CN1824814A - Full separating technique of non-saponification organic phase extracting rare-earth - Google Patents
Full separating technique of non-saponification organic phase extracting rare-earth Download PDFInfo
- Publication number
- CN1824814A CN1824814A CNA2006100579081A CN200610057908A CN1824814A CN 1824814 A CN1824814 A CN 1824814A CN A2006100579081 A CNA2006100579081 A CN A2006100579081A CN 200610057908 A CN200610057908 A CN 200610057908A CN 1824814 A CN1824814 A CN 1824814A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- organic phase
- extraction
- acid
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
This invention is a non saponification organic phase extracting rare earth whole separating technique. It uses acidic organophosphorus acid or organophosphorus ester type extracting agent, for example, P204, P507, C272, P229. Blended mixed extracting agent of one or 2-3 kinds of them is used to extract and separate rare earth element in rare earth chloride solution or rare earth nitrate solution. The organic extracting agent doesn't need saponification, and there is no ammonia nitrogen waste water appears during extracting process. The pollution of the waste water to water resources can be eliminated; the chemical industry materials cost is reduced more than 25%, and lot of ammonia nitrogen waste water processing cost is saved. Its technique is simple and easy to control, and the rare earth separating effect is good.
Description
Technical Field
The invention relates to a process technology for separating rare earth by solvent extraction. In particular to a novel process for extracting and separating rare earth by taking one or 2-3 mixed extracting agents prepared from non-saponified acidic organic phosphoric acid (phosphonic acid) or organic phosphoric acid (phosphonic acid) esters as an organic phase and taking a rare earth chloride solution or a rare earth nitrate solution containing at least two rare earth elements as a raw material.
Background
The rare earth element is a general term for lanthanoid elements and 17 elements of yttrium and scandium. They are difficult to separate due to their similar properties. At present, the separation and purification of rare earth generally adopts a solvent extraction method, which is based on the extraction separation of rare earth elements existing in an aqueous solution by an organic solvent immiscible with the aqueous solution, and the rare earth elements or rare earth element groups (easily-extracted rare earth elements RE) with high separation coefficientsb) Preferentially extracted into an organic phase (extractant), and rare earth elements or rare earth element groups (rare earth elements RE difficult to extract) with lower separation coefficienta) Is enriched in the water phase and is subjected to multi-section and multi-stage extraction exchange, so that the separation of various rare earth elements is realized. The most common industrial processes for rare earth separation are: extracting and separating rare earth elements ([1]by saponifying extractants such as P507, P204 and the like in a hydrochloric acid system]Rare earth chemical collection of discourse, changchun institute of reaction, 1982, science press; [2]Xu Xiong constitution eds, rare earth, 2 nd edition (registered), Metallurgical Press, 2002, P542-547); a full separation process ofrare earth of medium-yttrium europium-rich ion type rare earth ore (ammoniation P507 extraction separation, CN 87101822); ammoniation P507 solvent extraction separation mixed rare earth technology (CN 85102210); organic phase continuous saponification technique (CN 95117989.6); the saponified naphthenic acid system is used for extraction, separation and purification of yttrium oxide (Xuguangxian Shuitai, rare earth, 2 nd edition (registered), publication of metallurgy industry, 2002, P582, 590), etc. The extracting agent used for the extraction and separation belongs to an acidic extracting agent, the extraction and separation are required to be carried out under low acidity, the extraction capacity (distribution ratio) of the extracting agent is inversely proportional to the equilibrium acidity of a water phase, generally, 3 hydrogen ions are replaced by one rare earth ion for extraction, the rare earth extracting capacity of the extracting agent is rapidly reduced along with the increase of the acidity, therefore, the extracting agent needs to be saponified by adopting ammonia water or inorganic bases such as sodium hydroxide, ammonium bicarbonate and the like, the hydrogen ions are removed (see reactions 1 and 1 '), and the ammoniated extracting agent and the rare earth ions are subjected to exchange extraction (see reactions 2 and 2'). At present, most rare earth separation plants adopt ammonia water for saponification, 0.8-1.5 tons of liquid ammonia (2500 yuan/ton or so) are consumed for extracting and separating one ton of rare earth oxide, the production cost is greatly increased, and a large amount of ammonia nitrogen wastewater (35-40 tons of rare earth oxide are generated for separating one ton of rare earth oxide) is generated, so that serious water resource is causedAnd the cost of the rare earth separation plant is 1-2 times higher than that of liquid ammonia due to the fact that NaOH is adopted for saponification, and the rare earth separation plant is difficult to bear. The method is a great problem in the rare earth separation industry at present.
Or ------------2
HA or (HA)2Represents an extractant, RE3+Represents trivalent rare earth ions
The purpose of the invention is as follows:
because acid extractant is used in the extraction and separation of rare earth, inorganic alkali such as ammonia water or ammonium bicarbonate is needed to saponify the extractant, the process not only consumes a large amount of alkali and causes the increase of production cost, but also generates a large amount of ammonia nitrogen wastewater and causes serious pollution to water resources.
The purpose of this patent is to cancel ammonium (sodium) saponification, directly adopts unsaponifiable organic extractant to carry out the rare earth extraction separation, eliminates the pollution of ammonia nitrogen waste water, reduces tombarthite product manufacturing cost by a wide margin.
Disclosure of Invention
In order to realize the separation of rare earth elements in an aqueous solution containing at least two rare earth elements, the invention takes a chlorinated rare earth solution or a nitric acid rare earth solution containing at least two rare earth elements obtained by processing rare earth ore as a raw material (extraction liquid), and adopts one of nonsaponifiable acidic organic phosphoric acid (phosphonic acid) or organic phosphoric acid esters or 2-3 prepared mixed extractants (organic phase) to extract and separate the rare earth elements in a hydrochloric acid or nitric acid medium (aqueous phase).
The used extracting agent comprises one of P204(D2EHPA, di (2-ethylhexyl phosphate)), P507(HEH/EHP, 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester), P229 (di (2-ethylhexyl) phosphonic acid), C272 (di (2, 4, 4-trimethylpentyl) phosphonic acid), C301 (di (2, 4, 4-trimethylpentyl) thiophosphonic acid), C302 (di (2, 4, 4-trimethylpentyl) monothiophosphonic acid), HEOPPA or 2-3 mixed extracting agents prepared by diluting to 0.5-1.7mol/l by using one or more organic solvents of aliphatic hydrocarbon, kerosene, solvent oil, paraffin, aromatic hydrocarbon and organic alcohol; the organic phase is one of P204, P507 and C272 or 2 kinds of mixed extractant, and is diluted to 1-1.5mol/l with kerosene and solvent oil.
The raw materials are rare earth chloride or rare earth nitrate solution prepared by dissolving rare earth oxide and rare earth carbonate obtained by processing rare earth ore with hydrochloric acid or nitric acid or by dissolving rare earth chloride and rare earth nitrate with water, or rare earth chloride or rare earth nitrate raffinate or strip liquor obtained by extracting and grouping, the acidity is 5-1.0mol/l, and the rare earth content REO is 0.3-2.5 mol/l. The raw material is preferably a rare earth chloride solution, the rare earth content REO of the rare earth chloride solution is 0.8-2.0mol/l, the acidity is 4-0.3mol/l, and the rare earth chloride solution is adjusted by adding a small amount of liquid alkali.
The invention is divided into four procedures.
A first step: the organic phase pre-extraction process is to mix an organic extractant and RE containing rare earth elements difficult to extractaThe rare earth solution is mixed and extracted (reaction 3, 3 '), so that rare earth ions in the solution exchange with hydrogen ions in the extracting agent, the rare earth ions are extracted into an organic phase, and the extracting agent containing rare earth ions which are difficult to extract at a certain concentration is directly introduced into a first-stage mixing chamber of a rare earth separation and extraction section for extraction and separation (reaction 4.4').
Or ----------3’
HA or (HA)2Represents an extractant, REa 3+Represents a hardly extractable trivalent rare earth ion, REb 3+Represents an easily extracted trivalent rare earth ion.
The organic phase pre-extraction operation steps are as follows: continuously flowing a blank organic phase flowing out of the last stage of the rare earth extraction separation stripping section into an organic phase pre-extraction tank through metering; metering a part of raffinate flowing out from the first stage of the rare earth extraction separation and extraction section or rare earth solution with similar components to the raffinate, and then continuously flowing into an organic phase pre-extraction tank; adding a proper amount of water into a mixing chamber of several stages behind the organic phase pre-extraction tank; through multi-stage countercurrent or co-current extraction, more than 99% of rare earth ions in the solution are extracted into an organic phase; the obtained organic phase containing rare earth ions with certain concentration difficult to extract is directly introduced into a first-stage mixing chamber of the rare earth separation and extraction section. Preferably, the blank organic phase flowing out from the last stage of the back extraction section of the rare earth extraction separation continuously flows into the first-stage mixing chamber of the organic phase pre-extraction tank through metering; metering a part of raffinate flowing out of the first stage of the rare earth extraction separation extraction section or rare earth solution with similar components to the raffinate, and then continuously flowing into a last stage mixing chamber of an organic phase pre-extraction tank; adding a proper amount of water into a rear 1-3 stages of mixing chambers of the organic phase pre-extraction tank; after 2-8 levels of countercurrent extraction, more than 99.5 percent of rare earth ions in the water phase are extracted into the organic phase.
Rare earth raffinate for organic phase pre-extraction or chlorinated rare earth or rare earth nitrate solution with similar components to the raffinate, wherein the rare earth concentration REO is 0.03-2.0mol/l, and the acidity is pH1-pH 5; the pre-extraction two-phase flow ratio (organic phase/water phase) is 1: 1-10, preferably 1: 1-5, the mixing time is 3-10 minutes, and the clarification time is 5-20 minutes; the pre-extraction organic phase contains 0.06-0.21mol/l of rare earth REO, preferably 0.12-0.19 mol/l; h in raffinate+Less than 0.4mol/l, REO less than 0.1g/l, and the part is returned for use or used for dissolving rare earth raw materials after being neutralized by lime or oxides containing calcium and magnesium and carbonates.
After the organic phase is pre-extracted, the organic phase contains about 0.16mol/l l Rare Earth (REO), when the organic phase enters the extraction section, firstly, the acidity of the aqueousphase in the extraction section can be prevented from being increased, and secondly, the concentration of the rare earth in the raffinate can be greatly increased, so that the equipment processing capacity of further separating the raffinate is improved.
A second step: and (5) rare earth extraction. A rare earth element or group of rare earth elements with a high partition coefficient (the easy-to-extract rare earth elements) is preferentially extracted into the organic phase, and a rare earth element or group of rare earth elements with a lower partition coefficient (the difficult-to-extract rare earth elements) is enriched in the aqueous phase (the raffinate).
The ratio of the extraction ratio or the flow rate of the organic phase to the aqueous phase depends on factors such as the concentration of the extractant, the concentration of the rare earth elements contained in the feed liquid, and the ratio of the rare earth elements to be extracted, and the flow rate is determined by experts according to a well-known calculation method.
Aqueous phase H during extraction+The concentration is 4-0.3mol/l, and the acidity is realized by controlling the acidity of the extraction feed liquid and the rare earth concentration in the organic phase entering the extraction section.
Raffinate H+The concentration is 3-0.3mol/l, and is adjusted by controlling the concentration of rare earth in the organic phase at the first inlet of the extraction sectionAnd (4) saving.
A third step: and (3) an organic phase washing procedure. In order to completely extract the rare earth elements desired to be extracted into the organic phase, a portion of the refractory rare earth elements that should remain in the aqueous phase are also extracted into the organic phase, and therefore, a washing process is required in which the organic phase is selectively washed with an acid solution or a rare earth solution to remove the refractory rare earth elements that have been extracted by the organic phase in a small amount. The washing liquid is hydrochloric acid or nitric acid aqueous solution with acidity of 1-6mol/l, preferably 2-5mol/l, or washing with rare earth chloride solution or rare earth nitrate solution containing easily-extractable rare earth elements with rare earth concentration of 0.3-2.0mol/l and acidity of 4-2 mol/l.
A fourth step: and (4) carrying out back extraction and regeneration on the loaded organic phase by using an acid solution. The rare earth elements extracted into the organic phase are contacted with an acid solution to be enriched into the water phase, and the blank organic phase is returned to the organic phase pre-extraction section for recycling.
The acid solution (back extraction acid) is hydrochloric acid or nitric acid aqueous solution, and the acidity is 1-7mol/l, preferably 2-5 mol/l.
The invention has the advantages that:
the invention adopts non-saponification acidic organic phosphoric acid (phosphonic acid) or organic phosphoric acid (phosphonic acid) ester extractant to extract and separate rare earth elements in rare earth chloride or rare earth nitrate solution, does not generate ammonia nitrogen wastewater in the extraction process, can eliminate the pollution of the ammonia nitrogen wastewater to water resources, reduces the cost of chemical materials by more than 25 percent, and saves a large amount of ammonia nitrogen wastewater treatment cost. And the process is simple and easy to control, the concentration of the rare earth is improved in the extraction and separation process, and the processing capacity of the extraction and separation equipment is increased.
Brief description of the drawings
FIG. 1 is a schematic diagram of extraction agent saponification and extraction separation in the prior art
1- saponification tank 2, 3, 4-extraction section, washing section, back-extraction section for rare earth separation
5-rare earth raw material 6-back extraction and washing acid
7-Back extract (containing RE)b 3+) 8-extractant (blank organic phase)
9-containing NH4 +、REa 3+Raffinate 10-ammonia or NH4HCO3Etc. of
11-post saponification extractant (containing NH)4A or NH4HA2) 12-saponified raffinate
FIG. 2 is a schematic diagram of extraction agent saponification and extraction separation in the present invention
1-organic phase pre-extraction section 2, 3, 4-rare earth separation extraction section, washing section, back extraction section
5-rare earth raw material 6-back extraction and washing acid
7-Back extract (containing RE)b 3+) 8-extractant (blank organic phase)
9-raffinate (containing RE)a 3+) 10-aqueous solution
11-Pre-extracted organic phase (containing RE)aA3Or REa(HA2)3) 12-Pre-extraction raffinate
Detailed Description
The process of the present invention is further illustrated by the following examples. The scope of the invention is not limited by theseexamples, but is defined by the claims.
The invention is realized by a conventional multi-stage countercurrent extraction mode. The serial numbers of the extraction-washing-stripping tanks are increased progressively according to the flowing direction of the organic phase, and the inlet of the organic phase is the 1 st stage.
Example 1
The raw material is mischchloride (REO 45%) produced by bastnaesite, and is dissolved in water to obtain mixed mischchloride solution, the rare earth concentration REO is 1.5mol/l, the acidity is pH4, and the composition is (La-Nd)2O398％、(Sm-Y)2 O 32％；
The organic phase is a mixed extractant prepared from P507 and P204 (the proportion of P507 is 60 percent, the proportion of P204 is 40 percent), and the concentration of the mixed extractant is 1.2mol/l (diluted by kerosene);
performing Nd/Sm extraction grouping by adopting a multi-stage mixing clarification extractor, wherein an organic phase is pre-extracted by 5 stages, an extraction section is 10 stages, a washing section is 15 stages, and a back extraction section is 10 stages;
the feed liquid continuously flows into the 10 th stage of a neodymium-samarium grouped extraction tank at the speed of 80 liters/minute for extraction and separation, and the (La-Nd) Cl-containing material is obtained at the 1 st stage3Raffinate (84 l/min, REO 1.49mol/l, pH1, Sm2O3<0.005%) of which 5.0 l/min of raffinate flowed into the 5 th mixing chamber of the organic phase pre-extraction section; the organic phase flowed into the stage 1 mixing chamber of the organic phase pre-extraction section at a rate of 51.3 liters/min; adding 50 liters/minute of water into a 4 th-stage mixing chamber and a 5 th-stage mixing chamber; mixing time 5 minutes, clarification time 15 minutes. After 5-stage countercurrent pre-extraction, the acidity of the extracted water phase is 0.21N, the rare earth concentration REO is 0.02g/l, the rare earth recovery rate is 99.8%, part of the extracted water phase is used for dissolving rare earth chloride after magnesium oxide neutralization, and part of the extracted water phase is returned to the pre-extraction section for recycling; the organic phase after pre-extraction contains rare earth (La-Nd)2O30.145mol/l，Directly flows into the first stage of the neodymium-samarium grouped extraction section.
The stripping and washing acid adopts 5.0mol/l HCl, flows into the 10 th stage of the stripping section at the flow rate of 5.6 liters/min, and the rare earth chloride solution (REO 1.45mol/l, H) of SmEuGd enrichment is discharged from the 1 st stage of the stripping section+0.61N，Nd2O3Less than 0.05 percent) and the flow rate is 1.65 liters/minute, and the rest strip liquor is introduced into a washing section 15 grade to wash La-Nd ions which are extracted by organic phase in small quantity.
And the organic phase is subjected to back extraction and water washing and then returned to the organic phase pre-extraction section for recycling.
Example 2
The extraction separation feed liquid is a rare earth chloride solution containing gadolinium and terbium, the rare earth concentration REO is 1.3mol/l, the acidity is pH2, wherein Gd2O3Content 56%, Tb4O737% and the other 7%.
The organic phase was diluted with 1.4mol/L of P507 in mineral spirits No. 200.
Gd/Tb extraction and separation are carried out by adopting a mixed clarification extraction tank countercurrent extraction mode, the organic phase is pre-extracted for4 grades, the extraction section is 32, the washing section is 25 grades, and the back extraction section is 12 grades.
The feed liquid continuously flows into the 32 th level of the Gd/Tb separation extraction section at the speed of 1 liter/minute for extraction separation, and gadolinium-rich raffinate (1.4 liters/minute, REO 1.38mol/l, pH2, Gd) is obtained at the 1 st level of the extraction section2O391%) of the raffinate stream, 0.82 l/min of which flowed into the mixing chamber of stage 4 of the organic phase pre-extraction section; the blank organic phase flows into the mixing chamber of the 1 st stage of the pre-extraction tank at the speed of 7 liters/min, 8.5 liters/min of water is added into the 3 rd stage and the 4 th stage, and the organic phase containing 0.161mol/l of REO is obtained by 4 stages of countercurrent extraction and is directly introduced into the 1 st stage of the extraction section for extraction and separation.
HCl with an acidity of 5.5mol/l is introduced into the 12 th stage of the stripping section at a flow rate of 0.75 l/l, and terbium chloride solution (1.6mol/l, Tb) is discharged from the 1 st stage of the stripping section4O799.99%) 0.31 l/min, a small amount of Dy enrichment is discharged from the 8 th stage of the stripping section, and the rest stripping solution is introduced into the 25 th stage of the washing section to wash trivalent gadolinium ions and the like which are extracted by a small amount of organic phase.
The organic phase is subjected to back extraction and water washing and then returned to the organic phase pre-extraction section for recycling, and the recovery rate of the rare earth is more than 99.5 percent.
Example 3
The extraction separation feed liquid is rare earth nitrate solution containing lanthanum and cerium, the concentration REOof the rare earth is 1.63mol/l, the acidity is pH3, wherein the content of La2O3 is 74.22%, CeO225.73%, and Pr6O11 is less than 0.02%.
The organic phase was 1.5mol/l P204, diluted with kerosene.
A multi-stage mixed clarifying extraction tank is adopted for La/Ce extraction and separation, the organic phase is pre-extracted at 6 levels, the extraction section is 20, the washing section is 22 levels, and the back extraction section is 7 levels.
The feed liquid continuously flows into the 20 th stage of the La/Ce separation and extraction section at the speed of 5 liters/minute for extraction and separation, and raffinate (8.6 liters/minute, REO 1.54mol/l, pH2, La) containing lanthanum nitrate is obtained at the 1 st stage of the extraction section2O399.95％，CeO2<0.05%), wherein 4.7 l/min of the raffinate flowed into the mixing chamber of stage 6 of the organic phase pre-extraction section; the blank organic phase flows into the mixing chamber of the 1 st stage of the pre-extraction tank at the speed of 38 liters/min, 40 liters/min of water is added into the 4 th stage and the 5 th stage, and the La is obtained after 6 stages of countercurrent extraction2O30.19mol/l of organic phase is directly introduced into the 1 st stage of the extraction section for La/Ce extraction separation.
The back extraction and washing acid adopts 4.8mol/l HNO3, the flow rate of the back extraction and washing acid flows into the 7 th stage of the back extraction section at the flow rate of 5.0 l/min, cerium nitrate solution (REO 1.524mol/l, H +0.12N, CeO299.9% La2O3<0.03%, Pr6O11<0.05%) is discharged from the 1 st stage of the back extraction section at the flow rate of 1.38 l/min, and the rest back extraction solution is introduced into the 22 stages of the washing section to wash the trivalent lanthanum ions which are extracted by the organic phase in a small amount. The organic phase is subjected to back extraction and water washing and then returned to the organic phase pre-extraction section for recycling, and the recovery rate of the rare earth is more than 99%.
Claims (17)
1. A non-saponifying organic phase extracting process for separating rare-earth elements from the aqueous solution containing at least two rare-earth elements features that the rare-earth elements are extracted from the aqueous solution by a non-saponifying organic phase extracting process. The method is characterized in that: rare earth is extracted and separated by taking a rare earth chloride solution or a rare earth nitrate solution containing at least two rare earth elements obtained by treating rare earth ore as a raw material and adopting an organic phase of a mixed extracting agent prepared from one or more of non-saponified acidic organic phosphoric acid (phosphonic acid) or organic phosphoric acid (phosphonic acid) esters. The operation steps are as follows:
(1) organic phase pre-extraction procedure: continuously flowing a blank organic phase flowing out of the last stage of the rare earth extraction separation stripping section into an organic phase pre-extraction tank through metering; metering a part of raffinate flowing out from the first stage of the rare earth extraction separation and extraction section or rare earth solution with similar components to the raffinate, and then continuously flowing into an organic phase pre-extraction tank; adding a proper amount of water into a mixing chamber of several stages behind the organic phase pre-extraction tank; through multi-stage countercurrent or co-current extraction, more than 99% of rare earth ions in the solution are extracted into an organic phase; the obtained organic phase containing rare earth ions with certain concentrationdifficult to extract is directly introduced into a first-stage mixing chamber of a rare earth separation and extraction section;
(2) rare earth extraction procedure: the organic phase containing rare earth ions which are difficult to extract enters an extraction section to exchange with the easily-extracted rare earth ions in the aqueous phase;
(3) an organic phase washing procedure: the organic phase for extracting a large amount of rare earth ions enters a washing section, and the rare earth ions which are difficult to extract are washed by acid solution or rare earth solution;
(4) an organic phase back extraction process: the loaded organic phase mainly containing easily-extracted rare earth ions is obtained through continuous extraction and washing, rare earth is reversely extracted by using an inorganic acid, and the blank organic phase is returned to the organic phase pre-extraction section for recycling.
2. The process as claimed in claim 1, wherein the organic phase comprises one of P204, P507, P229, C272, C301, C302, HEOPPA or 2-3 mixed extractants, and is diluted to 0.5-1.7mol/l with one or more organic solvents selected from aliphatic hydrocarbon, kerosene, mineral spirits, paraffin wax, aromatic hydrocarbon, and organic alcohol.
3. The process of claim 2, wherein the organic phase comprises a mixed extractant prepared from one or two of P204, P507 and C272, and is diluted to 1-1.5mol/l by kerosene and solvent oil.
4. The process according to claim 1(1), wherein the blank organic phase flowing out of the last stage of the back extraction section of the rare earth extraction separation is metered and continuously flows into the first stage mixing chamber of the organic phase pre-extraction tank; metering a part of raffinate flowing out of the first stage of the rare earth extraction separation extraction section or rare earth solution with similar components to the raffinate, and then continuously flowing into a last stage mixing chamber of an organic phase pre-extraction tank; adding a proper amount of water into a rear 1-3 stages of mixing chambers of the organic phase pre-extraction tank; after 2-8 levels of countercurrent extraction, more than 99.5 percent of rare earth ions in the water phase are extracted into the organic phase.
5. The process according to claim 1(1), wherein the rare earth raffinate for the pre-extraction or the chlorinated rare earth or rare earth nitrate solution having a similar composition to the raffinate has a rare earth concentration REO of 0.03 to 2.0mol/l and an acidity of 1 to 5.
6. The process according to claim 1(1), wherein the organic phase of the pre-extraction contains 0.06-0.21mol/l of rare earth REO.
7. The process according to claim 6, wherein the pre-extracted organic phase contains rare earth REO in the range of 0.12 to 0.19 mol/l.
8. The process of claim 1(1), wherein the organic phase is used to pre-extract H in the raffinate+Less than 0.4mol/l, REO less than 0.1g/l, and the part is returned for use after being neutralized by lime or oxides containing calcium and magnesium and carbonates or used for dissolving rare earth raw materials by complex acid.
9. The process of claim 1, wherein the raw material is rare earth oxide obtained by treating rare earth ore, rare earth carbonate dissolvedby hydrochloric acid or nitric acid, or rare earth chloride or rare earth nitrate solution obtained by dissolving rare earth chloride or rare earth nitrate by water, or rare earth chloride or rare earth nitrate raffinate or strip liquor obtained by extracting and grouping, the rare earth content REO is 0.3-2.5mol/l, and the acidity is pH 5-1.0 mol/l.
10. The process as claimed in claim 9, wherein the raw material is a rare earth chloride solution having a rare earth content REO of 0.8-2.0mol/l and an acidity of pH4-0.3mol/l, adjusted by adding a small amount of liquid alkali.
11. The process as claimed in claim 1(2), wherein the aqueous phase H is extracted+The concentration is 4-0.3 mol/l.
12. The process of claim 1(2), wherein raffinate H+The concentration is 3-0.3mol/l, and is adjusted by controlling the concentration of rare earth in the organic phase at the first inlet of the extraction section.
13. The process according to claim 1(3), wherein the washing liquid is an aqueous solution of hydrochloric acid or nitric acid having an acidity of 1 to 6 mol/l.
14. The process according to claim 1(3), wherein the washing liquid is a rare earth chloride solution or a rare earth nitrate solution containing a readily extractable rare earth element, and has a rare earth concentration of 0.3 to 2.0mol/l and an acidity of 4 to 2 mol/l.
15. The process according to claim 1(4), wherein the stripping acid is an aqueous solution of hydrochloric acid or nitric acid, and the acidity is 1 to 7 mol/l.
16. The process according to claim 15, wherein the stripping acid is an aqueous solution of hydrochloric acid or nitric acid having an acidity of 2 to 5 mol/l.
17. A process according to any one of claims 1 to 16 wherein in the first step an organic phase comprising a diluent and an acidic organic phosphoric (phosphonic) acid or phosphoric acid ester is contacted with the rare earth solution, the organic phase carrying a quantity of rare earth ions; in the second procedure, an easily extracted rare earth element is preferentially extracted into the organic phase, and a difficultly extracted rare earth element is enriched in the aqueous phase; in a third process step, the organic phase is selectively washed with an acid solution or a rare earth solution to remove rare earth elements which are difficult to extract by a small amount from the organic phase; in the fourth step, the loaded organic phase is stripped and regenerated with an acid solution.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100579081A CN1824814A (en) | 2006-02-27 | 2006-02-27 | Full separating technique of non-saponification organic phase extracting rare-earth |
| CN2006100764059A CN1880489B (en) | 2006-02-27 | 2006-04-25 | Non-saponifiable extraction full-separating process for high concentration rare earth solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006100579081A CN1824814A (en) | 2006-02-27 | 2006-02-27 | Full separating technique of non-saponification organic phase extracting rare-earth |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1824814A true CN1824814A (en) | 2006-08-30 |
Family
ID=36935654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006100579081A Pending CN1824814A (en) | 2006-02-27 | 2006-02-27 | Full separating technique of non-saponification organic phase extracting rare-earth |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1824814A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100584970C (en) * | 2008-02-28 | 2010-01-27 | 五矿（北京）稀土研究院有限公司 | A kind of hybrid extraction method of extracting and separating rear earth element and extraction agent |
| CN101260466B (en) * | 2007-02-08 | 2010-07-14 | 有研稀土新材料股份有限公司 | Pretreatment method for organic extracting agent and application thereof |
| CN101994004B (en) * | 2009-08-11 | 2012-07-11 | 北京有色金属研究总院 | Process for extracting and separating rare-earth elements |
| CN103060560A (en) * | 2013-02-04 | 2013-04-24 | 广东珠江稀土有限公司 | Extracting agent for separating heavy rare earth element |
| CN103526055A (en) * | 2013-10-09 | 2014-01-22 | 南昌航空大学 | Process for grouping quasi-fractionated extraction of neodymium/samarium through bastnaesite |
| CN104451191A (en) * | 2014-12-03 | 2015-03-25 | 紫金矿业集团股份有限公司 | Dilution extraction process capable of improving copper recovery rate |
| CN106319218A (en) * | 2015-06-16 | 2017-01-11 | 有研稀土新材料股份有限公司 | Method for recovering rare earth, aluminum and silicon from rare earth-containing aluminum and silicon wastes |
| CN107699715A (en) * | 2016-08-08 | 2018-02-16 | 有研稀土新材料股份有限公司 | The method of extracting and enriching recovering rare earth from low concentration of rare earth solution |
| CN108300878A (en) * | 2018-01-26 | 2018-07-20 | 中国科学院长春应用化学研究所 | A kind of extraction process with acid phosphine enriching and recovering scandium from secondary resource leachate |
-
2006
- 2006-02-27 CN CNA2006100579081A patent/CN1824814A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260466B (en) * | 2007-02-08 | 2010-07-14 | 有研稀土新材料股份有限公司 | Pretreatment method for organic extracting agent and application thereof |
| CN100584970C (en) * | 2008-02-28 | 2010-01-27 | 五矿（北京）稀土研究院有限公司 | A kind of hybrid extraction method of extracting and separating rear earth element and extraction agent |
| CN101994004B (en) * | 2009-08-11 | 2012-07-11 | 北京有色金属研究总院 | Process for extracting and separating rare-earth elements |
| CN103060560A (en) * | 2013-02-04 | 2013-04-24 | 广东珠江稀土有限公司 | Extracting agent for separating heavy rare earth element |
| CN103526055A (en) * | 2013-10-09 | 2014-01-22 | 南昌航空大学 | Process for grouping quasi-fractionated extraction of neodymium/samarium through bastnaesite |
| CN103526055B (en) * | 2013-10-09 | 2014-12-03 | 南昌航空大学 | Process for grouping quasi-fractionated extraction of neodymium/samarium through bastnaesite |
| CN104451191A (en) * | 2014-12-03 | 2015-03-25 | 紫金矿业集团股份有限公司 | Dilution extraction process capable of improving copper recovery rate |
| CN106319218A (en) * | 2015-06-16 | 2017-01-11 | 有研稀土新材料股份有限公司 | Method for recovering rare earth, aluminum and silicon from rare earth-containing aluminum and silicon wastes |
| US10280482B2 (en) | 2015-06-16 | 2019-05-07 | Grirem Advanced Materials Co., Ltd. | Method of recovering rare earth aluminum and silicon from rare earth-containing aluminum-silicon scraps |
| CN107699715A (en) * | 2016-08-08 | 2018-02-16 | 有研稀土新材料股份有限公司 | The method of extracting and enriching recovering rare earth from low concentration of rare earth solution |
| CN107699715B (en) * | 2016-08-08 | 2019-10-01 | 有研稀土新材料股份有限公司 | The method of extracting and enriching recovering rare earth from low concentration of rare earth solution |
| CN108300878A (en) * | 2018-01-26 | 2018-07-20 | 中国科学院长春应用化学研究所 | A kind of extraction process with acid phosphine enriching and recovering scandium from secondary resource leachate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1824814A (en) | Full separating technique of non-saponification organic phase extracting rare-earth | |
| CN101319275B (en) | Process for solvent extraction separation purification of rare earth element | |
| CN1872377A (en) | Method for saponifying extraction agent | |
| CN101787451B (en) | Method for improving efficiency of acidic organophosphorus extractant for extraction separation of rare-earth elements | |
| CN100529123C (en) | Method of acidic extractant complexing extraction separation rare-earth element | |
| CN100513600C (en) | Technique for extracting and separating rare earth elements from non-saponification system | |
| CN101994004A (en) | Process for extracting and separating rare-earth elements | |
| CN101781706A (en) | Process for separating rare-earth element by extraction | |
| CN1804063A (en) | Process for extracting rare earth element by non-saponifiable phosphorous mixing extractant | |
| CN100584969C (en) | Technique for extraction separation of quadravalence cerium, thorium and cerium less tervalence rare earth from sulphuric acid rare earth solution | |
| CN111440945A (en) | Method for removing aluminum by refining rare earth gadolinium with ionic liquid method | |
| CN1880489B (en) | Non-saponifiable extraction full-separating process for high concentration rare earth solution | |
| CN108950249A (en) | A kind of vanadium aluminum separation method of vanadium-containing shale pickle liquor | |
| CN111020196B (en) | Method for separating thorium and enriching rare earth from radioactive waste residue leachate based on POAA | |
| CN1257290C (en) | Method of extracting rare earth from apatite | |
| CN86105043A (en) | Extracting and separating rear earth element from sulfuric acid system | |
| CN112981144B (en) | Method for extracting rare earth and use of aqueous solution containing ammonia | |
| CN100417734C (en) | No-saponifying pre-grouped extraction and separation process of ion adsorbing RE mineral | |
| CN1162558C (en) | Process for extracting and separating thorium and extracting rare earth chloride from sulfuric and phosphoric mixed acid system | |
| CN1891839A (en) | Extracting agent for metal extraction, and its method and use | |
| CN113699376B (en) | Method for separating calcium ions in rare earth transformation type calcium magnesium containing rare earth sulfate solution by extraction method | |
| CN1212411C (en) | Ce extraction from nitric acid rare earth solution | |
| CN104561611B (en) | The process of the three fully loaded fractional extraction rare-earth separatings of outlet | |
| CN1019639B (en) | Solvent extraction | |
| CN1087388A (en) | The extracting technological method of purifying separating rare earth element |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |