CN104611560A - Method for enriching rare earth from rare-earth leaching mother liquor - Google Patents
Method for enriching rare earth from rare-earth leaching mother liquor Download PDFInfo
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- CN104611560A CN104611560A CN201510036804.1A CN201510036804A CN104611560A CN 104611560 A CN104611560 A CN 104611560A CN 201510036804 A CN201510036804 A CN 201510036804A CN 104611560 A CN104611560 A CN 104611560A
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Abstract
The invention discloses a method for enriching rare earth from rare-earth leaching mother liquor. The method comprises the following steps: (1) preparing an active carbon adsorption material; (2) performing column packing; (3) performing column saponification; (4) performing column enrichment; (5) performing column washing; (6) performing column circulation. The active carbon adsorption material is used for enriching the rare-earth leaching mother liquor, so that an environmental pollution problem caused by a settling method is solved, a problem of difficult phase splitting in conventional solvent extraction is solved, and a new method is provided for enriching the rare-earth leaching mother liquor; active carbon has an oil absorption characteristic and is free of COD (chemical oxygen demand) pollution problems caused by saponification wastewater and extraction wastewater.
Description
Technical field
The present invention relates to rare earth element recovery technology field, particularly relate to a kind of method leaching enrichment rare earth mother liquor from rare earth.
Background technology
Ion type rareearth ore middle-weight rare earths is composed with " ion " form and is stored in granite weathering crust, obtain re dip solution, but gained leach liquor middle-weight rare earths concentration is low, complex chemical composition, impurity ion content are many through ammonium sulfate in_situ leaching technology.The rare-earth process method leached in mother liquor for enrichment at present mainly contains carbon ammonium precipitation method, oxalate precipitation method and solvent extration, carbon ammonium precipitation method poor selectivity, easy and other foreign ions form co-precipitation, add to the difficulties to the purification of follow-up rare earth feed liquid, extracting and separating operation; The mother liquor of precipitation of ammonium that carbon ammonium precipitation method produces simultaneously contains a large amount of ammonia nitrogen waste waters, contaminate environment.Oxalate precipitation method rare earth yield is low, and condition is harsh, and oxalic acid consumption is large, expensive simultaneously, is toxicant.Adopt solvent extration enrichment rare earth to leach mother liquor, rare earth concentration is low, foreign matter content is high causes easily producing when extracting operation third phase, extraction agent easily problem such as " poisoning ", shorten the work-ing life of extraction agent; Re dip solution mother amount is large, adopts solvent extration process rare earth to leach mother liquor cost high, and organic phase solution loss in water is large, and in waste water, COD content is high, also can bring certain pollution to environment.In recent years country also been proposed new requirement in the green extraction of rare earth, and the enrichment rare earth that therefore development research is new leaches mother liquor method becomes crucial.
Summary of the invention
Leaching the efficiently concentrating of mother liquor for realizing rare earth, the invention provides a kind of method leaching enrichment rare earth mother liquor from rare earth.Gac belongs to a kind of unformed Carbon Materials, and it is made up of graphite microcrystal and the hydrocarbon polymer that connects these crystallites.The stable chemical nature of gac, can resistance to strong acid, highly basic, high temperature, High Pressure, and it has flourishing microvoid structure and huge specific surface area, has good absorption property to organic substance and granule foreign.Invention utilizes the adsorbable organic characteristic of gac, adopts pickling process by extraction agent absorption on the activated carbon, then realizes with active carbon adsorption material the enrichment that rare earth leaches mother liquor.
The present invention adopts following technical scheme:
The concrete steps of the method for enrichment rare earth from rare earth leaching mother liquor of the present invention are as follows:
(1) preparation of active carbon adsorption material:
By phosphorus extractant and sulfonated kerosene by volume for the ratio of 1:0 ~ 4 is mixed to form organic phase, the ratio of to be 5 ~ 500 object gacs by organic phase and granularity be in mass ratio 0.1 ~ 5:1 mixes formation active carbon adsorption material;
(2) post is filled:
Active carbon adsorption material wet method dress post method loading post footpath step (1) obtained is 1 ~ 300cm, aspect ratio is the ion exchange column of 1 ~ 80:1;
(3) post saponification:
In separator column, add ammoniacal liquor that concentration is 0.1 ~ 14.8mol/L or sodium hydroxide solution carries out saponification to active carbon adsorption material, then use distilled water wash separator column to elutant without muddiness;
(4) post enrichment:
The ion exchange column that step (3) dress post obtains carries out multicolumn series connection and obtains separator column, and series system is as Fig. 2; Separator column is divided into column extractor and re-extraction column according to pillar jointing, and post trend is along column extractor and re-extraction column direction; Mother liquor is leached with 0.1 ~ 20cmmin with the rare earth that pH value is 2 ~ 5
-1flow velocity flow through separator column from the first column extractor, be that the hydrochloric acid of 0.1 ~ 6mol/L is with 0.1 ~ 20cmmin by concentration
-1flow velocity flow through separator column from the first re-extraction column, until first column extractor absorption saturated after, the first column extractor enters stripping section, obtains rareearth enriching material at the n-th re-extraction column place;
(5) post washing:
Being washed with distilled water to elutant pH value being greater than 2 containing acid separation column after using, obtains blank post;
(6) post circulation:
Blank post recirculation step (3) ~ (5) after washing realize the enrichment that rare earth leaches mother liquor.
In step (1), described phosphorus extractant comprises two (2-ethylhexyl phosphoric acids) or 2-ethylhexyl phosphoric acid single 2-ethyl polyhexamethylene.
In step (1), described organic phase is phosphorus extractant and sulfonated kerosene is the organic phase that the ratio of 1:0 ~ 4 is mixed to form by volume, and the granularity of described gac is 5 ~ 500 orders, and organic phase is 0.1 ~ 5:1 with quality of activated carbon ratio.
In step (2), described ion exchange column post footpath is 1 ~ 300cm, aspect ratio is 1 ~ 80:1.
In step (3), described saponifying agent is ammoniacal liquor or sodium hydroxide, and saponifying agent concentration is 0.1 ~ 14.8mol/L.
In step (4), it is 3 ~ 5 that described rare earth leaches mother liquor pH value.
Ion exchange column described in process of enriching technical scheme can substitute with steel basin.
Positively effect of the present invention is as follows:
(1) leach mother liquor with active carbon adsorption material enrichment rare earth, solve the problem of environmental pollution that the precipitator method are brought;
(2) gac has oil absorption, there is not the COD pollution problem of saponification waste-water and extraction wastewater generation;
(3) leach mother liquor with active carbon adsorption material enrichment rare earth, eliminate the phase-splitting difficult problem that traditional solvent extraction brings;
(4) activated carbon property is stablized, and recycle is effective, easy to operate, nontoxic, pollution-free, and the enrichment of leaching mother liquor for rare earth provides a kind of novel method.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the inventive method;
Fig. 2 is the series system figure of the ion exchange column of the inventive method;
In figure, F-column extractor, H-re-extraction column, F
1-the first column extractor, Fn-n-th column extractor, H
1-the first re-extraction column, Hn-n-th re-extraction column, V
f-feed velocity, V
h-back extraction acid flow velocity.
Embodiment
The following examples describe in further detail of the present invention.
As shown in figure 1 and 2, the concrete steps of the method for concentration and separation rare earth from rare earth leaching mother liquor of the present invention are as follows:
(1) preparation of active carbon adsorption material:
By phosphorus extractant and sulfonated kerosene by volume for the ratio of 1:0 ~ 4 is mixed to form organic phase, the ratio of to be 5 ~ 500 object gacs by organic phase and granularity be in mass ratio 0.1 ~ 5:1 mixes formation active carbon adsorption material;
(2) post is filled:
Active carbon adsorption material wet method dress post method loading post footpath step (1) obtained is 1 ~ 300cm, aspect ratio is the ion exchange column of 1 ~ 80:1;
(3) post saponification:
In separator column, add ammoniacal liquor that concentration is 0.1 ~ 14.8mol/L or sodium hydroxide solution carries out saponification to active carbon adsorption material, then use distilled water wash separator column to elutant without muddiness;
(4) post enrichment:
The ion exchange column that step (3) dress post obtains carries out multicolumn series connection and obtains separator column, and series system is as Fig. 2; Separator column is divided into column extractor F and re-extraction column H according to pillar jointing, and post trend is along column extractor F and re-extraction column H direction; Mother liquor is leached with 0.1 ~ 20cmmin with the rare earth that pH value is 3 ~ 5
-1flow velocity from the first column extractor F
1place flows through separator column, is that the hydrochloric acid of 0.1 ~ 6mol/L is with 0.1 ~ 20cmmin by concentration
-1flow velocity from the first re-extraction column H
1place flows through separator column, treats the first column extractor F
1adsorb saturated after, the first column extractor F
1enter stripping section, at the n-th re-extraction column H
nplace obtains rareearth enriching material;
(5) post washing:
Being washed with distilled water to elutant pH value being greater than 2 containing acid separation column after using, obtains blank post;
(6) post circulation:
Blank post recirculation step (3) ~ (5) after washing realize the enrichment that rare earth leaches mother liquor.
Embodiment 1
Be that 80 ~ 100 object gacs are in mass ratio for 1:1.5 mixes formation active carbon adsorption material by 2-ethylhexyl phosphoric acid single 2-ethyl polyhexamethylene (P507) and granularity; Active carbon adsorption material wet method dress post method is loaded post footpath is 20mm, post is high is the ion exchange column of 1000mm, dress post height is 850mm.
The ammonia soln of separator column 2.5mol/L carries out saponification to the organic phase of active carbon adsorption material, is neutral form saponification post with distilled water wash separator column to effluent liquid again after saponification is complete.
Process of enriching route is as Fig. 1, and multicolumn series connection is as Fig. 2.Technique contains separator column 8, wherein column extractor 4, re-extraction column 4.Mother liquor is leached with 1.5cmmin with the rare earth that pH value is 4.0
-1flow velocity from F
1place flows through separator column, is that the hydrochloric acid of 5.0mol/L is with 0.5cmmin by concentration
-1flow velocity from H
1place flows through separator column, treats F
1after post absorption is saturated, F
1post moves into stripping section.At H
4place obtains rare-earth enrichment solution, and the concentration measuring earth solution is 1.47mol/L.
Be washed with distilled water to elutant pH value containing acid separation column and be greater than 2, then return and use ammoniacal liquor saponification, so recycle separator column.
Although illustrate and describe embodiments of the invention, for the ordinary skill in the art, be appreciated that and can carry out multiple change, amendment, replacement and modification to these embodiments without departing from the principles and spirit of the present invention, scope of the present invention is by claims and equivalents thereof.
Claims (7)
1. leach a method for enrichment rare earth mother liquor from rare earth, it is characterized in that: the concrete steps of described method are as follows:
(1) preparation of active carbon adsorption material:
By phosphorus extractant and sulfonated kerosene by volume for the ratio of 1:0 ~ 4 is mixed to form organic phase, the ratio of to be 5 ~ 500 object gacs by organic phase and granularity be in mass ratio 0.1 ~ 5:1 mixes formation active carbon adsorption material;
(2) post is filled:
Active carbon adsorption material wet method dress post method loading post footpath step (1) obtained is 1 ~ 300cm, aspect ratio is the ion exchange column of 1 ~ 80:1;
(3) post saponification:
In separator column, add ammoniacal liquor that concentration is 0.1 ~ 14.8mol/L or sodium hydroxide solution carries out saponification to active carbon adsorption material, then use distilled water wash separator column to elutant without muddiness;
(4) post enrichment:
The ion exchange column that step (3) dress post obtains carries out multicolumn series connection and obtains separator column, and series system is as Fig. 2; Separator column is divided into column extractor (F) and re-extraction column (H) according to pillar jointing, and post trend is along column extractor (F) and re-extraction column (H) direction; Mother liquor is leached with 0.1 ~ 20cmmin with the rare earth that pH value is 2 ~ 5
-1flow velocity from the first column extractor (F
1) place flows through separator column, is that the hydrochloric acid of 0.1 ~ 6mol/L is with 0.1 ~ 20cmmin by concentration
-1flow velocity from the first re-extraction column (H
1) place flows through separator column, treats the first column extractor (F
1) adsorb saturated after, the first column extractor (F
1) enter stripping section, at the n-th re-extraction column (H
n) place obtains rareearth enriching material;
(5) post washing:
Being washed with distilled water to elutant pH value being greater than 2 containing acid separation column after using, obtains blank post;
(6) post circulation:
Blank post recirculation step (3) ~ (5) after washing realize the enrichment of rare earth turnover mother liquor.
2. a kind of method leaching enrichment rare earth mother liquor from rare earth as claimed in claim 1, it is characterized in that: in step (1), described phosphorus extractant comprises two (2-ethylhexyl phosphoric acids), 2-ethylhexyl phosphoric acid single 2-ethyl polyhexamethylene.
3. a kind of method leaching enrichment rare earth mother liquor from rare earth as claimed in claim 1, it is characterized in that: in step (1), described organic phase is phosphorus extractant and sulfonated kerosene is organic phase that the ratio of 1:0 ~ 4 is mixed to form by volume, the granularity of described gac is 5 ~ 500 orders, and organic phase is 0.1 ~ 5:1 with quality of activated carbon ratio.
4. a kind of method leaching enrichment rare earth mother liquor from rare earth as claimed in claim 1, is characterized in that: in step (2), described ion exchange column post footpath is 1 ~ 300cm, aspect ratio is 1 ~ 80:1.
5. a kind of method leaching enrichment rare earth mother liquor from rare earth as claimed in claim 1, it is characterized in that: in step (3), described saponifying agent is ammoniacal liquor or sodium hydroxide, and saponifying agent concentration is 0.1 ~ 14.8mol/L.
6. a kind of method leaching enrichment rare earth mother liquor from rare earth as claimed in claim 1, it is characterized in that: in step (4), it is 2 ~ 5 that described rare earth leaches mother liquor pH value.
7. a kind of method leaching enrichment rare earth mother liquor from rare earth as described in any one of claim 1-6, is characterized in that: ion exchange column steel basin described in process of enriching technical scheme substitutes.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107365909A (en) * | 2016-05-12 | 2017-11-21 | 中国科学院上海应用物理研究所 | A kind of extraction separating method |
| CN113201649A (en) * | 2020-09-18 | 2021-08-03 | 厦门钨业股份有限公司 | Phenoxy carboxylic acid solid-phase extracting agent, and preparation method and application thereof |
| CN115554981A (en) * | 2022-10-18 | 2023-01-03 | 江西理工大学 | Method for adsorbing and enriching low-concentration ionic rare earth by adopting residual sludge carbonized product |
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| CN85101874A (en) * | 1985-04-01 | 1986-07-30 | 中国科学院长春应用化学研究所 | P507 extration resin chromatography is separated and extraction HIGH PURITY THULIUM OXIDE and lutecium oxide |
| CN101012501A (en) * | 2007-02-05 | 2007-08-08 | 金坛市西南化工研究所 | Method for separating highly-pure rare-earth oxide from yttrium-rich rare earth mine |
| WO2014071510A1 (en) * | 2012-11-08 | 2014-05-15 | Electrochem Technologies & Materials Inc. | Process for recovering rare earth oxides from phosphors, fluorescent lamps and light bulbs, cathode ray tubes and other industrial wastes |
| CN104120258A (en) * | 2014-07-25 | 2014-10-29 | 广西师范大学 | Method for non-saponification extraction and separation of light rare earth elements |
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2015
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN85101874A (en) * | 1985-04-01 | 1986-07-30 | 中国科学院长春应用化学研究所 | P507 extration resin chromatography is separated and extraction HIGH PURITY THULIUM OXIDE and lutecium oxide |
| CN101012501A (en) * | 2007-02-05 | 2007-08-08 | 金坛市西南化工研究所 | Method for separating highly-pure rare-earth oxide from yttrium-rich rare earth mine |
| WO2014071510A1 (en) * | 2012-11-08 | 2014-05-15 | Electrochem Technologies & Materials Inc. | Process for recovering rare earth oxides from phosphors, fluorescent lamps and light bulbs, cathode ray tubes and other industrial wastes |
| CN104120258A (en) * | 2014-07-25 | 2014-10-29 | 广西师范大学 | Method for non-saponification extraction and separation of light rare earth elements |
Non-Patent Citations (1)
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| 方家远等: "负载N-1923活性炭富集~(230)Th的快速测定", 《铀矿地质》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107365909A (en) * | 2016-05-12 | 2017-11-21 | 中国科学院上海应用物理研究所 | A kind of extraction separating method |
| CN113201649A (en) * | 2020-09-18 | 2021-08-03 | 厦门钨业股份有限公司 | Phenoxy carboxylic acid solid-phase extracting agent, and preparation method and application thereof |
| CN115554981A (en) * | 2022-10-18 | 2023-01-03 | 江西理工大学 | Method for adsorbing and enriching low-concentration ionic rare earth by adopting residual sludge carbonized product |
| CN115554981B (en) * | 2022-10-18 | 2024-01-26 | 江西理工大学 | Method for adsorbing and enriching low-concentration rare earth ions by using excess sludge carbonized product |
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