CN1019639B - Solvent extraction - Google Patents
Solvent extractionInfo
- Publication number
- CN1019639B CN1019639B CN90100135A CN90100135A CN1019639B CN 1019639 B CN1019639 B CN 1019639B CN 90100135 A CN90100135 A CN 90100135A CN 90100135 A CN90100135 A CN 90100135A CN 1019639 B CN1019639 B CN 1019639B
- Authority
- CN
- China
- Prior art keywords
- main process
- extraction
- component
- concentration
- body technology
- 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.)
- Expired
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
The present invention relates to an extraction method with a branch body, which is a purification method for intermediate components led out of a multi-outlet rare earth extraction technology. The multi-outlet extraction technology is used as a main body technology, an extraction technology for purifying the intermediate components is used as the branch technology of the main body technology, the branch technology is used for only producing intermediate component products, an organic phase containing easy-extraction components and/or water phase containing difficult-extraction components flow back to the main body technology from the stage approximating to the components of the main body technology and are continuously extracted and separated in the main body technology, and therefore, the number of outlets for the whole extraction technology with a branch body is the same as that of outlets for the original main body technology. The present invention is more economical than that of a method for enhancing the quality of the intermediate components by increasing the stage number of the main body technology, is much simpler than a method for purifying the intermediate components by using an independent extraction technology and has no by-product generation.
Description
The invention belongs to the method for solvent extraction and separation rare earth in the hydrometallurgy.
Solvent extraction method has the cross-flow extraction process, counter-current extraction, countercurrent washing method, fractional-distillation extraction, reflux extraction method etc., the fractional-distillation extractions that adopt in the Rare Earth Separation more.In recent years, the method for fractionation cascade extraction rare-earth separating from traditional two outlets to three outlets, four outlets so that the direction of more a plurality of outlets develop, solve better in theory at present and comparatively sophisticated on using be three outlet technologies." Chinese rare-earth journal " the 2nd phase in 1985 was once reported " novel process of a step extracting and separating La, Pr, Nd ".This technology makes rare earth element be distributed as easy collection component, intermediate component and difficult collection component in extraction tank, draws from three outlets respectively.Multiple exit technology is based in the tandem fractionation extraction of polycomponent lucium, intermediate component can form this fact of accumulation peak in tandem under certain condition, so, can draw the enriched substance or the thick product of intermediate component from peak level or its adjacent levels opening.In cascade extraction, what intermediate component had forms the accumulation peak at aqueous phase, and then forming in organic phase of having accumulates the peak.Since some component of lucium must from the phase at middle component accumulation peak or its relative mutually pass through, make and to contain a certain amount of non-intermediate component (component of easily coming together is or/and difficult collection component) in the accumulation peak, the intermediate component that Here it is goes out with the multiple exit isolated in form is difficult for reaching high purity, generally the reason that exists with enriched substance or thick product.Give the grade that enough progression can improve accumulation peak intermediate component, the accumulation peak need the progression of increase many more, but this is irrational economically more near extreme value.In general, intermediate component enriched substance or the thick product needed that the centre is exported out further separated purification.The intermediate component cost not high with Solvent Extraction Separation purification grade is lower, widely adopts.Because intermediate component enriched substance of coming out in the multiple exit technology or thick product contain easy collection component and difficult collection component, obtain the intermediate component product of higher degree, need separate respectively with two independently fractionation extraction series and remove easy collection component and difficult collection component, thisly pass through three independently fractionation extraction series (contain multiple exit extraction series) to produce the technical process of higher degree intermediate component long, it is many that technology is connected, and produce the by product of a plurality of non-intermediate component.
The objective of the invention is to make full use of and bring into play the advantage that three outlet technologies are isolated intermediate component, simplify the technology of further extracting and separating purification intermediate component simultaneously, overcome the above-mentioned shortcoming that three independently fractionation extraction series of separate purification intermediate component technical process are long, operation is many, by product is many of passing through.
Feature of the present invention:
Under certain processing parameter condition, the polycomponent lucium can be divided into easy collection component in cascade extraction, intermediate component, difficult collection component, and intermediate component forms accumulation peak (this technology of invention person is main process) in organic phase or aqueous phase, draw intermediate component from the centre outlet, continue to separate purification intermediate component (this is a body technology invention person) with solvent extration, and this body technology only goes out the intermediate component product, contain easy collection component organic phase and/or difficult collection component water then from the organic phase therewith of main process and/or the close level of water-phase component flow back to main process corresponding mutually, and participate in the extraction process of main process.The above-mentioned corresponding organic phase fluid that contains easy collection component that is meant that mutually a body technology produces is got back in the organic phase of main process, and the water that contains difficult collection component that a body technology produces then flow back into the aqueous phase of main process.The close level of the composition of above-mentioned main process is meant the extractor of the close level of composition that contains easy collection component organic phase and/or difficult collection component water that produces with a body technology, and this is not doubt through the analysis to solution in the main process extractor.The solvent extration of above-mentioned body technology can be counter-current extraction, countercurrent washing, fractionation extraction or its combination, decides on the intermediate component grade and the intermediate component product grade of raw material.
The present invention will produce the extraction process at intermediate component accumulation peak and the extraction process of purification intermediate component (body technology) and unite as a wholely, become a kind of extracting process with support body.From integral body, the extracting process of band support body has still kept the outlet number of former main process, but the grade of intermediate component greatly improves; The extraction equipment that props up body technology simultaneously is more much smaller than the extraction equipment of main process, thus the present invention than with increase main process progression improve the intermediate component grade method economy many; On the other hand, because body technology produces contains easy extracted component organic phase and/or difficult collection component water directly flow back in the main process extractor, participate in the extraction process of main process, so in fact, former some extraction process that carries out in a body technology is moved on in the main process and carry out, thereby reduced the progression of a body technology, simplify a body technology greatly, and do not produced by product.
Further specify the present invention below in conjunction with embodiment.
Embodiment 1: intermediate component forms the accumulation peak in organic phase.Draw intermediate component from the central exit of main process, as organic feed liquid of a body technology.Prop up body technology and form, see Fig. 1 by the countercurrent washing and the fractionation extraction that link to each other.The organic feed liquid of intermediate component is at first through the difficult collection of multi-stage countercurrent washing flush away component, the scrub raffinate (2) that has a difficult collection component flows out and flows back to the main process water from the close level of composition with it of main process from support body countercurrent washing charging level, continues extracting and separating in main process; The back extraction liquid (3) of washing of removing difficult collection component flows out multi-stage countercurrent washing extractor, then carries out fractionation extraction, separates and removes easy collection component.The extraction liquid (6) that has an easy collection component flows back to the organic phase of main process from the close level of composition of main process, and continues extracting and separating in main process; The raffinate of fractionation extraction (7) outflow is the intermediate component product after the purification.Because the main task of fractionation extraction is an easily collection component of extraction, and the extraction liquid (6) that has easy collection component flows back to the extracting and separating that main body participates in main process, therefore, the washing section of fractionation extraction can save many levels in the body technology, just can satisfy processing requirement and only need 2～3 grades.
Embodiment 2: intermediate component forms the accumulation peak at aqueous phase.Draw intermediate component from the central exit of main process, as the aqueous phase liquid of a body technology.Prop up body technology and form, see Fig. 2 by counter-current extraction and fractionation extraction that front and back link to each other.The intermediate component aqueous phase liquid at first separates through multi-stage counter current extraction removes easy collection component, the load organic phases 9 that collection has an easy collection component flows out and flows back to the main process organic phase from the close level of composition with it of main process from a body technology counter-current extraction charging level, continues extracting and separating in main process; The water raffinate (10) of removing easy collection component flows out the multi-stage counter current extraction groove, then carries out fractionation extraction, separates and removes difficult collection component.The water raffinate (13) that has a difficult collection component flows back to the water of main process from the close level of composition of main process, and continues extracting and separating in main process; The extraction liquid of fractionation extraction (14) outflow is the intermediate component after the purification.Through back extraction, intermediate component can be transferred to aqueous phase again.Because being washing, the main task of fractionation extraction removes difficult collection component, and the raffinate (13) that has difficult collection component flows back to main process and continues to participate in extracting and separating, therefore, the extraction section of fractionation extraction can be saved many levels in the body technology, just can satisfy processing requirement and only need 2～3 grades.
Above-mentioned embodiment 1 and 2 is comparatively general situations, and promptly the intermediate component that comes out of main process contains higher difficulty collection component and Yi Cui component, and the grade of intermediate component product requirement is again than higher simultaneously.In particular cases, the contained difficulty of the intermediate component that main process the comes out collection component or the component of easily coming together are very low, and it is still desired low after a body technology enrichment than intermediate component product, then the present invention has following embodiment, wherein embodiment 3 and 4 is simplification of scheme 1, and embodiment 5 and 6 is simplification of scheme 2.
Embodiment 3: intermediate component forms the accumulation peak in organic phase, and contained easy collection component is very low and need not separate from the intermediate component that main process is drawn, with scheme 1 relatively, only need this moment to separate difficult collection component through the multi-stage countercurrent washing, see Fig. 3.Draw the organic feed liquid of intermediate component from main process as a body technology, in the extractor of multi-stage countercurrent washing after the difficult collection of the flush away component, the scrub raffinate that has difficult collection component flows back to the main process water from the outflow of support body process feeds level and from the close level of composition, continues extracting and separating in main process; Wash back extraction liquid (3) then from the outlet of body technology, be the intermediate component after the purification, can be through back extraction with the intermediate component back extraction to aqueous phase.
Embodiment 4: intermediate component forms the accumulation peak in organic phase, and the contained difficulty collection component of the intermediate component of drawing from main process is very low and need not separate, and at this moment only needs to separate easily collection component through fractionation extraction, see Fig. 4.Draw the organic feed liquid of intermediate component from main process as a body technology, remove easy collection component through fractionation extraction, the extraction liquid (6) that has easy collection component flows back to the organic phase of main process from the close level of composition, and in main process, continuing extracting and separating, the raffinate of fractionation extraction (7) is from propping up the intermediate component after the body technology outlet is purification.Identical with embodiment 1, the washing section of fractionation extraction only needs 2～3 grades can satisfy processing requirement.
Embodiment 5: intermediate component forms the accumulation peak at aqueous phase, and contained difficulty collection component is very low and need not separate from the intermediate component that main process is drawn, with scheme 2 relatively, only need this moment to separate and remove easy collection component through multi-stage counter current extraction, see Fig. 5.Draw the aqueous phase liquid of intermediate component from main process as a body technology, after multi-stage counter current extraction separates the component of easily coming together, the load organic phases (9) that has an easy collection component flows out and flows back to the main process organic phase from the close level of composition of main process from support body process feeds level, continuation is extracting and separating in main process, raffinate (10) is then from the outlet of body technology, is the intermediate component product after the purification.
Embodiment 6: intermediate component forms the accumulation peak at aqueous phase, and contained easy collection component is very low and need not separate from the intermediate component that main process is drawn, and only needs this moment remove difficult collection component through fractionation extraction, sees Fig. 6.Draw the aqueous phase liquid of intermediate component as a body technology from main process, remove difficult collection component through fractionation extraction, the raffinate (13) that has difficult collection component flows back to the main process water from the close level of composition, and continues extracting and separating in main process; Extraction liquid load organic phases 14 is from propping up the intermediate component after the body technology outlet is purification.Identical with embodiment 2, the extraction section of fractionation extraction only needs 2～3 grades can satisfy processing requirement.
Description of drawings: the m representative washing progression of each figure, n representative extraction progression.
Fig. 1 is the synoptic diagram of embodiment 1, and a body technology is made up of multi-stage countercurrent washing and fractionation extraction that front and back link to each other.Wherein 1 is the main process flow process, the 2nd, the scrub raffinate of multi-stage countercurrent washing, the 3rd, multi-stage countercurrent washing wash the back extraction liquid, the 4th, wash sour II, the 5th, wash sour I, the 6th, the extraction liquid of fractionation extraction, the 7th, the raffinate of fractionation extraction, intermediate component after promptly purifying, the 8th, the intermediate component enriched substance or the thick product of drawing from main process.
Fig. 2 is the synoptic diagram of embodiment 2, and a body technology is made up of multi-stage counter current extraction and fractionation extraction that front and back link to each other.Wherein 9 is load organic phases of multi-stage counter current extraction, the 10th, and the water raffinate of multi-stage counter current extraction, the 11st, extraction agent II, the 12nd, extraction agent I, the 13rd, the water raffinate of fractionation extraction, the 14th, the extraction liquid of fractionation extraction, the intermediate component after promptly purifying.
Fig. 3 is the synoptic diagram of embodiment 3, and wherein 2 is scrub raffinates of a body technology, the 3rd, prop up the back extraction liquid of washing of body technology, the intermediate component after promptly purifying.
Fig. 4 is the synoptic diagram of embodiment 4, and wherein 6 is extraction liquids of a body technology, the 7th, and the raffinate of a body technology, the intermediate component after promptly purifying.
Fig. 5 is the synoptic diagram of embodiment 5, and wherein 9 is load organic phases of a body technology, the 10th, and the raffinate of a body technology, the intermediate component after promptly purifying.
Fig. 6 is the synoptic diagram of embodiment 6, and wherein 13 is raffinates of a body technology, the 14th, and the extraction liquid of a body technology, the intermediate component after promptly purifying.
Be specific embodiments of the invention below:
Embodiment 1: yttrium mixed rare earth Dy-Ho grouping in the rich europium, band support body extracting and separating intermediate component Dy.
Mishmetal ore deposit composition sees Table 1 material 1, after the HCI dissolving purifies, gets aqueous solution of rare earth chloride, make its PH=2, rare earth concentration 1.15～1.25M, extraction agent are HEH(EHP)-kerosene, HEH(EHP) concentration is 1.5N, uses the ammoniacal liquor saponification, ammonification concentration 0.50～0.53N.Adopt band support body extraction process shown in Figure 4.Main process Dy-Ho grouping, totally 34 grades, wash sour HCI concentration 3.1～3.8N, stream is than being extraction agent: feed liquid: wash acid=450: 40: 71, organic being on good terms of main process flow process extraction section forms the accumulation peak of 75～85%Dy.Drawing intermediate component Dy enriched substance, is that the small-sized extraction tank of main process flow sheet equipment 9% is as the support body technological process apparatus with processing power.Body technology n=16 level, the m=3 level, it is identical with main process to wash acid and extraction agent, and stream is than being extraction agent: the organic feed liquid of intermediate component: wash acid=31: 11: 5.7.Behind the extraction equilibrium, main process flow process water exports out the La-Tb component, contains Dy
2O
3＜0.5%, Ho
2O
3＜0.1%, organic phase exports out the Ho-Y-Lu component, contains Dy
2O
3＜0.5%, Tb
4O
7＜0.01%; Support body technical process outlet Dy product, Dy
2O
3＞98%.
Embodiment 2: Longnan low yttrium mischmetal Dy-Ho grouping band support body extracting and separating intermediate component Dy.
The rare earth composition of low yttrium mischmetal aqueous chloride solution sees Table 1 material 2, PH=2, rare earth concentration 1.0M, extraction agent are HEH(EHP)-kerosene, HEH(EHP) concentration 1.0N, ammonification concentration is 0.34～0.36N, adopts the band support body extraction process of Fig. 3.Main process flow process Dy-HO grouping, totally 44 grades, wash sour HCI concentration 3.1～3.9N, stream is than being extraction agent: feed liquid: wash acid=141: 10: 9.5, form the accumulation peak of Dy in the main process flow process extraction section organic phase.Draw the Dy enriched substance, the extraction tank that with processing power is main process equipment 27% is as the support body processing unit, support body technical process m=12 level, and it is identical with main process to wash acid, and stream is than being the organic feed liquid of intermediate component: wash acid=40: 2.7.Behind the extraction equilibrium, main process flow process water exports out the La=Tb component, contains Dy
2O
3＜1%, Ho
2O
3＜0.1%, organic phase exports out the Ho-Y-Lu component, contains Dy
2O
3＜1%, Tb
4O
7＜0.01%, support body technical process outlet Dy product, Dy
2O
3＞97%.
Embodiment 3: yttrium mixed rare earth Dy-HO grouping in the rich europium, band support body extracting and separating intermediate component Dy.
Mishmetal ore deposit composition sees Table 1 material 3, through HNO
3Get rare earth nitrate aqueous solution after dissolving purifies, making its free acid is 0.05～0.1N, the dense rate 1.47～1.53M of rare earth, extraction agent is HEH(EHP)-kerosene, HEH(EHP) concentration 1.5N, ammonification concentration 0.48～0.54N, the band support body extraction process of employing Fig. 1.Main process flow process Dy-Ho grouping, is washed sour HNO by totally 41 grades
3Concentration 3.0～3.7N, stream are than for extraction agent: feed liquid: wash acid=151: 10: 18, can form Dy accumulation peak in the main process flow process extraction section organic phase.Drawing intermediate component, is that the small-sized extraction tank of main process extraction tank 14% is made the support body processing unit, support body technical process progression n with processing power
1=35 grades, m
1=3 grades, m
2=30 grades, it is identical with main process with extraction agent to wash sour II, washes the HNO of sour I
3Concentration 4.8～5.5N, stream are than for the organic feed liquid of intermediate component: wash sour II: extraction agent: wash sour I=21.6: 1.86: 7.03: 2.5.Behind the extraction equilibrium, main process flow process water exports out the La-Tb component, contains Dy
2O
3＜0.8%, Ho
2O
3＜0.1%, organic phase exports out the Ho-Y-Lu component, contains Dy
2O
3＜0.5%, Tb4O
7＜0.01%, support body technical process outlet Dy product, Dy
2O
3＞99.5%.
Embodiment 4: mishmetal Dy-Ho grouping during rich europium is light, band support body extracting and separating Dy.
Rare earth feed liquid is an aqueous chloride solution, and the rare earth composition sees Table 1 material 4, concentration 1.0M, and PH=3, extraction agent are D
2EHPA-kerosene, D
2EHPA concentration 1.0N, ammonification rate 20% adopts Fig. 4 technical process.Main process flow process Dy-HO grouping, totally 34 grades, wash sour HCI concentration 3.1～3.6N, main process stream is than being extraction agent: feed liquid: wash acid=152: 10: 19.4, form the accumulation peak of Dy in the main process flow process extraction section organic phase, draw intermediate component, with processing power is that the small-sized extraction tank of main process flow process 7% is made the support body processing unit, support body technical process n=15 level, the m=3 level, extraction agent is with to wash acid identical with the main process flow process, and stream is than being extraction agent: the organic feed liquid of intermediate component: wash acid=8.3: 2.9: 1.5.Behind the extraction equilibrium, main process flow process water exports out the La-Tb component, contains Dy
2O
3＜0.3%, Ho
2O
3＜0.1%, organic phase exports out the Ho-Y-Lu component, contains Dy
2O
3＜0.2%, Tb
4O
7＜0.01%; Support body technical process outlet Dy product, Dy
2O
3＞98%.
Embodiment 5: mishmetal Dy-Ho grouping in light, the band support body separates Dy.
The rare earth nitrate aqueous solution composition sees Table 1 material 5, concentration 1.55～1.85M, PH=2, extraction agent are HEH(EHP)-kerosene, HEH(EHP) concentration is 1.0N, ammonification concentration 0.32～0.37N, Fig. 3 is seen in technical process.Main process flow process Dy-Ho grouping, is washed sour HNO by totally 32 grades
3Concentration 3.2～3.7N, main process flow process stream is than being extraction agent: feed liquid: wash acid=151: 5: 17, form Dy in the main process flow process extraction section organic phase and be about 75% accumulation peak.Drawing intermediate component, is that the small-sized extraction tank of main process equipment 2% is made the support body processing unit with processing power, the m=12 level, and it is identical with main process to wash acid, and the support body process flow is than being the organic feed liquid of intermediate component: wash acid=28: 2.1.Behind the extraction equilibrium, main process flow process water exports out the La-Tb component, contains Dy
2O
3＜0.3%, Ho
2O
3＜0.1%, organic phase exports out the Ho-Y-Lu component, contains Dy
2O
3＜0.3%, Tb
4O
7＜0.01%; Support body technical process outlet Dy product, Dy
2O
3＞97%.
Embodiment 6: sm-eu-gd lucium Sm/ support body Eu/Gd separates.
The rare earth chloride feed liquid sees Table 1 material 6, concentration 0.98～1.02M, and PH=3, extraction agent are D
2EHPA-kerosene, D
2EHPA concentration 1.0N, ammonification rate 20%, Fig. 3 is seen in technical process.Main process flow process Eu-Gd grouping, totally 64 grades, washing sour HCI is 2.5～3.0N, stream is than being extraction agent: feed liquid: wash acid=126: 5: 16, form Eu accumulation peak in the main process flow process extraction section organic phase.Draw intermediate component, with processing power be the small-sized extraction tank of main process flow process 9% as the support body processing unit, the m=9 level, it is identical with the main process flow process to wash acid, stream is than being the organic feed liquid of intermediate component: wash acid=10.4: 0.35.Behind the extraction equilibrium, main process flow process water exports out Sm product, Sm
2O
3＞99%, organic phase exports out Gd product, Gd
2O
3＞99.5%; Prop up body technology outlet Eu, Eu
2O
3＞82%.
Embodiment 7: heavy rare earth mixture Tm-Yb grouping, the band support body separates intermediate component Tm.
Longnan rare earth ore is after separating yttrium and Dy-Ho grouping, obtain the muriate rare earth aqueous solution, its composition sees Table 1 material 7, concentration 0.80M, PH=1.0, extraction agent are HEH(EHP)-kerosene, HEH(EHP wherein) concentration 1.0N, use the ammoniacal liquor saponification, ammonification concentration 0.33～0.37N, Fig. 1 is seen in technical process.Main process flow process Tm-Yb grouping, totally 46 grades, washing acid is 3.1～3.9N, main process stream is than being extraction agent: feed liquid: wash acid=448: 60: 20.7, Tm accumulation peak is arranged in the main process flow process extraction section organic phase, drawing intermediate component, is that the small-sized extractor of main process equipment 23% is made support body processing unit, m with processing power
2=25 grades, n
1=30 grades, m
1=3 grades, the HCI that washes sour I is 4.5～5.5N, and extraction agent is with to wash sour II identical with the main process flow process, stream is than for the organic feed liquid of intermediate component: wash sour II: extraction agent: wash sour I=110: 6: 30.8: 5.2, behind the extraction equilibrium, main process flow process water exports out the Ho-Er component, contains TM
2O
3＜0.07%, Yb
2O
3＜0.05%, organic phase exports out Yb, Lu component, contains Tm
2O
3＜0.05%; Support body technical process outlet Tm product, Tm
2O
3＞99.95%.
Embodiment 8: heavy rare earth mixture Er-Tm grouping, the band support body separates intermediate component Tm.
In the rich europium divide into groups through Dy-Ho in the yttrium ore deposit, after carrying yttrium, get aqueous solution of rare earth chloride, its composition sees Table 1 material 8, concentration 1.15～1.25M, PH=1～3, extraction agent is HEH(EHP)-kerosene, HEH(EHP) concentration is 1.5N, uses the ammoniacal liquor saponification, ammonification concentration 0.49～0.54N, Fig. 2 is seen in technical process.Main process Er-Tm grouping, totally 29 grades, wash sour HCI3.1～3.9N, main process stream is than being extraction agent: feed liquid: wash acid=484: 100: 51.6, main process flow process washing section aqueous phase forms Tm accumulation peak.Drawing intermediate component, is that the small-sized extractor of main process equipment 13% is made support body processing unit, m with processing power
1=17 grades, n
1=2 grades, n
2=15 grades, extraction agent is with to wash acid identical with main process, and the support body process flow is than being the intermediate component aqueous phase liquid: extraction agent II: extraction agent I: wash acid=9.0: 43.3: 29: 0.93.Behind the extraction equilibrium, the main process water exports out the Ho-Er component, contains Tm
2O
3＜0.01%, organic phase exports out Yb, Lu component, contains Tm
2O
3＜3%; Support body technical process outlet Tm product, Tm
2O
3＞99.95%.
Embodiment 9:
Feed liquid sees Table 1 material 8, concentration 1.45～1.55M, and PH=1～3, extraction agent is HEH(EHP)-kerosene, HEH(EHP) concentration 1.0N uses the ammoniacal liquor saponification, ammonification concentration 0.33～0.37N, Fig. 5 is seen in technical process.Main process flow process Er-Tm grouping, totally 36 grades, wash sour HCI concentration 3.1～3.9N, main process stream is than being extraction agent: feed liquid: wash acid=88: 10: 6.45, main process washing section water has Tm accumulation peak.Drawing intermediate component, is that the small-sized extractor of main process equipment 9% is made the support body processing unit with processing power, the n=9 level, and extraction agent is identical with main process, and the support body process flow is than being the intermediate component aqueous phase liquid: extraction agent=0.9: 8.2.Behind the extraction equilibrium, the main process water exports out the Ho-Er component, contains Tm
2O
3＜0.01%, organic phase exports out Yb, Lu component, contains Tm
2O
3＜1%; Support body technical process outlet Tm product, Tm
2O
3＞95%, can Tm be stripped into aqueous phase from organic phase with back extraction acid.
Embodiment 10:
Rare earth feed liquid sees Table 1 material 8, and concentration 1.15～1.25M, PH=1～3, extraction agent is HEH(EHP)-kerosene, wherein HEH(EHP) concentration is 1.5N, uses the ammoniacal liquor saponification, ammonification concentration 0.48～0.54N, Fig. 6 is seen in technical process.Main process flow process Er-Tm grouping, totally 29 grades, wash sour HCI concentration 3.1～3.9N, main process stream is than being extraction agent: feed liquid: wash acid=463: 100: 51.6, main process washing section water forms Tm accumulation peak.Draw intermediate component and make the support body processing unit with small-sized extractor, the n=3 level, the m=13 level, it is identical with main process to wash acid, and the support body process flow is than being the intermediate component aqueous phase liquid: extraction agent: wash acid=5.7: 45: 3.6.Behind the extraction equilibrium, the main process water exports out the Ho-Er component, contains Tm
2O
3＜0.01%, organic phase exports out Yb, Lu component, contains Tm
2O
3＜2%, a body technology outlet Tm product, Tm
2O
3＞96%.
Solvent extraction has compared with prior art been simplified technological process, saves industrial investment, The institute's generation fund that retains organic extractant and amount of metal overstocks obviously and reduces, thereby the Rare Earth Production cost. Available a plurality of the body technologies of multiple exit main process are attached thereto. The present invention also may be used for the multicomponent extract and separate of other metallic elements.
Claims (13)
1, the extraction process of a band body technology, it comprises that producing intermediate component accumulates the rare earth extraction technology at peak and the extraction process of purification intermediate component, is characterized in that:
A. the extraction process that produces intermediate component accumulation honeybee is a main process, and the extraction process of purification intermediate component is a body technology;
B. prop up body technology and only export the intermediate component product, contain easy collection component organic phase and/or difficult collection component water, continue extracting and separating in main process from close grade of corresponding phase that flows back to main process of main process composition.
2, according to the method for claim 1, it is characterized in that from the intermediate component that main process is drawn be organic phase, prop up body technology and be made up of multi-stage countercurrent washing and fractionation extraction that front and back link to each other, the scrub raffinate of multi-stage countercurrent washing and the extraction liquid of fractionation extraction flow back to the mutually corresponding of main process respectively.
3, according to the method for claim 1, it is characterized in that from the intermediate component that main process is drawn be water, prop up body technology and be made up of multi-stage counter current extraction and fractionation extraction that front and back link to each other, the load organic phases of multi-stage counter current extraction flows back to the mutually corresponding of main process respectively with the raffinate of fractionation extraction.
4, according to the method for claim 1, it is characterized in that from the intermediate component that main process is drawn be organic phase, a body technology is the multi-stage countercurrent washing, its scrub raffinate flows back to the water of main process.
5, according to the method for claim 1, it is characterized in that from the intermediate component that main process is drawn be organic phase, a body technology is fractionation extraction, its extraction liquid flows back to the organic phase of main process.
6, according to the method for claim 1, it is characterized in that from the intermediate component that main process is drawn be water, a body technology is a multi-stage counter current extraction, its load organic phases flows back to the organic phase of main process.
7, according to the method for claim 1, it is characterized in that from the intermediate component that main process is drawn be water, a body technology is fractionation extraction, its raffinate flows back to the water of main process.
8, according to the method for claim 2, it is characterized in that main process is to contain free acid 0.05～0.1N, the nitrate aqueous solution in ruthenium ion adsorptive type rare earth ore deposit is a raw material in the rich europium of rare earth concentration 1.47～1.53M, extraction agent HEH(EHP) concentration 1.5N, dilute with kerosene, ammonification concentration 0.48～0.54N washes sour HNO
3Concentration 3.0～3.7N carries out Dy-Ho grouping, and stream is than being extraction agent: feed liquid: wash acid=151: 10: 18, the organic phase D y enriched substance that the main process central exit is drawn is purified in a body technology; It is identical with main process with extraction agent that body technology is washed sour II, washes the HNO of sour I
3Concentration 4.8～5.5N, stream are than for the organic feed liquid of intermediate component: wash sour II: extraction agent: wash sour I=21.6: 1.86: 7.03: 2.5; Main process outlet La-Tb component and Ho-Y-Lu component, the Dy product after a body technology outlet is purified.
9, according to the method for claim 4, it is characterized in that main process is a raw material with Longnan low yttrium mischmetal aqueous chloride solution after purifying, feed liquid rare earth concentration 1.0M, PH=2, extraction agent HEH(EHP) concentration 1.0N, dilute with kerosene, ammonification concentration 0.34～0.36N washes sour HC1 concentration 3.1～3.9N, carries out the Dy-Ho grouping, stream is than for extraction agent: feed liquid: wash acid=141: 10: 9.5, the organic phase D y enriched substance that the main process central exit is drawn is purified in a body technology; It is identical with main process that body technology is washed acid, and stream is than being the organic feed liquid of intermediate component: wash acid=40: 2.7; Main process outlet La-Tb component and Ho-Y-Lu component, the Dy product after a body technology outlet is purified.
10, according to the method for claim 4, it is characterized in that main process is a feed liquid based on the nitrate aqueous solution in the mishmetal ore deposit of the light middle-weight rare earths of ion adsorption type, rare earth concentration 1.55～1.85M, PH=2, extraction agent HEH(EHP) concentration 1.0N, with the kerosene dilution, ammonification concentration 0.32～0.37N washes sour HNO
3Concentration 3.2～3.7N carries out Dy-Ho grouping, and stream is than being extraction agent: feed liquid: wash acid=151: 5: 17, the main process central exit is drawn organic phase Dy enriched substance and is purified in a body technology; It is identical with main process that body technology is washed acid, and stream is than being the organic feed liquid of intermediate component: wash acid=28: 2.1; Main process outlet La-Tb component and Ho-Y-Lu component, the Dy product after a body technology outlet is purified.
11, according to the method for claim 5, it is characterized in that main process is a feed liquid based on the aqueous chloride solution in the mishmetal ore deposit of the light middle-weight rare earths of the rich europium of ion adsorption type, rare earth concentration 1.0M, PH=3, extraction agent D2EHPA concentration 1.0N dilutes with kerosene, ammonification rate 20%, wash sour HC1 concentration 3.1～3.6N, stream is than for extraction agent: feed liquid: wash acid=152: 10: 19.4, the main process central exit is drawn organic phase Dy enriched substance and is purified in a body technology; It is identical with main process with extraction agent that body technology is washed acid, and the stream ratio is an extraction agent: the organic feed liquid of intermediate component: wash acid=8.3: 2.9: 1.5; Main process outlet La-Tb component and Ho-Y-Lu component, the Dy product after a body technology outlet is purified.
12, according to the method for claim 5, it is characterized in that main process is a raw material with the aqueous chloride solution in yttrium mixed rare earth ore deposit in the rich europium of ion adsorption type, rare earth concentration 1.15～1.25M, PH=2, extraction agent HEH(EHP) concentration 1.5N, dilute with kerosene, ammonification concentration 0.50～0.53N, wash sour HC13.1～3.8N, stream is than for extraction agent: feed liquid: wash acid=450: 40: 71, the main process central exit is drawn the enriched substance of organic phase Dy and is purified in a body technology; It is identical with main process with extraction agent that body technology is washed acid, and the stream ratio is an extraction agent: the organic feed liquid of intermediate component: wash acid=31: 11: 5.7; Main process outlet La-Tb component and Lo-Y-Lu component, the Dy product after a body technology outlet is purified.
13, according to the method for claim 3, it is characterized in that main process is a feed liquid with the aqueous solution of the heavy rare earth mixture of ruthenium ion adsorptive type rare earth ore deposit in the rich europium behind Dy-HO grouping and purification yttrium, concentration 1.15～1.25M, PH=1～3, extraction agent HEH(EHP) concentration 1.5N, with kerosene dilution and ammonification, ammonification concentration is 0.49～0.54N, wash sour HCI concentration 3.1～3.9N, carry out the Er-Tm grouping, stream is than for extraction agent: feed liquid: wash acid=484: 100: 51.6, the main process central exit is drawn water Tm enriched substance and is purified in a body technology; Body technology extraction agent and to wash acid identical with main process, the stream ratio is the intermediate component aqueous phase liquid: extraction agent II: extraction agent I: wash acid=9.0: 43.3: 29: 0.93; Main process outlet Ho-Er component and Yb-Lu component, the Tm product after a body technology outlet is purified.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90100135A CN1019639B (en) | 1990-01-10 | 1990-01-10 | Solvent extraction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90100135A CN1019639B (en) | 1990-01-10 | 1990-01-10 | Solvent extraction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1044409A CN1044409A (en) | 1990-08-08 |
| CN1019639B true CN1019639B (en) | 1992-12-30 |
Family
ID=4876492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90100135A Expired CN1019639B (en) | 1990-01-10 | 1990-01-10 | Solvent extraction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1019639B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1086424C (en) * | 1998-01-13 | 2002-06-19 | 北京大学 | Process for producing rare-earth with various kinds of pureness specifications by separation method |
| CN1872377B (en) * | 2006-01-04 | 2010-08-18 | 有研稀土新材料股份有限公司 | Method for saponifying extraction agent |
| CN102115822B (en) * | 2010-11-18 | 2015-06-10 | 吴泉锦 | Method for recovering rare earth oxide from fluorescent powder and polishing powder waste |
| CN102676811B (en) * | 2012-03-29 | 2013-11-06 | 江西稀有稀土金属钨业集团有限公司 | Method and system for extracting EuCl3-rich solution |
| CN103757446B (en) * | 2014-01-28 | 2015-05-20 | 福建省长汀金龙稀土有限公司 | Novel process for separating low-Y content heavy rare earth |
| CN103773976B (en) * | 2014-01-28 | 2015-07-29 | 福建省长汀金龙稀土有限公司 | The high-purity Gadolinium trichloride technique of a kind of fuzzy interlock extracting and separating output |
| CN105087965B (en) * | 2014-12-30 | 2017-05-10 | 江西农业大学 | Method for extractive separation of La-Nd light rare earth |
| CN109022836B (en) * | 2018-08-30 | 2021-03-12 | 江西农业大学 | Light rare earth ore pre-separation belt branch body extraction separation process method |
-
1990
- 1990-01-10 CN CN90100135A patent/CN1019639B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN1044409A (en) | 1990-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105256157B (en) | Pre-separation is extracted to light rare earth ore deposit and the method for middle ruthenium ion Rare Earth Mine combined separation | |
| CN105256155B (en) | The load organic phases of extract and separate light rare earth ore deposit are used for the method for ion Rare Earth Mine extract and separate | |
| WO1996011737A1 (en) | Red mud dewatering and washing process | |
| CN105543507B (en) | The method that light rare earth ore deposit and low ruthenium ion Rare Earth Mine extract combined separation with pre-separation | |
| CN105568008B (en) | Divide high-purity three outlet extraction in advance | |
| CN1019639B (en) | Solvent extraction | |
| CN108754190A (en) | Light rare earth mine divides the middle heavy rare earth separating process of extraction and load organic phases in advance | |
| CN103060580A (en) | Method for separating titanium, scandium and zirconium in scandium extraction with titanium white waste acid | |
| CN1824814A (en) | Full separating technique of non-saponification organic phase extracting rare-earth | |
| CN106498191A (en) | The method of three charging aperture fractional extraction separation of mixed rare-earth | |
| CN109897976B (en) | La-Nd light rare earth pre-separation three-outlet extraction separation process | |
| CN102010999B (en) | Method for separating impurities from cobalt and/or nickel solution by non-saponifiable extraction | |
| CN101294245A (en) | Technique for extraction separation of quadravalence cerium, thorium and cerium less tervalence rare earth from sulphuric acid rare earth solution | |
| CN85102210A (en) | Process for seperation of mixed rare-earths by ammoniated HEH (EHP) | |
| CN104593593A (en) | Method for two-inlet three-outlet full-load fractionation extraction separation of samarium-europium-gadolinium enriched product | |
| CN1710119A (en) | Process for removing impurity element aluminium from rate-earth solution by fatty acid extraction | |
| CN101117663A (en) | Rare earth backflow extraction method and rare earth fully separating process employing the method | |
| CN1049695C (en) | Method for purifying noble metal with double function extracting agent containing nitrogen and phosphorus | |
| CN110423902A (en) | A kind of preparation method and system of high-purity carbonated rare earth | |
| CN102676811B (en) | Method and system for extracting EuCl3-rich solution | |
| CN101824535B (en) | Process for gathering trace rare earth from phosphoric acid by using centrifugal extracting equipment | |
| CN109022836B (en) | Light rare earth ore pre-separation belt branch body extraction separation process method | |
| CN87101822A (en) | Medium-gadolinium and rich-europium ion type rare-earth mineral rare earth complete-separation process | |
| CN1058994A (en) | One-step extracting and seperating pure yttrium, thick erbium and heavy rare earths | |
| CN104561611A (en) | Three-outlet fully-loaded fractional extraction separation process of rare earth |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |