II) is single rare earth solution; In the step (VII), the rare earth saponification reaction obtains contains single rare earth solution of the same race that acid rare earth solution and step (III) obtain and merges the back and adopt the method precipitating rare earth ion in the step (IV).
Further; In the step (V); Oxalic acid precipitation waste water is 0.5-5 with the volume ratio of using the extraction agent B behind the organic solvent diluting: 1; Extraction agent B is tributyl phosphate (TBP) and/or methyl acid phosphate diformazan heptyl ester (P350), and said organic solvent is selected from one or more in industrial kerosene, sulfonated kerosene, solvent oil, isooctyl alcohol, the secondary octanol, and the concentration of extraction agent B is 0.1-1.8mol/L.
Further, when reclaiming oxalic acid in the step (V), make the organic phase of water back extraction load oxalic acid, obtain oxalic acid solution, oxalic acid returns does step (IV) precipitating rare earth ion; Or the organic phase of use earth solution back extraction load oxalic acid, obtain the rare earth oxalate throw out; Or the organic phase of use ammoniacal liquor or sodium hydroxide solution back extraction load oxalic acid, obtain ammonium oxalate or sodium oxalate sub product.
Further; In the step (VI); The balance water that contains mineral acid returns before step (I) use; Make in advance the balance water that contains mineral acid with the 0.1-20 by volume of the extraction agent C behind the organic solvent diluting: 1 mixed extraction concentrates, and the mineral acid after concentrating returns step (I) and uses, and end water or the sedimentary wash water of rare earth oxalate that water is done to dissolve the end water of material or prepare oxalic acid solution recycle.
Further again; Said extraction agent C is selected from secondary carbon primary amine (N1923), trialkyl methylamine, N-laurylene (trialkyl methyl) amine, two (1-isobutyl--3; 5-dimethyl-hexyl) amine, two (1-methylheptyl) amine, N; In N-two (1-methylheptyl) ethanamide, tri-n-octyl amine, tri-iso-octylamine, three octyl tertiary amines (N235), the trilaurylamine (Tridodecylamine and three (2-DEHA) one or more; Said organic solvent is selected from one or more in industrial kerosene, sulfonated kerosene, solvent oil, isooctyl alcohol, the secondary octanol, and the concentration of extraction agent C is 0.1-1.8mol/L.
The Rare Earth Separation method of another kind of material interlock recycle provided by the invention; Comprise molten material, extracting and separating, oxalic acid precipitation and washing procedure; The extracting and separating operation comprises saponification supported rare earth and rare earth exchanged purification step; Inorganic acid solution that extracting and separating, oxalic acid precipitation and washing procedure are produced or the earth solution that contains mineral acid with the 0.1-20 by volume of the extraction agent C behind the organic solvent diluting: 1 ratio thorough mixing; Extraction concentrates mineral acid; Mineral acid after concentrating returns and dissolves material process and recycle, and the low sour water that contains rare earth returns saponification supported rare earth step mutually, and the low sour water that does not contain rare earth does to dissolve the end water of material mutually or the end water or the sedimentary wash water of rare earth oxalate of preparation oxalic acid solution recycles.
" inorganic acid solution or contain the earth solution of mineral acid " that this method is mentioned is meant that the solution that does not contain oxalic acid and contain mineral acid, mineral acid are mainly hydrochloric acid and/or nitric acid and/or sulfuric acid.
Above-mentioned " inorganic acid solution or contain the earth solution of mineral acid " comprise and contain the inorganic acid solution that produces when adopting lower concentration acid removal of impurities in the earth solution that contains mineral acid that produces under acid rare earth solution, the excessive situation of oxalic acid precipitation step middle-weight rare earths and the washing step after the rare earth saponification of rare earth saponification generating step, or the like.
Further; Said extraction agent C is selected from secondary carbon primary amine (N1923), trialkyl methylamine, N-laurylene (trialkyl methyl) amine, two (1-isobutyl--3; 5-dimethyl-hexyl) amine, two (1-methylheptyl) amine, N; In N-two (1-methylheptyl) ethanamide, tri-n-octyl amine, tri-iso-octylamine, three octyl tertiary amines (N235), the trilaurylamine (Tridodecylamine and three (2-DEHA) one or more; The concentration of extraction agent C is 0.1-1.8mol/L, and said organic solvent is selected from one or more in industrial kerosene, sulfonated kerosene, solvent oil, isooctyl alcohol, the secondary octanol.
Further, the blank extraction agent A after saponification supported rare earth step adopts the rare earth soap stock and uses organic solvent diluting is 1-20 by volume: 1 ratio thorough mixing, directly carry out the rare earth saponification reaction; Said extraction agent A is selected from one or more in 2-ethylhexyl phosphoric acid, di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester, two (2,4, the 4-tri-methyl-amyl) phosphonic acids and two (2-ethylhexyl) phosphonic acid ester, and the concentration of extraction agent A is 0.5-1.8mol/L.
Further again, the rare earth soap stock is single rare earth solution or the earth solution that after extraction is divided into groups, obtains, and its content of rare earth is counted 0.1-2.5mol/L with REO.
The Rare Earth Separation method of material interlock recycle provided by the invention makes each self-contained process under the prerequisite that fully reaches enabling objective, to be able to united and coordinating and to carry out.Can see from the reactional equation in each stage of sepn process: it is corresponding (seeing reaction (1), (2) and reaction (7)) with the hydrochloric acid that the rare earth oxalic acid precipitation produces that rare earths material dissolves needed hydrochloric acid; Saponification, extraction step reaction (3), (4) (5) can be merged into and directly carry out rare earth saponification reaction (8); Hydrochloric acid that the acidic extractant extracting rare-earth cements out and washing and the required hydrochloric acid of stripping are (the seeing reaction (6), (8)) of coupling.Under the situation that guarantees extraction efficiency, like cancellation alkali soap process (seeing reaction (3), (4)), replace direct rare earth saponification process (seeing reaction (8)), and the mineral acid that produces is recycled; The back reuse is suitably handled in the acid (square journey (7)) that simultaneously current technology need be neutralized in the oxalic acid precipitation mother liquor of discharging in addition; Should satisfy material dissolution, extraction separation process demand just for acid; Can realize material dissolution, extracting and separating; Process intermediate materials such as rare-earth precipitation washing carry out the interlock recycle of whole process scope, and the Rare Earth Separation whole process is equivalent to equation (9) like this, only need to consume the oxalic acid of equivalent:
RE
2(CO
3)
3+3H
2C
2O
4=RE
2(C
2O
4)
3+3H
2O+3CO
2↑ （9）。
Adopt method of the present invention, compared with prior art, have following advantage:
1) separation method that adopts material of the present invention to link; In whole material interlock recycle process; Adopt the mode that directly prepares rare earth loaded organic phase, and with the whole cyclically utilizing of isolated acid in saponification and the mother liquor of precipitation of ammonium in the Rare Earth Separation process, make the chemical reagent of the Rare Earth Separation whole process consumption that comprises material dissolution, extracting and separating and oxalic acid precipitation that oxalic acid only arranged; Its hydrogen ion is used for dissolving raw material, and oxalate is used for the precipitating rare earth ion.
2) the spent acid recycle that links such as rare earth saponification, oxalic acid precipitation, washing is generated; Spent acid is applied to production link after extraction is reclaimed; Whole Rare Earth Separation process does not all need extra interpolation mineral acid from dissolving the ore deposit to extraction, back extraction; Also save the alkali that adds for the neutralizing acid wastewater accordingly, significantly reduced the reagent cost in producing.
3) directly prepare the organic phase of supported rare earth, contain the sour water reuse that is separated, solved the low problem of the direct non-saponified loading capacity of ordinary method, also do not produce the saliniferous saponification waste-water simultaneously.
4) the oxalic acid precipitation waste water reclamation utilizes, and reclaims hydrochloric acid, oxalic acid respectively, need not the step of consumption alkali neutralization precipitation waste water in the ordinary method, the corresponding discharging of avoiding brine waste.
5) oxalic acid precipitation waste water, saponification waste-water, extracting and washing water all recycle after extracting oxalic acid and/or mineral acid, improve water use efficiency, reduce the unit consumption of water of production process.
6) do not produce saponification waste-water and deposition waste water, do not produce NaCl, NH accordingly yet
4Cl, CaCl
2, MgCl
2, salt such as oxalate discharging.This technology need not to carry out any terminal Pollution abatement, realizes preventing to pollute from the source, and environment protection is had obvious effects.
This technology has also realized optimum of an economy when pursuing environment protection, be an innovative rare earth green separating and producing.
Description of drawings
Fig. 1 is the schema of the Rare Earth Separation method of material interlock recycle provided by the invention.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is further described.
Embodiment 1
Lanthanum cerium carbonate (La, Ce mol ratio are 60: 40) with dissolving with hydrochloric acid; The solution that dissolving obtains is as treating extraction feed; Employing P204 is an extraction agent; In 60 grades of 30L master's extraction tanks, carry out La/Ce and separate, the organic phase flow is 6L/min, and concentration is 1.5mol/L (adopting the mixed organic solvents dilution of 30% secondary octanol+70% sulfonated kerosene).Other establishes the extraction recovery that the secondary extraction tank of 10 grades of 30L carries out acid, adopts the trialkyl methylamine as extraction agent, flow 5L/min, concentration 1.0mol/L (adopting the sulfonated kerosene dilution).The organic phase of two extraction tanks all flows from front to back.
(LaCe) Cl in the main extraction tank
3Feed concentration is 1mol/L, with the flow of 1.5L/min from the 30th grade of adding, 3.0mol/L wash acid with 0.4L/min from the 50th grade of adding, 3.0mol/L back extraction acid with 0.7L/min from the 60th grade of adding.The component Ce that is prone to come together gets into organic phase, through repeatedly extracting, wash the acid elution purifying, after back extraction acid back extraction, amounts to outflow 0.7L/min solution of cerium chloride by oxidation, the about 0.89mol/L of rare earth concentration, acidity 0.33mol/L from the 51st grade; Difficult collection component is stayed aqueous phase, behind abstraction purification, amounts at the 11st grade and flows out the 1.9L/min lanthanum chloride solution, the about 0.9mol/L of content of rare earth wherein, acidity 0.3mol/L; Water all flows from back to front.
Autonomous extraction tank flows out the 1.9L/min lanthanum chloride solution for the 11st grade; Wherein to carry out saponification reaction as rare earth soap stock and blank organic phase (be saponification supported rare earth step shown in Figure 1 to the 0.9L/min lanthanum chloride solution; Down together); Simultaneously, to this part contains the process that acid rare earth solution extracts concentrated mineral acid after the saponification.Concrete operations are: in main extraction tank, secondary extraction tank preceding 10 grades; After 0.9L/min lanthanum chloride solution at first contacts with the trialkyl methylamine of the 10th grade of secondary extraction tank and extracts; Contact with the P204 of the 10th grade of main extraction tank again and extract; Contact with the P204 of the 9th grade of the trialkyl methylamine of the 9th grade of secondary extraction tank, main extraction tank successively again from extraction major trough the 10th grade of effusive lanthanum chloride solution and to extract; And the like, up to the 1st grade of autonomous extraction tank output 0.9L/min do not contain rare earth basically, pH value is about 4 the aqueous solution, recycle.In above-mentioned saponification process, the load of P204 organic phase La, the load of trialkyl methylamine organic phase the hydrochloric acid of 0.54mol/L.
The other 1.0L/min lanthanum chloride solution of the 11st grade of output of main extraction tank (another part that is saponification supported rare earth generating step shown in Figure 1 contains acid rare earth solution) is used the solid oxalic acid precipitation; Oxalic acid precipitation waste water and 1.5mol/L tributyl phosphate (adopting secondary octanol dilution) were by 20: 1 the mixing of comparing; After wherein a small amount of oxalic acid is reclaimed in extraction; Obtain the aqueous solution that 1.0L/min acidity is 3.0mol/L, wherein 0.4L/min returns main extraction tank as washing acid, and the hydrochloric acid that the hydrochloric acid of residue 0.6L/min extracts through the trialkyl methylamine in secondary extraction tank carries out the dissolving of Phosbloc cerium; Obtain treating the lanthanum-cerium chloride solution of extracting and separating, the concrete operations flow process is seen Fig. 1.
Autonomous extraction tank amounts to for the 51st grade and flows out 0.7L/min solution of cerium chloride by oxidation, the about 0.89mol/L of rare earth concentration, acidity 0.33mol/L; After adopting the solid oxalic acid precipitation; Oxalic acid precipitation waste water and 0.5mol/L tributyl phosphate (adopting secondary octanol dilution) be by 0.5: 1 the mixing of comparing, and extraction obtains 0.7L/min 3.0mol/L hydrochloric acid after reclaiming wherein on a small quantity oxalic acid; As back extraction acid, the concrete operations flow process is seen Fig. 1.Oxalic acid in the tributyl phosphate obtains oxalic acid solution after adding water washing, and organic phase is able to regeneration.
Embodiment 2
With dissolving with hydrochloric acid lanthanum cerium carbonate (La, Ce mol ratio are 60: 40); The solution that obtains is as treating extraction feed; Adopting 60%P204 and 40%P507 is extraction agent; In 60 grades of 30L master's extraction tanks, carry out La/Ce and separate, organic flow is 6L/min, and concentration is 1.2mol/L (adopting No. 200 solvent oil dilutions).Other establishes the extraction that the secondary extraction tanks of 10 grades of 30L carry out acid and reclaims, and adopts N, and N-two (1-methylheptyl) ethanamide is as extraction agent, flow 5L/min, concentration 0.8mol/L (adopting No. 20%200 solvent oil+40% isooctyl alcohol+40% industrial kerosene to dilute).The organic phase of two extraction tanks all flows from front to back.
The outlet and the rare earth saponification process of back extraction acid, the adding of washing acid and La, Ce feed liquid are identical with embodiment 1; Lanthanum trichloride soap stock and blank P204/P507 mixed extractant carry out saponification reaction; The load of P204/P507 organic phase La; N, the load of N-two (1-methylheptyl) ethanamide organic phase hydrochloric acid.
After earth solution after the extracting and separating adopts oxalic acid precipitation; Oxalic acid precipitation waste water and 0.5mol/L methyl acid phosphate diformazan heptyl ester (adopting the isooctyl alcohol dilution) were by 1: 1 the mixing of comparing; After wherein a small amount of oxalic acid is reclaimed in extraction, water hydrochloric acid and N, the hydrochloric acid that N-two (1-methylheptyl) ethanamide organic phase is extracted is handled with embodiment 1 mode; Oxalic acid in the methyl acid phosphate diformazan heptyl ester adds the rare earth back extraction and obtains rare earth oxalate, and organic phase is able to regeneration.
Embodiment 3
With nitric acid dissolve lanthanum cerium oxide (La, Ce mol ratio are 60: 40); The solution that obtains is as treating extraction feed; Employing P507 is an extraction agent; Extractant concentration 1.8mol/L (adopting No. 20%200 secondary octanol dilutions of solvent oil+40% industrial kerosene+40%) carries out La/Ce and separates in 60 grades of 30L master's extraction tanks, organic flow is 6L/min.Other establishes the extraction recovery that the secondary extraction tank of 10 grades of 30L carries out acid, adopts trilaurylamine (Tridodecylamine as extraction agent, flow 5L/min, concentration 1.5mol/L (adopting No. 20%200 solvent oil+80% sulfonated kerosenes dilutions).The organic phase of two extraction tanks all flows from front to back.
(LaCe) (NO in the main extraction tank
3)
3Feed concentration 1mol/L, with the flow of 1.5L/min from the 30th grade of adding, 3.0mol/L wash acid with the flow of 0.4L/min from the 50th grade of adding, 3.0mol/L back extraction acid with the flow of 0.7L/min from the 60th grade of adding.Be prone to collection component Ce and get into organic phase, repeatedly extract, wash the acid elution purifying, after back extraction acid back extraction, flow out 0.7L/min cerous nitrate solution, the about 0.89mol/L of rare earth concentration, acidity 0.33mol/L from the 51st grade of total; Difficult collection component is stayed aqueous phase, behind abstraction purification, amounts at the 11st grade and flows out the 1.9L/min lanthanum nitrate hexahydrate, the about 0.9mol/L of content of rare earth wherein, acidity 0.3mol/L; Water all flows from back to front.
Autonomous extraction tank flows out the 1.9L/min lanthanum nitrate hexahydrate for the 11st grade, and get 1.5L/min and carry out saponification reaction as rare earth soap stock and blank organic phase, simultaneously, to this part contains the process that acid rare earth solution extracts concentrated mineral acid after the saponification.Concrete operations are: in main extraction tank, secondary extraction tank preceding 10 grades; 1.5L/min lanthanum nitrate hexahydrate is at first after the 10th grade of secondary extraction tank is by trilaurylamine (Tridodecylamine extraction spent acid wherein; Contact with P507 for the 10th grade at main extraction tank and to extract; Autonomous the 10th grade of effusive lanthanum nitrate hexahydrate of extraction tank contacts with the 9th grade of organic phase of secondary extraction tank, main extraction tank successively and extracts; And the like, final P507 organic phase load the lanthanum of 0.135mol/L, the load of trilaurylamine (Tridodecylamine organic phase the nitric acid of 0.53mol/L., the 1st grade of main extraction tank contain acid rare earth solution after flowing out the 1.5L/min saponification, Lanthanum trinitrate 0.36mol/L wherein, acidity 0.15mol/L.
Contain acid rare earth solution after the saponification and adopt oxalic acid precipitation, and with behind the oxalic acid in the tributyl phosphate recovery oxalic acid precipitation waste water, water is the nitric acid of 1.5L/min, concentration 1.23mol/L.The nitric acid that this nitric acid and trilaurylamine (Tridodecylamine extract merges dissolved oxygen lanthanum cerium, obtains Lanthanum trinitrate cerium feed liquid to be extracted.
The other 0.4L/min lanthanum nitrate hexahydrate of the 11st grade of output of main extraction tank; Use the solid oxalic acid precipitation; Oxalic acid precipitation waste water and of the compare mixing of 1.0mol/L tributyl phosphate by 10: 1; Extraction obtains the aqueous solution that 0.4L/min acidity is 3.0mol/L after reclaiming wherein a small amount of oxalic acid, advances to return main extraction tank as washing acid.
Autonomous extraction tank amounts to for the 51st grade and flows out the 0.7L/min cerous nitrate solution; The about 0.89mol/L of rare earth concentration, acidity 0.33mol/L is behind the employing solid oxalic acid precipitation; Oxalic acid precipitation waste water and of the compare mixing of 1.0mol/L tributyl phosphate by 0.2: 1; Extraction obtains 0.7L/min 3.0mol/L hydrochloric acid after reclaiming wherein a small amount of oxalic acid, as back extraction acid.Oxalic acid in the tributyl phosphate obtains oxalic acid solution after adding water washing, and organic phase is able to regeneration.
Embodiment 4
The rare earth soap stock is the difficulty collection component that sulfuric acid rare earth leach liquor that mishmetal ore deposit, packet header obtains after sulfuric acid baking, water logging removal of impurities obtains after extracting and separating, REO content 15g/L wherein, and pH is 3, principal constituent is the earth solution that contains La, Ce.
The rare earth soap stock is carried out the rare earth soap reaction, P204 concentration 1.2mol/L (adopting No. 200 solvent oils to dilute) with mixing with the blank organic phase of P204.Rare earth saponification process adopts 8 grades of extraction tank counter flow in series extractions; The volume ratio of water and oil phase is 2: 1; Hydrogen ion in this process organic phase is got into water by rare earth exchanged, and most of rare earth gets in the organic phase in the water, and containing in the acid rare earth solution of obtaining after the final rare earth saponification contains H
+0.27mol/L, REO 0.5g/L, effusive organic phase is the organic phase of supported rare earth, gets into the rare earth extraction separator tank and carries out follow-up interlock extracting and separating.
Containing of after the rare earth saponification, obtaining adds oxalic acid solution precipitating rare earth ion in the acid rare earth solution, control deposition terminal point oxalic acid is excessive, filters, and washing obtains containing H
+0.08mol/L sulfuric acid and the oxalic acid precipitation waste water of 0.01mol/L oxalic acid.
Oxalic acid precipitation waste water and methyl acid phosphate diformazan heptyl ester extraction agent extract oxalic acid according to 10: 1 mixed of volume ratio, methyl acid phosphate diformazan heptyl ester concentration 0.5mol/L (adopting No. 260 solvent oils dilutions).Through 5 stage countercurrent extracting and separating, the balance organic phase of load oxalic acid obtains sodium oxalate solution with the back extraction of 1mol/L NaOH solution, and the balance water is a dilution heat of sulfuric acid.
The above-mentioned dilution heat of sulfuric acid that separation is obtained mixes according to 20: 1 volume ratio with 1.8mol/L primary amine N1923 (adopting the sulfonated kerosene dilution); Through the extraction of 2 stage countercurrents; Sulfuric acid is got into organic phase by the amine extractant extraction, and water is able to the infusion of reprocessing cycle as the sulfuric acid baking ore deposit; Sulfuric acid after extraction concentrates is used to dissolve the baotite mixed rare earth carbonate of 40wt%, obtains the mix sulphur acid rare earth feed liquid of 30g/L.
Embodiment 5
SmCl with the 1.5mol/L that obtains after the extracting and separating
3Solution mixes with the blank organic phase that with P507 is extraction agent and carries out the rare earth soap reaction, and P507 concentration is 0.5mol/L (adopting the mixed organic solvents of 10% isooctyl alcohol+90% sulfonated kerosene to dilute).Rare earth saponification process adopts 4 grades of extraction tank counter flow in series extractions, and the volume ratio of water and oil phase is 20: 1, and the hydrogen ion in this process organic phase is got into water by rare earth exchanged, and effusive water is for containing H
+0.01mol/L contain acid rare earth solution, effusive organic phase is the organic phase of supported rare earth, gets into the rare earth extraction separator tank and carries out follow-up interlock extracting and separating.
The acid rare earth solution that contains that obtains after the rare earth saponification is mixed according to 20: 1 volume ratio with 1.8mol/L three octyl tertiary amine extraction agents (sulfonated kerosene dilution); Through the extraction of 2 stage countercurrents; Hydrochloric acid is got into organic phase by the amine extractant extraction, and water is the SmCl that pH equals 4
3Solution, circulation is as the rare earth soap stock of preparation rare earth soap.
Hydrochloric acid after the extraction of three octyl tertiary amine extraction agents concentrates is used to dissolve southern ore deposit mixed rare earth oxide (REO content 92%), the dissolved mishmetal feed liquid that obtains 64g/L of rare earth.
Embodiment 6
The single rare earth solution D y (NO that obtains to extracting and separating
3)
3Add the oxalic acid precipitation rare earth ion in the solution, control precipitation process rare earth is excessive, obtains containing HNO
30.5mol/L, Dy (NO
3)
30.1mol/L oxalic acid precipitation waste water.
Oxalic acid precipitation waste water and 0.3mol/L two (1-isobutyl--3; 5-dimethyl-hexyl) amine extractant (adopting secondary octanol dilution) mixes according to 0.5: 1 volume ratio; Through the extraction of 2 stage countercurrents, nitric acid is got into organic phase by the amine extractant extraction, and water is the Dy (NO that pH equals 4
3)
3Solution is circulated to the oxalic acid precipitation step.Nitric acid after the extraction of two (1-isobutyl--3,5-dimethyl-hexyl) amine extractant concentrates is used to dissolve southern ore deposit mixed rare earth carbonate (REO content 30%), the dissolved mishmetal feed liquid that obtains 20g/L of rare earth.
Embodiment 7
That will drag for certainly that yttrium washes that calcium extraction tank (utilizing low-concentration hcl load to be dragged for the calcium back extraction in the organic phase of yttrium) obtains contains HCl 1mol/L, CaCl
20.1mol/L acid waste water and 1.5mol/L two (1-methylheptyl) amine (adopting No. 200 solvent oils dilutions) extraction agent mix according to 1: 1 volume ratio; Hydrochloric acid is got into organic phase by the amine extractant extraction, and the hydrochloric acid after extraction concentrates is used to dissolve southern ore deposit mixed rare earth oxide (REO content 92%).
The foregoing description just illustrates of the present invention, and the present invention also can implement with other ad hoc fashion or other particular form, and does not depart from main idea of the present invention or essential characteristic.Therefore, the embodiment of description all should be regarded as illustrative from any aspect but not be determinate.Scope of the present invention should be by additional claim explanation, and any intention and equivalent variation of scope with claim also should be within the scope of the present invention.
Claims (12)
1. the Rare Earth Separation method of material interlock recycle may further comprise the steps:
(I) is dissolved in mishmetal infusion that mix sulphur acid rare earth infusion that mixed rare earth solution that inorganic acid solution obtains or sulfuric acid roasting method obtain or the IX of southern ore deposit obtains as treating extraction feed with rare earth carbonate or oxide compound;
(II) is 0.1-20 with the rare earth soap stock with using the blank extraction agent A behind the organic solvent diluting by volume: 1 ratio thorough mixing, directly carry out the rare earth saponification reaction, and obtain the organic phase of supported rare earth and contain acid rare earth solution;
The organic phase of treating the supported rare earth that extraction feed and step (II) obtain that (III) obtains step (I) is mixed in the cascade extraction groove and is carried out the rare earth exchanged purification reaction; Through repeatedly the washing, the back extraction organic phase; Obtain single rare earth solution and blank extraction agent A respectively, blank extraction agent A returns step (II) and utilizes again;
Single rare earth solution and oxalic acid mixed precipitation rare earth ion that (IV) obtains step (III) separate, wash the rare earth oxalate throw out, obtain containing the oxalic acid precipitation waste water of oxalic acid and mineral acid;
The oxalic acid precipitation waste water that (V) obtains step (IV) with the 0.1-20 by volume of the extraction agent B behind the organic solvent diluting: 1 ratio thorough mixing; The balance water that obtains the organic phase of load oxalic acid and contain mineral acid, the oxalic acid in organic phase precipitating rare earth ion again after reclaiming;
The balance water that contains mineral acid that (VI) step (V) obtains returns step (I) dissolving rare earth carbonate or oxide compound, perhaps returns step (III) washing, back extraction organic phase;
The acid rare earth solution that contains that obtains after (VII) step (II) middle-weight rare earths saponification reaction adopts the method precipitating rare earth ion in the step (IV), and adopts the method for step (V)-(VI) to handle oxalic acid precipitation waste water.
2. the Rare Earth Separation method of a kind of material interlock recycle according to claim 1; It is characterized in that; In the step (II), the rare earth soap stock is 1-5 with the volume ratio of using the blank extraction agent A behind the organic solvent diluting: 1, and said extraction agent A is selected from 2-ethylhexyl phosphoric acid, di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester, two (2; 4; The 4-tri-methyl-amyl) one or more in phosphonic acids and two (2-ethylhexyl) phosphonic acid ester, said organic solvent is selected from one or more in industrial kerosene, sulfonated kerosene, solvent oil, isooctyl alcohol, the secondary octanol, and the concentration of extraction agent A is 0.5-1.8mol/L.
3. the Rare Earth Separation method of a kind of material interlock recycle according to claim 1 and 2; It is characterized in that; Rare earth soap stock in the step (II) is single rare earth solution or the earth solution that after extraction is divided into groups, obtains, and its content of rare earth is counted 0.1-2.5mol/L with REO.
4. the Rare Earth Separation method of a kind of material interlock recycle according to claim 3; It is characterized in that; When the rare earth soap stock in the step (II) is single rare earth solution; In the step (VII), the rare earth saponification reaction obtains contains single rare earth solution of the same race that acid rare earth solution and step (III) obtain and merges the back and adopt the method precipitating rare earth ion in the step (IV).
5. the Rare Earth Separation method of a kind of material interlock recycle according to claim 1 and 2; It is characterized in that; In the step (V), oxalic acid precipitation waste water is 0.5-5 with the volume ratio of using the extraction agent B behind the organic solvent diluting: 1, and extraction agent B is tributyl phosphate and/or methyl acid phosphate diformazan heptyl ester; Said organic solvent is selected from one or more in industrial kerosene, sulfonated kerosene, solvent oil, isooctyl alcohol, the secondary octanol, and the concentration of extraction agent B is 0.1-1.8mol/L.
6. the Rare Earth Separation method of a kind of material interlock recycle according to claim 1 and 2; It is characterized in that, when reclaiming oxalic acid in the step (V), make the organic phase of water back extraction load oxalic acid; Obtain oxalic acid solution, oxalic acid returns does step (IV) precipitating rare earth ion; Or the organic phase of use earth solution back extraction load oxalic acid, obtain the rare earth oxalate throw out; Or the organic phase of use ammoniacal liquor or sodium hydroxide solution back extraction load oxalic acid, obtain ammonium oxalate or sodium oxalate sub product.
7. the Rare Earth Separation method of a kind of material interlock recycle according to claim 1 and 2; It is characterized in that; In the step (VI); The balance water that contains mineral acid returns before step (I) use; Make in advance the balance water that contains mineral acid with the 0.1-20 by volume of the extraction agent C behind the organic solvent diluting: 1 mixed extraction concentrates, and the mineral acid after concentrating returns step (I) and uses, and end water or the sedimentary wash water of rare earth oxalate that water is done to dissolve the end water of material or prepare oxalic acid solution recycle.
8. the Rare Earth Separation method of a kind of material interlock recycle according to claim 7; It is characterized in that; Said extraction agent C is selected from secondary carbon primary amine, trialkyl methylamine, N-laurylene (trialkyl methyl) amine, two (1-isobutyl--3; 5-dimethyl-hexyl) amine, two (1-methylheptyl) amine, N; In N-two (1-methylheptyl) ethanamide, tri-n-octyl amine, tri-iso-octylamine, three octyl tertiary amines, the trilaurylamine (Tridodecylamine and three (2-DEHA) one or more, said organic solvent is selected from one or more in industrial kerosene, sulfonated kerosene, solvent oil, isooctyl alcohol, the secondary octanol, and the concentration of extraction agent C is 0.1-1.8mol/L.
9. the Rare Earth Separation method of material interlock recycle; Comprise molten material, extracting and separating, oxalic acid precipitation and washing procedure; The extracting and separating operation comprises saponification supported rare earth and rare earth exchanged purification step; It is characterized in that; Inorganic acid solution that extracting and separating, oxalic acid precipitation and washing procedure are produced or the earth solution that contains mineral acid with the 0.1-20 by volume of the extraction agent C behind the organic solvent diluting: 1 ratio thorough mixing, extraction concentrates mineral acid, the mineral acid after concentrating returns molten material process and recycles; The low sour water that contains rare earth returns saponification supported rare earth step mutually, and the low sour water that does not contain rare earth does to dissolve the end water of material mutually or the end water or the sedimentary wash water of rare earth oxalate of preparation oxalic acid solution recycles.
10. the Rare Earth Separation method of a kind of material interlock recycle according to claim 9; It is characterized in that; Said extraction agent C is selected from secondary carbon primary amine, trialkyl methylamine, N-laurylene (trialkyl methyl) amine, two (1-isobutyl--3; 5-dimethyl-hexyl) amine, two (1-methylheptyl) amine, N; In N-two (1-methylheptyl) ethanamide, tri-n-octyl amine, tri-iso-octylamine, three octyl tertiary amines, the trilaurylamine (Tridodecylamine and three (2-DEHA) one or more, the concentration of extraction agent C is 0.1-1.8mol/L, said organic solvent is selected from one or more in industrial kerosene, sulfonated kerosene, solvent oil, isooctyl alcohol, the secondary octanol.
11. Rare Earth Separation method according to claim 9 or 10 described a kind of material interlock recycles; It is characterized in that; Blank extraction agent A after saponification supported rare earth step adopts the rare earth soap stock and uses organic solvent diluting is 1-20 by volume: 1 ratio thorough mixing, directly carry out the rare earth saponification reaction; Said extraction agent A is selected from one or more in 2-ethylhexyl phosphoric acid, di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester, two (2,4, the 4-tri-methyl-amyl) phosphonic acids and two (2-ethylhexyl) phosphonic acid ester, and the concentration of extraction agent A is 0.5-1.8mol/L.
12. the Rare Earth Separation method of a kind of material interlock recycle according to claim 11 is characterized in that, the rare earth soap stock is single rare earth solution or the earth solution that after the extraction grouping, obtains, and its content of rare earth is counted 0.1-2.5mol/L with REO.
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Also Published As
| Publication number | Publication date |
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| WO2013177729A1 (en) | 2013-12-05 |
| CN102676853B (en) | 2013-11-20 |
| MY170574A (en) | 2019-08-19 |
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