CN101182597A - Method of acidic extractant complexing extraction separation rare-earth element - Google Patents
Method of acidic extractant complexing extraction separation rare-earth element Download PDFInfo
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Abstract
The invention relates to a method for complexing, extracting and separating the rare earth element with an acid phosphate extraction agent; the point is that rare earth chloride solution is added with citric acid or salt citrate to form rare earth chloride-hydrochloric acid-citric acid mixing solution as the water phase and the P204 or P205 acid phosphate extraction agent for extraction and separation; diluted coal oil is taken as the organic phase for extraction and separation; the rare earth element is separated through processes of extraction, washing and reverse extraction in an extraction groove; the extraction residual liquid which contains the citric acid is returned for recycling. The invention is characterized in that with the complexion action of the citric acid and the rare earth element, the separation effect of the acid phosphate extraction agent on the rare earth element is enhanced and especially the rare earth element in the high-consistency rare earth solution, the REO of which equals to 200 to 300g/l can be separated; at the same time, the acid phosphate extraction agent also has comparatively high capability and effect for extracting the rare earth element without saponification process. The invention needs a small amount of investment and the production cost is low; moreover, according to the method, the environmental pollution is reduced.
Description
Technical field
The present invention relates to a kind of method of acidic organophosphorus extractant for extraction separation of rare-earth elements, be specifically related to from contain multiple rare earth element chloride soln, adopt the acidic organophosphorus extractant complexometric extraction to isolate the method for single or a few group rare-earth elements.
Background technology
Rare earth element is the general name of lanthanum in the periodic table of elements and lanthanon and scandium, yttrium.These elements have special physics and chemical property, and in metallurgy, petrochemical complex, glass-ceramic field and various functional materials, normal a kind of or certain several element wherein of selecting use as additive and necessary moiety.
Symbiosis is together in natural mineral for rare earth element.Rare earth element in hamartite, solitary stone ore and fluorine carbon cerium and the monazite mixed type rare-earth mineral is based on lanthanum, cerium, praseodymium, neodymium and a spot of other rare earth elements, so be called the light rare earths mineral.With yttrium is that the mineral of main rare earth composition are called the heavy rare earths mineral.Hamartite often adopts oxidizing roasting to decompose, and solitary stone ore and fluorine carbon cerium and monazite mixed type rare-earth mineral mainly adopt sulfuric acid baking or sodium hydroxide to decompose.Mineral after the decomposition add mineral acid (hydrochloric acid, sulfuric acid, nitric acid) solution, through leaching and removing the non-rare earth impurity technological process and can prepare the identical mixing solutions of rare earth element (hereafter is a light rare earths ore deposit partition) that contains with former mineral.
In order to obtain the product that single rare earth element or certain several rare earth element are formed, industrial organic solvent extract extraction process commonly used separates its rare earth element.The technology of typical organic solvent extract extracting and separating rear earth element can be divided into following several types by the molecular structure of extraction agent:
1. neutral extraction agent: TBP (tbp) or P350 (the hot fat of methyl-phosphorous acid di-secondary) separation of rare earth elements method.At first neutral extraction agent is diluted to the organic phase that contains the finite concentration extraction agent with kerosene in this technology, then organic phase separates rare earth element with rare earth nitrate solution through repeatedly mixing with the clarification operation again.Because this technology is main industrial chemicals with nitric acid, become to produce the cost height, and operating environment is relatively poor existing seldom employing.
2. carboxylic acid extraction agent: naphthenic acid separation of rare earth elements method.At first naphthenic acid is diluted to the organic phase that contains the finite concentration extraction agent with kerosene and alcohol mixture in this technology, then organic phase separates rare earth element with hydrochloric acid or rare earth sulfate solution through repeatedly mixing with the clarification operation again.Because naphthenic acid and acidic organophosphorus extractant for extraction rare earth element order difference, this technology has remarkable advantages aspect the high-purity yttrium extracting, still for the full separation of rare earth element far away from other several extraction agents.
3. acidic organophosphorus extractant: two (2-ethylhexyl phosphoric acid) (P204 hereinafter referred to as) or 2-ethylhexyl phosphonic acid list ethylhexyl fat (being called P507) extraction agent separation of rare earth elements.At first P204 or P507 are diluted to the organic phase that contains the finite concentration extraction agent with kerosene in this technology, then organic phase separates rare earth element with hydrochloric acid or rare earth sulfate solution through repeatedly mixing with the clarification operation again.
Naphthenic acid, P204 and P507 belong to the acid type extraction agent, hydrogen ion generation replacement(metathesis)reaction in the hydroxyl of the carboxyl of the metallic cation of extraction process aqueous phase and naphthenic acid or P204 and P507, metal ion and extraction agent help collection, hydrogen ion enters organic phase, with constantly carrying out of extraction process, the acidity of aqueous phase increases.Because acid type extraction agent extracting metals ionic ability increases and significantly reduces with the acidity in the aqueous solution, causes extraction agent to lose extracting power the most at last.Solution to this problem is before the extracting metals ion, at first extraction agent is carried out saponification, promptly with containing Na
+, NH
4 +Or Ca
2+The ionic basic solution is handled extraction agent, with Na
+, NH
4 +Or Ca
+The tradable H of part in the ionic replacement extraction agent
+Ion.Extraction agent after the saponification has the good extracting power and the effect of separation of rare earth elements, makes P204 and P507 extraction agent can satisfy the requirement of the full separation industries of rare earth, and particularly the P507 extraction agent has been widely used in the separation of produced of rare earth element.
Na
+Or NH
4 +Method for saponification need be with a large amount of alkali, and saponification again at every turn in organic phase recycles, and production cost is increased, and has reduced economic benefit.Patent 200410050948.4 discloses a kind of Ca
2+Or Mg
2+The method of basic solution saponification acid type extraction agent.This kind method replaces sodium hydroxide and ammoniacal liquor and bicarbonate of ammonia with the oxide compound or the carbonate of inexpensive calcium or magnesium, and production cost is reduced.But find in producing that the calcium of industrial level or the oxide compound or the carbonate of magnesium contain a spot of aluminium impurity, when using as saponifying agent with it, aluminium is enrichment in extraction tank, often causes the purity of rare-earth products not reach customer requirements.If oxide compound or carbonate with highly purified calcium or magnesium then do not have remarkable advantages on the price.
Comparatively speaking, be the NH of raw material with ammoniacal liquor or bicarbonate of ammonia
4 +The method for saponification production cost is moderate, and the purity of rare-earth products is not subjected to the influence of saponifying agent, is present industrial separation of rare earth elements main method.The shortcoming of this kind method is to contain a large amount of ammonia nitriding compounds in the extraction wastewater, and directly discharging is with the polluted water resource.To this problem, once reclaimed ammonium chloride in the production, but seldom adopted because cost recovery is too high with evaporation concentration method.
This shows that in today of industrial production and nature harmonious coexistence, the solvent extraction method separation of rare earth elements technology of exploitation cleaning is imperative.In order to reach this purpose, preferred measure is under non-saponifying prerequisite, improves P204 and P507 extraction agent extracting metals ion ability.Patent 200510098261.4 discloses the method for non-saponified P204 and P507 extraction agent separation of rare earth elements in earth solution.This method in P204, add a certain proportion of P507, overcome P204 is easy to emulsification and the difficult back extraction of middle heavy rare earth element during the extracting rare-earth ion under low acidity feed liquid condition problem.No ammonia nitrogen waste water produces in this extraction process, and has reduced sour consumption.But patent 200510098261.4 application examples have only confirmed that (effect of extracting of REO≤48g/L) does not relate to earth solution (the rare earth extraction division technique of REO=200～300g/L) of high density to this method at lower following of concentration of metal ions.
Summary of the invention
The present invention seeks at the deficiencies in the prior art part, a kind of method of acidic organophosphorus extractant complexometric extraction separation of rare earth elements is provided.Promptly adopt the rare earth chloride-hydrochloric acid-citric acid mixing solutions that in re chloride, adds citric acid or Citrate trianion formation, utilize the complexing action of citric acid, strengthened the effect of acidic organophosphorus extractant separation of rare earth elements, especially solving the earth solution that goes for high density is the rare earth extraction separating effect of REO=200～300g/L.This kind is the method for the acidic phosphorus type extracting and separating rear earth element of complexing agent with the lemon, at acidic organophosphorus extractant under the saponification treatment condition, still have ability and the separation of rare earth elements effect identical with saponifiable extraction agent extracting rare-earth element, reach simultaneously and reduce production costs the minimizing environmental pollution.
The technical scheme that realizes the object of the invention is: being called P204 or 2-ethylhexyl phosphonic acid list ethylhexyl fat with two (2-ethylhexyl phosphoric acids), to be called P507 be acidic organophosphorus extractant, with the organic phase of kerosene dilution as extracting and separating, main points are to add citric acid or Citrate trianion forms the water of rare earth chloride-hydrochloric acid-citric acid mixing solutions as extracting and separating in re chloride, contain citric acid or citric acid salt concentration≤0.25mol/L in the solution; The organic phase of above-mentioned extracting and separating and water through extraction, washing and reextraction, separate rare earth element in extraction tank; The raffinate that contains citric acid returns and recycles.
As the kerosene that thinner is used, select 260 for use
#Sulfonated kerosene or aviation kerosene are 1.0～1.5mol/L with the acidic organophosphorus extractant dilution for concentration, with this organic phase as extracting and separating.
At least contain two kinds of rare earth elements in the above-mentioned re chloride.This solution is with the rare earth oxide summation meter, and concentration is REO=10～300 grams per liters.Selecting and choosing strength of solution earlier is REO=200～300 grams per liters.
The Citrate trianion that adds in re chloride recited above is selected Trisodium Citrate or citric acid lanthanum for use.
The present invention selects for use with two (2-ethylhexyl phosphoric acids) when being acidic organophosphorus extractant, the pH value of the rare earth chloride-hydrochloric acid-citric acid mixing solutions of preparation is 0.5～2, when being acidic organophosphorus extractant with 2-ethylhexyl phosphonic acid list ethylhexyl fat, the pH value of the rare earth chloride-hydrochloric acid of preparation-citric acid mixing solutions is 1～1.5.
The present invention returns use to the raffinate that contains citric acid through isolating rare earth element, be meant that with rare earth carbonate or rare-earth hydroxide precipitation circulation is used to prepare rare earth chloride-hydrochloric acid-citric acid mixing solutions or preparation citric acid rare-earth products to the rare earth Citrate trianion that obtains as additive.
The present invention compared with the prior art, outstanding feature is: select for use citric acid as helping the collection agent, add in the re chloride, utilize the complexing action of citric acid, strengthened the effect of acidic organophosphorus extractant separation of rare earth elements, this kind is the acidic organophosphorus extractant separation of rare earth elements of complexing agent with the citric acid, under the condition that does not need to handle through saponification at acidic organophosphorus extractant, still can reach the effect of the ability separation of rare earth elements identical with saponifiable extraction agent extracting rare-earth element.
In addition, the raffinate that contain citric acid of the present invention behind the extracting and separating rear earth element can obtain sufficient recycle.
By the characteristics that the invention described above had, and produced tangible positively effect:
1, do not need saponifying agent in the production, reduced production cost, omitted the saponification treating processes, saved the saponification facility investment, reduced pollution, more help production process control and management simultaneously environment;
2, with the citric acid be complexing agent,, can realize making the rare earth element among the earth solution REO=200～300g/L of high density to be separated as the method that helps collection agent separation of rare earth elements of acidic organophosphorus extractant.
3, owing to contain the recycle of the raffinate of citric acid, production cost can not improved because of the use of citric acid.
Embodiment
Related re chloride all is by hamartite in the example of the present invention, and solitary stone ore or hamartite and monazite mixed type rare-earth mineral are raw material, adopts known method formulated, to this, below no longer repeat among the embodiment.
Example 1
Is the organic phase that contains P204=1.5 ± 0.2mol/L with P204 (commercially available) extraction agent with 260# sulfonated kerosene (commercially available) dilution.By the re chloride that the preparation of solitary stone ore obtains, contain the total concn REO=280 ± 20g/L of rare earth element, partition of rare earth element wherein in the percentage ratio of each rare earth element quality of oxide compound and the ratio of total rare earth oxide compound REO quality is: La
2O
3/ REO=25%; CeO
2=51%; Pr
6O
11=6.5%; Nd
2O
3=15.5%; Middle heavy rare earths (in oxide compound)=2%.In this solution, add citric acid, be mixed with the rare earth aqueous solution that contains citric acid 0.23 ± 0.02mol/L, pH=0.5～1, the organic phase and the rare earth aqueous solution that prepare were charged into extraction tank in 1: 1 by volume, carrying out LaCePrNd in the fractionation extraction mode separates with middle heavy rare earths, the fractionation extraction progression that adopts is: extract 14 grades, wash 8 grades, strip 8 grades, stream than (enter the volumetric flow rate of the various liquid of extraction tank, unit represents with L/min) is: organic phase: earth solution: washing lotion=2.1: 1: 0.3; Collection has the salt acid elution of the organic phase of rare earth element with 3N, and the hydrochloric acid of 6N is stripped, and returns extraction cycle through the organic phase of stripping and uses.The solution of heavy rare-earth oxide 230g/L during this time extracting and separating obtains containing, this solution is used for producing the heavy rare-earth oxide product.
Separate with middle heavy rare earths through above-mentioned LaCePrNd and to obtain raffinate and contain La
2O
3+ CeO
2+ Pr
6O
11+ Nd
2O
3=230g/L, acidity=0.2N, this solution is neutralized to pH=1 with the carbonate of light rare earths, carries out NdPr in the fractionation extraction mode and separates with CeLa.The fractionation extraction progression that adopts is: extract 47 grades, wash 43 grades, strip 8 grades; Stream is than being: organic phase: earth solution: washing lotion=7.5: 1: 0.5; Collection has the salt acid elution of the organic phase of rare earth element with 3N, and the hydrochloric acid of 6N is stripped.Contain praseodymium neodymium rare earth oxide 210g/L in the anti-stripping agent after the extracting and separating, this solution is used for producing mixing praseodymium neodymium oxides product.
Separate the raffinate acidity that contains the lanthanum Ce elements that obtains with CeLa through NdPr and be about 0.1～0.2N.This solution can be neutralized to pH=1 with lanthanum cerium carbonated rare earth, 25 grades of extractions, washs 35 grades, carries out Ce in 8 grades the fractionation extraction groove of stripping and separates with La; Stream is than being organic phase: earth solution: washing lotion=8.5: 1: 0.2; Collection has the salt acid elution of the organic phase of Ce element with 3N, and the hydrochloric acid of 6N is stripped, and obtains containing CeO
2=230g/L, the solution of acidity=0.2N, this solution is used to produce cerium oxide product.
The raffinate acidity that contains lanthanum element is about 0.1N, can be neutralized to pH=4 with Phosbloc or lanthanum hydroxide earlier, makes citric acid in the solution and lanthanum form the solid rare earth Citrate trianion, and precipitates from solution and separate out.The solid rare earth Citrate trianion that obtains thus replaces citric acid to add in the mixed rare earth solution as additive, is recycled and reused for preparation muriate-citric acid mixing solutions or is used to prepare the citric acid rare-earth products.
The method that the above-mentioned various earth solutions that obtain through extracting and separating can be further used for producing rare earth oxide is: adopt oxalic acid or ammonium bicarbonate precipitation respectively, be converted into corresponding rare-earth salts, again through the baked for producing rare earth oxide.The purity of resulting rare earth oxide product is respectively: middle heavy rare-earth oxide=230g/L, Pr
6O
11+ Nd
2O
3/ REO 〉=99.9%; CeO
2/ REO 〉=99%; La
2O
3/ REO 〉=99%.The utilization ratio of whole process citric acid is greater than 85%, and the yield of rare earth element is greater than 95%.
Embodiment 2
The separation method that present embodiment adopted is identical with embodiment 1, and difference is: (1) with P204 (commercially available) extraction agent with commercially available 260
#Sulfonated kerosene (commercially available) dilution is for containing the organic phase of P204=1.0 ± 0.2mol/L.(2) mixed rare earth solution that obtains by fluorine carbon cerium and monazite mixed type rare-earth mineral, employing is obtained by the dissolving with hydrochloric acid mixed rare earth carbonate, this solution contains rare earth element, and (re chloride of REO=220 ± 20g/L), the partition of rare earth element in the solution in the percentage ratio of each rare earth element quality of oxide compound and the ratio of total rare earth oxide compound REO quality is: La
2O
3/ REO=53%; CeO
2=15%; Pr
6O
11=10%; Nd
2O
3=20%; Middle heavy rare earths (in oxide compound)=2%.(3) add citric acid, be mixed with the rare earth aqueous solution that contains citric acid 0.23 ± 0.02mol/L, pH=1.0～2.0.(4) LaCePrNd and middle heavy rare earth element are separated in 15 grades of extractions, wash 15 grades, carry out in 8 grades the fractionation extraction groove of stripping; Stream is than being: organic phase: earth solution: washing lotion=2.3: 1: 0.2; NdPr and CeLa are separated in 52 grades of extractions, washs 18 grades, carry out in 8 grades the fractionation extraction groove of stripping, and flow than being: organic phase: earth solution: washing lotion=6.8: 1: 1.09; Ce separates with La and is separated in 27 grades of extractions, washs 24 grades, carries out in 8 grades the fractionation extraction groove of stripping; Stream is than being organic phase: earth solution: washing lotion=4.5: 1: 0.7;
The purity of resulting rare earth oxide product is respectively Pr
6O
11+ Nd
2O
3/ REO 〉=99.9%; CeO
2/ REO 〉=99%; La
2O
3/ REO 〉=99%; Sm-eu-gd enriched substance (Eu
2O
3/ REO 〉=8%).The utilization ratio of whole process citric acid is greater than 85%, and the yield of rare earth element is greater than 95%.
Embodiment 3
Present embodiment the separation method of isolating rare earth fluoride solution and employing identical with embodiment 1, difference is: (1) with P507 (commercially available) extraction agent with aviation kerosene (commercially available) dilution for containing the organic phase of P507=1.5 ± 0.2mol/L.(2) re chloride pH=1～1.5; (3) LaCePrNd and middle heavy rare earth element are separated in 17 grades of extractions, wash 13 grades, carry out NdPr in 8 grades the fractionation extraction groove of stripping and separate with Sm (comprising heavy rare earth element in other); Stream is than being: organic phase: earth solution: washing lotion=5.7: 1: 1.1; NdPr and CeLa are separated in 51 grades of extractions, washs 46 grades, separate in 8 grades the fractionation extraction groove of stripping, and flow than being: organic phase: earth solution: washing lotion=12: 1: 0.6; Ce separates with La and is separated in 27 grades of extractions, washs 36 grades, carries out in 8 grades the fractionation extraction groove of stripping; The separated flow ratio is organic phase: earth solution: washing lotion=8.3: 1: 0.4.Collection has the salt acid elution of the organic phase of rare earth element with 3N, and the hydrochloric acid of 6N is stripped, and the purity of the rare earth oxide product that obtains is respectively: Pr
6O
11+ Nd
2O
3/ REO 〉=99.9%; CeO
2/ REO 〉=99%; La
2O
3/ REO 〉=99%; Sm-eu-gd enriched substance (Eu
2O
3/ REO 〉=8%).The utilization ratio of whole process citric acid is greater than 85%, and the yield of rare earth element is greater than 95%.
Embodiment 4
Use the dilute hydrochloric acid of 0.5mol/L to leach tervalent rare earth element earlier through the hamartite of oxidizing roasting, reach and CeO
2The purpose of initial gross separation.When leaching, add citric acid in order to suppress the stripping of fluorine element.The solution middle-weight rare earths concentration of element that this kind method obtains is lower, and contains citric acid.The present invention takes following method to reclaim rare earth element.
With P204 (commercially available) extraction agent with 260
#Sulfonated kerosene (commercially available) dilution is for containing the organic phase of P204=1.0 ± 0.2mol/L.(re chloride of REO=13 ± 3g/L) is added citric acid to contain rare earth element, be mixed with the rare earth aqueous solution that contains citric acid 0.04mol/L, pH=0.5～1, extract whole rare earth elements by 10 stage countercurrent modes, the stream ratio of counter-current extraction is, organic phase: earth solution: washing lotion=0.7: 1: 0.1, with the 6 stage countercurrent modes rare earth element of stripping, return counter-current extraction rare earth operation and recycle by organic phase with the 6N hydrochloric acid soln for the organic phase of extraction supported rare earth element.Still contain hydrochloric acid and citric acid in the raffinate behind the extracting rare-earth element, adding hydrochloric acid and citric acid, to be mixed with concentration be hydrochloric acid 0.5molL-1; Be recycled and reused for from hamartite oxidizing roasting product behind the citric acid 0.04molL-1 mixing solutions and leach rare earth element, the aqueous solution that the reextraction gained contains rare earth element can be used for further preparing mixed rare-earth oxide, rare earth chloride or separates the single rare earth product by the method for embodiment 1 or 2.The whole process rare earth element rate of recovery is 95%; The citric acid utilization ratio is 90%.
Claims (6)
1. the method for an acidic extractant complexing extraction separation rare-earth element, with two (2-ethylhexyl phosphoric acids) or 2-ethylhexyl phosphonic acid list ethylhexyl fat is acidic organophosphorus extractant, with the organic phase of kerosene dilution as extracting and separating, it is characterized in that in re chloride adding citric acid or Citrate trianion is mixed with the water of rare earth chloride-hydrochloric acid-citric acid mixing solutions as extracting and separating, this mixing solutions contains citric acid or citric acid salt concentration≤0.25mol/L; The organic phase of extracting and separating and water through extraction, washing and reextraction, separate rare earth element in extraction tank, and the raffinate that contains citric acid returns and recycles.
2. according to the method for the described a kind of acidic extractant complexing extraction separation rare-earth element of claim 1, it is characterized in that described kerosene selects 260 for use
#Sulfonated kerosene or aviation kerosene, the acidic organophosphorus extractant dilution is the organic phase of extracting and separating, and concentration is 1.0～1.5mol/L, and the rare earth oxide in the re chloride contains two kinds of rare earth elements at least, this solution is with the rare earth oxide summation meter, and concentration is REO=10～300 grams per liters.
3. according to the method for claim 1 or 2 described a kind of acidic extractant complexing extraction separation rare-earth elements, it is characterized in that the rare earth oxide summation meter in the re chloride, selecting and selecting strength of solution earlier for use is REO=200～300 grams per liters.
4. according to the method for the described a kind of acidic extractant complexing extraction separation rare-earth element of claim 1, the Citrate trianion that it is characterized in that in re chloride being added is selected Trisodium Citrate or citric acid lanthanum for use.
5. according to the method for the described a kind of acidic extractant complexing extraction separation rare-earth element of claim 1, it is characterized in that selecting for use with two (2-ethylhexyl phosphoric acids) when being extraction agent, the pH value of the rare earth chloride-hydrochloric acid-citric acid mixing solutions of preparation is 0.5～2, when being extraction agent with 2-ethylhexyl phosphonic acid list ethylhexyl fat, the pH value of the rare earth chloride-hydrochloric acid of preparation-citric acid mixing solutions is 1～1.5.
6. according to the method for the described a kind of acidic extractant complexing extraction separation rare-earth element of claim 1, it is with rare earth carbonate or rare-earth hydroxide precipitation that the raffinate that it is characterized in that containing citric acid returns when using, and circulation is used to prepare rare earth chloride-hydrochloric acid-citric acid mixing solutions or preparation citric acid rare-earth products to the rare earth Citrate trianion that obtains as additive.
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| CN109266871A (en) * | 2018-09-28 | 2019-01-25 | 中国恩菲工程技术有限公司 | The preparation method of submicron order scandium oxide |
| CN112126802A (en) * | 2020-08-14 | 2020-12-25 | 南昌大学 | Rare earth alkaline precipitation, conversion, decomposition and separation method |
| CN113073208A (en) * | 2021-03-29 | 2021-07-06 | 华中科技大学 | Pretreatment method of extracting agent for cobalt-nickel separation and corresponding extraction method |
| CN113249598A (en) * | 2021-05-18 | 2021-08-13 | 江西理工大学 | Method for complexing, separating and removing aluminum from rare earth feed liquid |
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| CN113387795B (en) * | 2021-06-09 | 2023-06-09 | 江苏南方永磁科技有限公司 | Method for extracting oxalic acid from rare earth waste liquid |
| CN114134325A (en) * | 2021-11-19 | 2022-03-04 | 湖南理工学院 | Method for improving selectivity of polymer containing membrane for separating different metal ions by using complexing agent |
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