CN105567963B - Using the method for the southern ion type rareearth of cellulose phosphate enriching and recovering extremely low concentration - Google Patents
Using the method for the southern ion type rareearth of cellulose phosphate enriching and recovering extremely low concentration Download PDFInfo
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- CN105567963B CN105567963B CN201510972541.5A CN201510972541A CN105567963B CN 105567963 B CN105567963 B CN 105567963B CN 201510972541 A CN201510972541 A CN 201510972541A CN 105567963 B CN105567963 B CN 105567963B
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- cellulose phosphate
- cellulose
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- rare earth
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/41—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds using a solution of normally solid organic compounds, e.g. dissolved polymers, sugars, or the like
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- 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
Phosphorus trichloride dichloromethane solution is slowly dropped into the pyridine solution of cellulose using the method for the southern ion type rareearth of cellulose phosphate enriching and recovering extremely low concentration, including (1), mixed liquor is poured into frozen water after backflow.Solution suction filtration, drying obtains the cellulose phosphate of high content of phosphorus after filter cake washing, pickling；(2) ditch-water for picking up from mining area is added into the pH value of ammoniacal liquor regulation solution to 5.2 5.6, filtering precipitate after stirring at ambient temperature；(3) cellulose phosphate is added in treated ditch-water, is stirred vigorously under room temperature condition 2 hours, it is to be mixed finish after by mixed liquor high speed centrifugation, filtering；(4) filter residue is acidified the rare earth ion of elution absorption using watery hydrochloric acid.The present invention reduces the entrainment problem of extractant, adsorption efficiency is high, and this realizes the high efficiente callback of extremely low concentration rare earth.Meanwhile, the source of cellulose is wide, cheap, the features such as nontoxic.Present invention elution is convenient, and the phosphorus loss content of cellulose phosphate is few, meets national phosphorus discharge standard.
Description
Technical field
The invention belongs to wet method gold metallurgy technical field, it is related to a kind of method of rare-earth enrichment recovery metal.
Background technology
Rare earth have the title of " industrial gold " and " industrial vitamin ".It is widely used in new energy, new material, e-mail
The fields such as breath, Aero-Space, military affairs, metallurgical industry, are a kind of important strategic resources.China is rare earth major producing country and gone out
Mouth state, rare earth yield accounts for the 90% of the whole world throughout the year.However, for a long time, rare earth mining brings a series of problem, such as environment
Pollution problem is more relatively low than the more prominent, level of resources utilization etc..
Due to the limitation of current wet process smelting technique, in the leachate and waste water that are produced during southern ion rare earth mining
Rare earth containing extremely low concentration, is discharged if these rare earths are not reclaimed, and is not only caused the waste of resource, be will also result in waste water stream
Environmental pollution through region.Therefore, development rare-earth enrichment recovery method has great importance.
The method that current rare earth is refined is to be realized by phosphoric acid or phosphate by the method to rare earth extraction, due to behaviour
Need organic phase to extract as extractant in process, and residual of the organic phase in aqueous phase prevents rare earth metal from dividing completely
From therefore, one class two-phase extraction agent of design may then solve above-mentioned problem.
The content of the invention
The purpose of the present invention is the deficiency for recycling technical method after existing southern ion type rareearth extraction, using height
The method that the cellulose phosphate of phosphorus content reclaims extremely low solubility rare earth, efficiently, simply realizes the rich again of extremely low concentration rare earth
Collection and recovery.
The present invention is achieved through the following technical solutions.
Method of the present invention comprises the following steps：
（1）Phosphorus trichloride dichloromethane solution is slowly dropped into the pyridine solution of cellulose, mixed liquor is poured into after backflow
In frozen water.Solution suction filtration, filter cake washing, after pickling drying obtain high content of phosphorus cellulose phosphate (P% >=4.0%, it is commercially available to contain
2%) phosphorus amount is.
（2）By the ditch-water for picking up from mining area add at ambient temperature ammoniacal liquor regulation solution pH value to 5.2-5.6, after stirring
Filtering precipitate, mother liquor measures rare earth concentration using ICP.
（3）Cellulose phosphate is added in treated ditch-water, be stirred vigorously under room temperature condition 2 hours, it is to be mixed complete
By mixed liquor high speed centrifugation after finishing, filtering.
（4）Filter residue is acidified the rare earth ion of elution absorption using watery hydrochloric acid.
Described extremely low concentration rare earth refers to concentration≤0.1g/L.
The cellulose phosphate of described high content of phosphorus, refers to weight percent content >=4.0% of its phosphorus.
ICP detects the concentration of filtrate middle rare earth, and extractant wash repeatedly with watery hydrochloric acid, measure eluent middle rare earth concentration with
And phosphorus element content.
Cellulose phosphate has hydrophilic phosphate and hydrophobic fiber part, therefore, is extracted using this kind of extractants dilute
Native waste water, it is not necessary to the extraction of organic phase and the separation of aqueous phase and extractant can be reached by the method for physics, reduce extraction
Take the entrainment problem of agent.In addition, the cellulose phosphate of high content of phosphorus is due to the adsorption site increase in unit fiber element so that
Higher than the adsorption efficiency of common phosphocellulose in the efficiency of rare earth extraction, this is realized in extremely low concentration leachate or RE waste water
The high efficiente callback of rare earth.Meanwhile, the source of cellulose is wide, cheap, the features such as nontoxic.The present invention to it is light, in, weight it is dilute
Soil has good effect of extracting.Also there is good effect of extracting, and elution for the ditch-water of mining area rare earth containing extremely low concentration
Convenient, the phosphorus loss content of cellulose phosphate is few, meets national phosphorus discharge standard.
Brief description of the drawings
Fig. 1 adsorbs for the present invention to ion type rareearth mining area ditch-water extremely low concentration rare earth metal to scheme.
Fig. 2 schemes for the present invention to ditch-water extremely low concentration rare earth metal absorption after pretreatment.
Fig. 3 is the present invention by adjusting pH value to Fe in the ditch-water of mining area, Al and its rare earth extraction figure.
Fig. 4 is concentration map of the present invention to rare earth after pH processing in the ditch-water of rare-earth mining area.
Fig. 5 is extraction figure of the present invention to middle rare earth after rare-earth mining area ditch-water pH processing.
Fig. 6 is elution amount and hydrochloric acid washing steps ratio chart after extracting rare-earth of the present invention.
Fig. 7 is the present invention to the multiple extracting rare-earth efficiency chart of Y rare earths.
Embodiment
The present invention will be described further by following examples.
Embodiment 1.
By quality:Volume（kg/L）Than for 1:20 ratio, dry cellulose is added in pyridine solution；By matter
Amount:Volume（kg/L）Than for 3:10 ratio, phosphorus trichloride is dissolved in dichloromethane.
Above-mentioned phosphorus trichloride mixture liquid is slowly dropped into the pyridine solution of containing cellulose, titration is heated to reflux 12 after finishing
Hour, reaction solution is poured into frozen water by reaction after stopping.Mixed liquor obtains solid, filter cake washing after suction filtration, and uses 0.1
The salt pickling of mol/L, air-dries and obtains cellulose phosphate, and it is 4.55% to determine phosphorus content.
Embodiment 2.
25mL is picked up from into the ditch-water in south jiangxi rare earth mining mining area, and (ditch water constituent is as follows：La, 5.36；Ce, 2.44；Nd,
4.85；Gd, 2.03；Dy, 3.49；Er：2.30；Y：20.89；Fe：6.31；Al, 15.54；Si, 6.28；Mg, 11.33；Mn,
3.17；Na, 7.40；K, 28.39；Pd, 2.20 ug/mL) add cellulose phosphate prepared by 50 mg.2 are stirred vigorously at room temperature
h。
Extract separates cellulose phosphate and extracting mother liquid using ultracentrifugal method.Mother liquor determines rare earth by ICP
The concentration of each composition in ditch-water, it is found that ditch-water middle rare earth change in concentration is little.And Fe3+With Al3+Concentration for 0.16 ug/mL and
3.29 ug/mL.Illustrate phosphocellulose extract ditch-water when by Fe, the interference of Al ions and solution acidity is very big.
Embodiment 3.
50 mL pH value are slowly dropped into ammoniacal liquor for 3.2 ditch-water, regulation to pH value is 4.0,4.5,5.2,5.6.Solution
In there is White Flocculus.It is filtered to remove floccule.ICP measures each metal cation component in filtrate, each rare earth metal total concentration
For 42.2,42.8,39.0,36.0 (ug/mL), illustrate under the conditions of these pH, the loss of stoste middle rare earth metal is smaller,
And Fe, Al ion loss ratio when pH value is 5.2,5.6 are larger.Respectively 0.07 ug/mL and 10.0 are reduced to from 1.3 ug/mL
Ug/mL reduces by 2.1 ug/mL.
25 mL filtrates are measured respectively, are added 50 mg and are prepared cellulose phosphate, 2 h are stirred vigorously at room temperature.
Extract separates cellulose phosphate and extracting mother liquid using ultracentrifugal method.Mother liquor determines metal by ICP
The concentration of each composition of ion.It was found that when pH value is 4.0,4.5, mother liquor middle rare earth total concentration is 36.3 and 30.78.In the pH conditions
Under, the effect of extracting of cellulose phosphate is bad.And pH value is 5.2 and 5.6, mother liquor middle rare earth total concentration is reduced to 14.2 ug/mL
This shows when pH value is 5.2 and 5.6 with 11.2 ug/mL..The effect of extracting of phosphocellulose is relatively good.
Embodiment 4.
Concentration is added to 250 mg phosphocellulose for the 58.28 ug/mL pretreated mL of rare earth ditch-water 125.Room
2 h are stirred vigorously under temperature.
Extract separates cellulose phosphate and extracting mother liquid using ultracentrifugal method.Mother liquor determines metal by ICP
The concentration of each composition of ion is 10.32 ug/mL.
Cellulose phosphate after extraction is respectively respectively 0.1M, 0.5M, 1.0M watery hydrochloric acid elution with 20 mL concentration.Wash
De- liquid uses the concentration of the Determination Staining rare earth ion of azo arsenic three.
When being eluted with 0.1M watery hydrochloric acid, the ug/mL of concentration 16.59 of eluent Rare Earth Ion.When the salt with 0.5M
During pickling dephosphorylation fiber, the concentration of eluent is 84.70 ug/mL.When eluting phosphocellulose with 0.1M watery hydrochloric acid, elution
The concentration of liquid is 76.12 ug/mL.When illustrating that the concentration of hydrochloric acid for eluting rare earth reaches 0.5 M, it is already possible to reach and preferably wash
De- effect.
Embodiment 5.
It is the phosphocellulose that earth solution 110 mLs of 93.23 ug/mL containing Y adds 200 mg by concentration.It is violent at room temperature
Stir 2 h.
Extract separates cellulose phosphate and extracting mother liquid using ultracentrifugal method.Mother liquor is dyed by azo arsenic three
The concentration that method determines each composition of metal ion is 14.01 ug/mL.
Cellulose phosphate after extraction is eluted four times with 20mL concentration for 0.5 M watery hydrochloric acid respectively.Eluent is using even
The concentration of the Determination Staining rare earth ion of nitrogen arsenic three.The concentration for determining the Rare Earth Y of four eluents is respectively 133.15 ug/mL,
54.29 ug/mL, 34.11 ug/mL, 21.41 ug/mL.
The phosphocellulose stripped is washed with distilled water to neutrality, in the earth solution for being then added to 100 mL Y, stirred
Mix the concentration that centrifugation Mother liquor uses Y-ion in the Determination Staining mother liquor of azo arsenic three.The concentration of mother liquor is 21.21 ug/mL.
Illustrate that the extractant phosphocellulose in the invention can be reused.
Embodiment 6.
By taking Rare Earth Y as an example：Concentration is fine for the phosphoric acid that the 99.87 ug/mL Y mL of earth solution 100 adds 500 mg
Dimension.2 h are stirred vigorously at room temperature.
Extract separates cellulose phosphate and extracting mother liquid using ultracentrifugal method.Mother liquor is dyed by azo arsenic three
The concentration that method determines each composition of metal ion is less than 5 ug/mL.
Cellulose phosphate after extraction is eluted four times with 100mL concentration for 0.5 M watery hydrochloric acid respectively.Put into again
100 mL concentration are stirring in 99.87 ug/mL Y earth solution.The ug/mL of concentration 5 of mother liquor is determined after centrifugation.
Cellulose phosphate after second of extraction is eluted four times with 100mL concentration for 0.5 M watery hydrochloric acid respectively.For the third time
Put into the Y earth solutions that 100 mL concentration are 99.87 ug/mL and stir.The ug/mL of concentration 6 of mother liquor is determined after centrifugation.
Cellulose phosphate after third time is extracted is eluted four times with 100mL concentration for 0.5 M watery hydrochloric acid respectively.4th time
Put into the Y earth solutions that 100 mL concentration are 99.87 ug/mL and stir.The ug/mL of concentration 23 of mother liquor is determined after centrifugation.
Cellulose phosphate after 4th extraction is eluted four times with 100mL concentration for 0.5 M watery hydrochloric acid respectively.5th time
Put into the Y earth solutions that 100 mL concentration are 99.87 ug/mL and stir.The ug/mL of concentration 24 of mother liquor is determined after centrifugation.
Cellulose phosphate after 5th extraction is eluted four times with 100mL concentration for 0.5 M watery hydrochloric acid respectively.6th time
Put into the Y earth solutions that 100 mL concentration are 99.87 ug/mL and stir.The ug/mL of concentration 24 of mother liquor is determined after centrifugation,
The phosphocellulose stripped is washed with distilled water to neutrality, in the earth solution for being then added to 100 mL Y, stirred
Mix the concentration that centrifugation Mother liquor uses Y-ion in the Determination Staining mother liquor of azo arsenic three.The concentration of mother liquor is 21.21 ug/mL.
Illustrate that the extractant that the invention is used can be reused.
Embodiment 7.
The cellulose phosphate that 50 mg have been adsorbed is eluted with 0.5 M watery hydrochloric acid, eluent is collected, ICP detections are therein
P elements concentration.
Testing result：P elements concentration is 0.2 ug/ml in eluent.Showing that the concentration Diluted Acid Washing is taken off will not divide substantially
Solution destruction cellulose phosphate.So that influence of the extractant used in the invention to environment is smaller.
Claims (1)
1. using the method for the southern ion type rareearth of cellulose phosphate enriching and recovering extremely low concentration, its feature comprises the following steps：
（1）Phosphorus trichloride dichloromethane solution is slowly dropped into the pyridine solution of cellulose, mixed liquor pours into frozen water after backflow
In；
Solution suction filtration, drying obtains the cellulose phosphate of high content of phosphorus after filter cake washing, pickling；
（2）The pH value that the ditch-water for picking up from mining area is added into ammoniacal liquor regulation solution at ambient temperature is filtered to 5.2-5.6 after stirring
Sediment；
（3）Cellulose phosphate is added in treated ditch-water, is stirred vigorously under room temperature condition 2 hours, it is to be mixed finish after
By mixed liquor high speed centrifugation；
（4）Filter residue is acidified the rare earth ion of elution absorption using watery hydrochloric acid；
The southern ion type rareearth of described extremely low concentration refers to concentration≤0.1g/L；
The cellulose phosphate of described high content of phosphorus refers to weight percent content >=4.0% of its phosphorus.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510972541.5A CN105567963B (en) | 2015-12-23 | 2015-12-23 | Using the method for the southern ion type rareearth of cellulose phosphate enriching and recovering extremely low concentration |
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| CN201510972541.5A CN105567963B (en) | 2015-12-23 | 2015-12-23 | Using the method for the southern ion type rareearth of cellulose phosphate enriching and recovering extremely low concentration |
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| CN105567963B true CN105567963B (en) | 2017-11-03 |
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| US3691154A (en) * | 1970-05-05 | 1972-09-12 | Kimberly Clark Co | Absorbent fibers of phosphorylated cellulose with ion exchange properties |
| JPS5210670B2 (en) * | 1973-05-16 | 1977-03-25 | ||
| CN104232948B (en) * | 2014-10-10 | 2016-02-24 | 江西理工大学 | A kind of processing method of recovering rare earth from ion type rareearth leaching at low-concentration liquid |
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