CN115927885A - Method for recovering rare earth elements from rare earth waste liquid - Google Patents
Method for recovering rare earth elements from rare earth waste liquid Download PDFInfo
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- CN115927885A CN115927885A CN202211733831.0A CN202211733831A CN115927885A CN 115927885 A CN115927885 A CN 115927885A CN 202211733831 A CN202211733831 A CN 202211733831A CN 115927885 A CN115927885 A CN 115927885A
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 220
- 239000007788 liquid Substances 0.000 title claims abstract description 117
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 114
- 239000002699 waste material Substances 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 61
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 117
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 109
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 109
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 69
- 239000010452 phosphate Substances 0.000 claims abstract description 69
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 68
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000012535 impurity Substances 0.000 claims abstract description 45
- 238000000498 ball milling Methods 0.000 claims abstract description 41
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 238000000926 separation method Methods 0.000 claims abstract description 24
- 238000011084 recovery Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 23
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 21
- 239000011575 calcium Substances 0.000 claims description 21
- 229910052791 calcium Inorganic materials 0.000 claims description 21
- 239000011777 magnesium Substances 0.000 claims description 21
- 229910052749 magnesium Inorganic materials 0.000 claims description 21
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 20
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 14
- 238000010828 elution Methods 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 6
- 229910052691 Erbium Inorganic materials 0.000 claims description 6
- 229910052693 Europium Inorganic materials 0.000 claims description 6
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 6
- 229910052689 Holmium Inorganic materials 0.000 claims description 6
- 229910052765 Lutetium Inorganic materials 0.000 claims description 6
- 229910052779 Neodymium Inorganic materials 0.000 claims description 6
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 6
- 229910052772 Samarium Inorganic materials 0.000 claims description 6
- 229910052771 Terbium Inorganic materials 0.000 claims description 6
- 229910052775 Thulium Inorganic materials 0.000 claims description 6
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 6
- 239000003929 acidic solution Substances 0.000 claims description 6
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 6
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 6
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 6
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 6
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 6
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 6
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 6
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 6
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 6
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 2
- 102000020897 Formins Human genes 0.000 claims 1
- 108091022623 Formins Proteins 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 31
- 238000012986 modification Methods 0.000 abstract description 12
- 230000004048 modification Effects 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 4
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 abstract description 4
- 239000003463 adsorbent Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- -1 ammonium salt rare earth Chemical class 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 239000010431 corundum Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 239000012716 precipitator Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009297 electrocoagulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for recovering rare earth elements from rare earth waste liquid, which comprises the following steps: the rare earth waste liquid and the phosphate kaolin are mixed, subjected to solid-liquid separation and eluted, and then the recovery of rare earth elements is completed; the phosphate kaolin is prepared by mixing, ball-milling, washing and drying kaolin and phosphoric acid; the concentration of rare earth elements in the rare earth waste liquid is 30-40mg/L; the concentration of impurity elements in the rare earth waste liquid is 500-800mg/L; the mass ratio of the kaolin to the phosphoric acid is (5-20) to 1. Phosphate modification is carried out on kaolin by using phosphoric acid, selective adsorption of rare earth elements is realized by the phosphate groups on the obtained phosphate kaolin and the rare earth elements through a bonding effect, the adsorption rate of the phosphate kaolin to the rare earth elements can reach over 90 percent, the adsorption rate of the phosphate kaolin to impurity elements is almost 0, and enrichment of low-concentration rare earth elements in rare earth waste liquid and separation of high-concentration impurity elements are realized.
Description
Technical Field
The invention belongs to the technical field of rare earth element recovery, and particularly relates to a method for recovering rare earth elements from rare earth waste liquid.
Background
Rare earth elements are known as "industrial gold", wherein light rare earth elements include lanthanum, cerium, praseodymium, neodymium, samarium and europium, and heavy rare earth elements include gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, yttrium and lutetium. The application of rare earth elements in military affairs, medical treatment, agriculture and other aspects is increased day by day, but with the excessive development of rare earth resources, the reserves and the grade of rare earth minerals are gradually reduced, and the forms of the rare earth resources are poorer. At present, low-concentration rare earth waste liquid generated by rare earth mining and extraction not only causes heavy metal pollution, but also causes the loss of rare earth resources. Therefore, the selective recovery of rare earth elements from low-concentration rare earth waste liquid is a problem to be solved in the aspects of rare earth resource and environmental protection.
Due to the generation of a large amount of ammonia nitrogen waste liquid, the ammonium salt leaching process of the ionic rare earth ore is gradually abandoned, and a magnesium salt leaching process is used as a substitute. At present, the rare earth content in the rare earth waste liquid is usually lower than 50mg/L, and because the prior ammonium salt rare earth waste liquid is not effectively treated, other impurities such as magnesium, ammonia nitrogen, calcium and the like are often accompanied in the rare earth waste liquid, and the concentration of the impurities is higher than that of rare earth elements by several orders of magnitude. Therefore, selective recovery of rare earth elements from rare earth waste liquids is a challenge. At present, the methods for recovering low-concentration rare earth from waste liquid mainly comprise a chemical precipitation method, a solvent extraction method, a biological method and an adsorption method. CN108893625A discloses a process for preparing high-purity lanthanum by an extraction method, wherein 3N industrial-grade lanthanum chloride aqueous solution is used as a feed liquid, P204-TBP is used as a composite extractant, and the process specifically comprises five steps of fractional extraction and separation of Na Mg Ca Pb Zn La/La Ce Pr Nd Sm Fe, fractional extraction and separation of Na Mg Ca Pb Zn/La, fractional extraction and separation of La/Ce Pr Nd Sm Fe, and a back-extraction section 1 and a back-extraction section 2.
CN105861831A discloses a method for precipitation recovery of rare earths from rare earth salt solutions, comprising the following steps: adding a precipitator containing calcium and/or magnesium basic compounds and an ammonium-containing solution into a rare earth salt solution, and carrying out mixed precipitation reaction, wherein the dosage of the precipitator is 101-130% of the theoretical dosage of rare earth in the rare earth salt solution, and the precipitator is solid or water slurry; then carrying out solid-liquid separation after rare earth precipitation to obtain rare earth precipitate and precipitation mother liquor, and calcining the rare earth precipitate to obtain rare earth oxide. The calcium and/or magnesium alkaline compound precipitant adopted by the method is cheap and easy to obtain, the preparation process is simple and controllable, the dosage of ammonium substances is greatly reduced, the ammonia nitrogen pollution is reduced, meanwhile, the dissolution of the calcium and/or magnesium alkaline compound is promoted due to the synergistic effect of ammonium ions and the calcium/magnesium alkaline compound, and the problem of the purity reduction of rare earth products in the process of recovering rare earth by precipitation only by adopting the calcium and/or magnesium precipitant is also solved.
Compared with other methods, the adsorption method has the advantages of low material price, simple operation, low energy consumption and the like, can be used for recovering the rare earth elements in the waste liquid, but the preparation process of the adsorbent is complex and high in cost, so that the adsorbent is difficult to use on a large scale, and how to realize the enrichment of the rare earth elements and the separation of high-concentration impurity elements is one of the problems to be solved urgently. Therefore, the development of a rare earth adsorbent with wide application range and high selectivity is of great significance.
The kaolin has the advantages of abundant resources, large reserves, wide distribution, low price, easy exploitation and the like. Kaolin has certain adsorption performance, but the adsorption capacity is limited due to the structure of the kaolin and the like. A large number of researches show that the modified kaolin has relatively superior performance in various waste liquid treatments. CN105126742A discloses a method for treating fluorine-containing wastewater by using a modified kaolin adsorbent, which comprises the following preparation processes: adding water into kaolin to prepare first ore pulp, adding sodium hexametaphosphate and sodium hydroxide, stirring in a water bath, and standing; taking the upper layer slurry for centrifugal separation, drying, immersing into a sulfuric acid solution, and performing suction filtration; adding water to prepare a second ore pulp, adding polydimethyldiallyl ammonium chloride, stirring for reaction, filtering, drying, crushing, and sieving to obtain the modified kaolin adsorbent, wherein the method for treating the fluorine-containing waste liquid by using the modified kaolin adsorbent comprises the following steps: flocculation precipitation, electrocoagulation and adsorption treatment processes. The method has the advantages of wide source of raw materials of the adsorbent, simple preparation process, high adsorption capacity, high waste liquid treatment efficiency, simple, mature, practical, economical and reasonable method. The modification of the kaolin can improve the adsorption capacity of the kaolin, expand the application field of the kaolin product and improve the added value of the kaolin product. However, this solution does not involve the recovery of rare earth elements.
As a potential adsorbent substrate, the cheap kaolin has wide application prospect in the aspect of designing and synthesizing the adsorbent for adsorbing the rare earth elements with high selectivity. Therefore, the invention provides a method for recovering rare earth elements from rare earth waste liquid by modifying kaolin, so as to realize the enrichment of low-concentration rare earth elements and the separation of high-concentration impurity elements in the rare earth waste liquid.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for recovering rare earth elements from rare earth waste liquid so as to realize the enrichment of low-concentration rare earth elements and the separation of high-concentration impurity elements in the rare earth waste liquid.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for recovering rare earth elements from rare earth waste liquid, which comprises the following steps:
the rare earth waste liquid and the phosphate kaolin are mixed, subjected to solid-liquid separation and eluted, and then the recovery of rare earth elements is completed;
the phosphate kaolin is prepared by mixing, ball-milling, washing and drying kaolin and phosphoric acid;
the concentration of rare earth elements in the rare earth waste liquid is 30-40mg/L;
the concentration of impurity elements in the rare earth waste liquid is 500-800mg/L;
the mass ratio of the kaolin to the phosphoric acid is (5-20) to 1.
According to the invention, phosphoric acid is used for carrying out phosphate modification on kaolin, and phosphate radicals on the obtained phosphate kaolin and rare earth elements realize selective adsorption of the rare earth elements through a bonding effect; the method has the advantages of short flow, low cost, wide raw material source and mild conditions, the adsorption rate of the rare earth elements can reach more than 90%, the adsorption rate of the impurity elements is almost 0, and the enrichment of low-concentration rare earth elements in the rare earth waste liquid and the separation of high-concentration impurity elements are realized.
The concentration of the rare earth element in the rare earth waste liquid is 30-40mg/L, for example, 30mg/L, 33mg/L, 35mg/L, 38mg/L or 40mg/L, but is not limited to the recited values, and other values in the range of the values are also applicable.
The concentration of the impurity elements in the rare earth waste liquid is 500-800mg/L, for example 500mg/L, 550mg/L, 600mg/L, 650mg/L,/700 mg/L, 750mg/L or 800mg/L, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
The molecular formulas of the kaolin and the phosphoric acid used in the invention are respectively Al 2 SiO 5 (OH) 4 And H 3 PO 4 。
The kaolin to phosphoric acid mass ratio is (5-20): 1, and can be, for example, 5.
The mass ratio of the kaolin to the phosphoric acid is controlled within the range of (5-20): 1, which is beneficial to realizing the phosphate modification of the kaolin; when the mass ratio is lower than 5; when the mass ratio is higher than 20.
Preferably, the ball milling rate is 200-400r/min, such as 200r/min, 250r/min, 300r/min, 350r/min or 400r/min, but not limited to the values recited, and other values not recited in the range of values are equally applicable.
The ball milling speed is controlled within the range of 200-400r/min, so that the phosphate modification of the kaolin is facilitated, and the phosphate kaolin has high selective adsorption capacity on rare earth elements; when the ball milling speed is lower than 200r/min, the phosphoric acid cannot be completely loaded on the kaolin due to insufficient mechanical energy; when the ball milling speed is higher than 400r/min, the kaolin structure is completely broken, the number of exchangeable hydrogen ions on the surface of the phosphate kaolin is reduced, and the adsorption capacity of the phosphate kaolin is reduced.
Preferably, the ball milling time is 5-20min, such as 5min, 8min, 10min, 13min, 15min, 18min or 20min, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
The ball milling time is controlled within the range of 5-20min, so that the phosphate modification of the kaolin is favorably realized; when the ball milling time is less than 5min, phosphoric acid cannot be sufficiently loaded on the kaolin, so that the number of phosphate groups on the surface of the kaolin is reduced; when the ball milling time is more than 20min, the kaolin structure is completely broken, the number of exchangeable hydrogen ions on the surface of the phosphate kaolin is reduced, and the adsorption capacity of the phosphate kaolin is reduced.
Preferably, the ball-milled mass ratio is (75-80): 1, which can be, for example, 75.
Illustratively, the ball mill used for ball milling in the invention comprises 2 corundum ball milling tanks, 2 zirconia balls with the diameter of 2cm, 8 zirconia balls with the diameter of 1.5cm and 6 zirconia balls with the diameter of 1 cm; the diameter of the corundum ball milling tank is 5.5cm, the height of the corundum ball milling tank is 5cm, and the effective volume of the corundum ball milling tank is 100cm 3 。
Preferably, the rare earth element comprises any one or combination of at least two of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, yttrium, or lutetium, with typical, but non-limiting combinations comprising lanthanum and cerium, praseodymium and neodymium, samarium and europium, gadolinium and terbium, dysprosium and holmium, erbium and thulium, or ytterbium, yttrium and lutetium.
Preferably, the impurity element comprises any one of calcium, magnesium or ammoniacal nitrogen or a combination of at least two of them, and typical but non-limiting combinations include a combination of calcium and magnesium, a combination of magnesium and ammoniacal nitrogen, a combination of calcium and ammoniacal nitrogen, or a combination of calcium, magnesium and ammoniacal nitrogen.
Preferably, the pH of the rare earth waste liquid is 5 to 7, for example 5, 5.5, 6, 6.5 or 7, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the solid-to-liquid ratio of the phosphate-based kaolin when mixed with the rare earth waste liquor is (1-3): 1, and can be, for example, 1.
Preferably, the phosphate kaolin is mixed with the rare earth waste solution at a temperature of 20-30 ℃, for example, 20 ℃, 23 ℃, 25 ℃, 28 ℃ or 30 ℃, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the mixing time of the phosphate kaolin and the rare earth waste liquid is 1-4h, for example, 1h, 1.5h, 2h, 3h or 4h, but the phosphate kaolin and the rare earth waste liquid are not limited to the listed values, and other values in the range of the values are also applicable.
Preferably, the phosphate kaolin is mixed with the rare earth waste liquid with stirring.
Preferably, the stirring rate is 200-300r/min, such as 200r/min, 220r/min, 240r/min, 260r/min, 280r/min or 300r/min, but not limited to the values recited, and other values not recited within the range of values are equally applicable.
Preferably, the eluent used for the elution comprises an acidic solution.
Preferably, the acidic solution comprises any one of hydrochloric acid, nitric acid or sulfuric acid or a combination of at least two thereof, typical but non-limiting combinations include a combination of hydrochloric acid and nitric acid, a combination of nitric acid and sulfuric acid, a combination of hydrochloric acid and sulfuric acid, or a combination of hydrochloric acid, nitric acid and sulfuric acid.
Preferably, the concentration of the acidic solution is 0.1 to 0.4mol/L, and may be, for example, 0.1mol/L, 0.2mol/L, 0.3mol/L, or 0.4mol/L, but is not limited to the recited values, and other values not recited in the numerical ranges are also applicable.
During elution, the concentration of the acid solution is controlled within the range of 0.1-0.4mol/L, so that the rare earth elements can fall off from the phosphate kaolin, and the enrichment of the rare earth elements is realized; when the concentration is lower than 0.1mol/L, the rare earth elements are not completely fallen off from the phosphate kaolin, so that the recovery rate of the rare earth metals is reduced; when the concentration is higher than 0.4mol/L, the structure of the phosphoric acid-based kaolin is destroyed, and the reusability is affected.
Reasonable and reasonable
Preferably, the elution time is 0.5 to 1 hour, for example 0.5 hour, 0.6 hour, 0.7 hour, 0.8 hour, 0.9 hour or 1 hour, but is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the elution temperature is 20-30 ℃, for example 20 ℃, 22 ℃, 24 ℃, 26 ℃, 28 ℃ or 30 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
According to the invention, the phosphate kaolin loaded with rare earth elements is desorbed and enriched by elution, and the desorbed phosphate kaolin can be repeatedly used after being washed and dried.
Preferably, the washing temperature is 20-30 ℃, for example 20 ℃, 22 ℃, 24 ℃, 26 ℃, 28 ℃ or 30 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the drying temperature is 60 to 80 ℃, for example 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, but not limited to the recited values, other values not recited in the range of values being equally applicable.
Preferably, the drying time is 8 to 16h, for example 8h, 10h, 12h, 14h or 16h, but is not limited to the values listed, and other values not listed in the range of values are equally applicable.
As a preferred technical scheme of the method, the method comprises the following steps:
mixing phosphate kaolin and rare earth waste liquid according to the solid-liquid ratio of (1-3) to 1g/L at 20-30 ℃ for 1-4h, and after solid-liquid separation, eluting by using an acid solution with the concentration of 0.1-0.4mol/L for 0.5-1h to complete the recovery of rare earth elements;
the concentration of rare earth elements in the rare earth waste liquid is 30-40mg/L, and the rare earth elements comprise any one or the combination of at least two of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, yttrium or lutetium; the concentration of impurity elements in the rare earth waste liquid is 500-800mg/L, and the impurity elements comprise any one or combination of at least two of calcium, magnesium or ammonia nitrogen;
the phosphate kaolin is prepared by mixing kaolin and phosphoric acid in a mass ratio of (5-20): 1, ball-milling for 5-20min, washing and drying; the ball milling speed is 200-400r/min.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, phosphate modification is carried out on kaolin by using phosphoric acid, and selective adsorption of rare earth elements is realized through the bonding effect of phosphate on the obtained phosphate kaolin and the rare earth elements; the method has the advantages of short flow, low cost, wide raw material source and mild conditions, the adsorption rate of the rare earth elements can reach more than 90%, the adsorption rate of the impurity elements is almost 0, and the enrichment of low-concentration rare earth elements in the rare earth waste liquid and the separation of high-concentration impurity elements are realized.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a method for recovering rare earth elements from rare earth waste liquid, which comprises the following steps:
mixing phosphate kaolin and rare earth waste liquid at 25 ℃ for 2h according to a solid-liquid ratio of 2.5;
the concentration of rare earth elements in the rare earth waste liquid is 36mg/L; the concentration of impurity elements in the rare earth waste liquid is 700mg/L, and the impurity elements comprise calcium, magnesium and ammonia nitrogen;
the phosphate kaolin is prepared by mixing kaolin and phosphoric acid in a mass ratio of 10; the ball milling speed is 300r/min.
Example 2
The embodiment provides a method for recovering rare earth elements from rare earth waste liquid, which comprises the following steps:
mixing phosphate kaolin and rare earth waste liquid for 4 hours at 20 ℃ according to the solid-liquid ratio of 1g/L, and after solid-liquid separation, eluting for 1 hour by using a hydrochloric acid solution with the concentration of 0.1mol/L to complete the recovery of rare earth elements;
the concentration of rare earth elements in the rare earth waste liquid is 30mg/L; the concentration of impurity elements in the rare earth waste liquid is 500mg/L, and the impurity elements comprise calcium, magnesium and ammonia nitrogen;
the phosphate kaolin is prepared by mixing kaolin and phosphoric acid in a mass ratio of 20; the speed of ball milling is 200r/min.
Example 3
The embodiment provides a method for recovering rare earth elements from rare earth waste liquid, which comprises the following steps:
mixing phosphate kaolin and rare earth waste liquid at 30 ℃ for 1h according to a solid-liquid ratio of 3g/L, and after solid-liquid separation, eluting for 0.5h by using a hydrochloric acid solution with the concentration of 0.4mol/L to complete the recovery of rare earth elements;
the concentration of the rare earth elements in the rare earth waste liquid is 40mg/L; the concentration of impurity elements in the rare earth waste liquid is 800mg/L, and the impurity elements comprise calcium, magnesium and ammonia nitrogen;
the phosphate kaolin is prepared by mixing kaolin and phosphoric acid in a mass ratio of 5; the speed of ball milling is 400r/min.
Example 4
The embodiment provides a method for recovering rare earth elements from rare earth waste liquid, which comprises the following steps:
mixing phosphate kaolin and rare earth waste liquid at 25 ℃ for 2h according to a solid-liquid ratio of 2 g/L, and after solid-liquid separation, eluting for 1h by using a hydrochloric acid solution with the concentration of 0.3mol/L to complete the recovery of rare earth elements;
the concentration of the rare earth elements in the rare earth waste liquid is 30mg/L; the concentration of impurity elements in the rare earth waste liquid is 600mg/L, and the impurity elements comprise calcium, magnesium and ammonia nitrogen;
the phosphate kaolin is prepared by mixing kaolin and phosphoric acid in a mass ratio of 10; the ball milling speed is 300r/min.
Example 5
The embodiment provides a method for recovering rare earth elements from rare earth waste liquid, which comprises the following steps:
mixing phosphate kaolin and rare earth waste liquid at 25 ℃ for 3h according to a solid-liquid ratio of 2.5;
the concentration of rare earth elements in the rare earth waste liquid is 34mg/L; the concentration of impurity elements in the rare earth waste liquid is 600mg/L, and the impurity elements comprise calcium, magnesium and ammonia nitrogen;
the phosphate kaolin is prepared by mixing kaolin and phosphoric acid in a mass ratio of 10; the speed of ball milling is 400r/min.
Example 6
The embodiment provides a method for recovering rare earth elements from rare earth waste liquid, which comprises the following steps:
mixing phosphate kaolin and rare earth waste liquid for 1.5h at 25 ℃ according to the solid-liquid ratio of 2 g/L, and after solid-liquid separation, eluting for 0.8h by using a hydrochloric acid solution with the concentration of 0.2mol/L to complete the recovery of rare earth elements;
the concentration of rare earth elements in the rare earth waste liquid is 40mg/L; the concentration of impurity elements in the rare earth waste liquid is 700mg/L, and the impurity elements comprise calcium, magnesium and ammonia nitrogen;
the phosphate kaolin is prepared by mixing kaolin and phosphoric acid in a mass ratio of 10; the ball milling speed is 250r/min.
Example 7
The embodiment provides a method for recovering rare earth elements from rare earth waste liquid, which comprises the following steps:
mixing phosphate kaolin and rare earth waste liquid at 23 ℃ for 3h according to a solid-liquid ratio of 3g/L, and after solid-liquid separation, eluting for 1h by using a hydrochloric acid solution with the concentration of 0.3mol/L to complete the recovery of rare earth elements;
the concentration of rare earth elements in the rare earth waste liquid is 33mg/L; the concentration of impurity elements in the rare earth waste liquid is 700mg/L, and the impurity elements comprise calcium, magnesium and ammonia nitrogen;
the phosphate kaolin is prepared by mixing kaolin and phosphoric acid in a mass ratio of 10; the speed of ball milling is 350r/min.
Example 8
The embodiment provides a method for recovering rare earth elements from rare earth waste liquid, which comprises the following steps:
mixing phosphate kaolin and rare earth waste liquid at 25 ℃ for 3h according to a solid-liquid ratio of 2.5:1g/L, and after solid-liquid separation, eluting for 0.7h by using a hydrochloric acid solution with the concentration of 0.2mol/L to complete the recovery of rare earth elements;
the concentration of rare earth elements in the rare earth waste liquid is 36mg/L; the concentration of impurity elements in the rare earth waste liquid is 500mg/L, and the impurity elements comprise calcium, magnesium and ammonia nitrogen;
the phosphate kaolin is prepared by mixing kaolin and phosphoric acid in a mass ratio of 10; the ball milling speed is 400r/min.
Example 9
This example provides a method for recovering rare earth elements from a rare earth waste solution, which is the same as example 1 except that the ball milling rate is 150 r/min.
Example 10
This example provides a method for recovering rare earth elements from a rare earth waste solution, which is the same as example 1 except that the ball milling rate is 450 r/min.
Example 11
This example provides a method for recovering rare earth elements from a rare earth waste solution, which is the same as example 1 except that the ball milling time is 3 min.
Example 12
This example provides a method for recovering rare earth elements from a rare earth waste solution, which is the same as example 1 except that the ball milling time is 25 min.
Example 13
This example provides a method for recovering rare earth elements from a rare earth waste solution, which is the same as that of example 1 except that the concentration of the hydrochloric acid solution used in elution is 0.05 mol/L.
Example 14
This example provides a method for recovering rare earth elements from a rare earth waste solution, which is the same as example 1 except that the concentration of the hydrochloric acid solution used in elution is 0.6 mol/L.
Comparative example 1
The comparative example provides a method for recovering rare earth elements from a rare earth waste liquid, which is the same as that in example 1 except that the mass ratio of kaolin to phosphoric acid is 3.
Comparative example 2
The comparative example provides a method for recovering rare earth elements from a rare earth waste liquid, which is the same as that in example 1 except that the mass ratio of kaolin to phosphoric acid is 25.
Comparative example 3
The comparative example provides a method for recovering rare earth elements from a rare earth waste liquid, in which the phosphate-based kaolin is the same as that in example 1 except that kaolin is replaced by equal mass.
Performance test
For the methods provided in examples 1 to 14 and comparative examples 1 to 3, the adsorption rates of the rare earth elements and impurity elements, the elution rates of the rare earth elements, and the concentrations of the rare earth elements in the eluates after enrichment were measured as follows:
the initial and final concentrations of rare earth elements or impurity elements in the rare earth waste liquid are tested by using an inductively coupled plasma emission spectrometer (ICP method), and the adsorption rate is calculated by using the following formula:
in the formula, C i Represents the initial concentration (mg/L) of rare earth elements or impurity elements in the rare earth waste liquid; c f Representing the final concentration (mg/L) of rare earth elements or impurity elements in the rare earth waste liquid.
In the formula, C e Represents the concentration (mg/L) of rare earth elements in the eluent in desorption equilibrium; v is the volume of the eluent (L); m is adsorbent mass (g); q. q.s e The adsorption capacity (mg/g) at adsorption equilibrium.
The results are shown in Table 1.
TABLE 1
From examples 1 to 8, it can be seen that in the method of the present invention, the adsorption rate of the rare earth element is 90% or more, the desorption rate of the rare earth element is 98% or more, the concentration of the rare earth element in the eluate after enrichment is about 3g/L, and the adsorption rate of the impurity element is almost 0, thereby realizing the enrichment of the low-concentration rare earth element in the rare earth waste liquid and the separation of the high-concentration impurity element.
As can be seen from the comparison between examples 9 and 10 and example 1, the ball milling rate of the invention is controlled within the range of 200-400r/min, which is beneficial to the realization of phosphate modification of kaolin and ensures that the obtained phosphate kaolin has higher selective adsorption capacity for rare earth elements; when the ball milling speed is lower than 200r/min, the phosphoric acid cannot be completely loaded on the kaolin due to insufficient mechanical energy; when the ball milling rate is higher than 400r/min, the kaolin structure is completely broken, and the number of exchangeable hydrogen ions on the surface of the phosphate kaolin is reduced, resulting in a reduction in the adsorption capacity thereof.
As can be seen from the comparison between examples 11 and 12 and example 1, the ball milling time is controlled within the range of 5-20min, which is beneficial to realizing the phosphate modification of kaolin; when the ball milling time is less than 5min, phosphoric acid cannot be sufficiently loaded on the kaolin, so that the number of phosphate groups on the surface of the kaolin is reduced; when the ball milling time is more than 20min, the kaolin structure is completely broken, the number of exchangeable hydrogen ions on the surface of the phosphate kaolin is reduced, and the adsorption capacity of the phosphate kaolin is reduced.
As can be seen from the comparison between the example 13 and the example 14 and the example 1, the concentration of the acidic solution is controlled within the range of 0.1 to 0.4mol/L during the elution, which is beneficial to the rare earth elements to fall off from the phosphate kaolin, thereby realizing the enrichment of the rare earth elements; when the concentration is lower than 0.1mol/L, the rare earth elements are not completely fallen off from the phosphate kaolin, so that the recovery rate of the rare earth metals is reduced; when the concentration is higher than 0.4mol/L, the structure of the phosphoric acid-based kaolin is destroyed, and the reusability is affected.
As is clear from the comparison between comparative example 1, comparative example 2 and example 1, the mass ratio of kaolin to phosphoric acid in the present invention is controlled in the range of (5-20): 1, which is advantageous for achieving phosphate group modification of kaolin; when the mass ratio is lower than 5; when the mass ratio is higher than 20.
As is clear from comparison between comparative example 3 and example 1, the rare earth ratio of kaolin modified without phosphoric acid in the present invention to rare earth elements is only 10.8%.
According to the invention, phosphate modification is carried out on kaolin by using phosphoric acid, and selective adsorption of rare earth elements is realized through the bonding effect of phosphate on the obtained phosphate kaolin and the rare earth elements; the method has the advantages of short flow, low cost, wide raw material source and mild conditions, the adsorption rate of the rare earth elements can reach more than 90%, the adsorption rate of the impurity elements is almost 0, and the enrichment of low-concentration rare earth elements in the rare earth waste liquid and the separation of high-concentration impurity elements are realized.
The applicant states that the process of the present invention is illustrated by the above examples, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A method for recovering rare earth elements from a rare earth waste liquid, which is characterized by comprising the following steps:
the rare earth waste liquid and the phosphate kaolin are mixed, subjected to solid-liquid separation and eluted, and then the recovery of rare earth elements is completed;
the phosphate kaolin is prepared by mixing, ball-milling, washing and drying kaolin and phosphoric acid;
the concentration of rare earth elements in the rare earth waste liquid is 30-40mg/L;
the concentration of impurity elements in the rare earth waste liquid is 500-800mg/L;
the mass ratio of the kaolin to the phosphoric acid is (5-20) to 1.
2. The method of claim 1, wherein the ball milling is performed at a rate of 200 to 400r/min.
3. The method according to claim 1 or 2, characterized in that the time of ball milling is 5-20min.
4. The method of any one of claims 1 to 3, wherein the ball milling has a mass ratio of (75-80): 1.
5. The method of any one of claims 1-4 wherein the rare earth element comprises any one or a combination of at least two of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, yttrium, or lutetium.
6. The method according to any one of claims 1 to 5, wherein the impurity elements comprise any one of calcium, magnesium or ammonia nitrogen or a combination of at least two thereof;
preferably, the pH of the rare earth waste liquid is 5-7.
7. The method according to any one of claims 1 to 6, wherein the phosphate-based kaolin is mixed with the rare earth waste liquor at a solid-to-liquid ratio of (1-3): 1, the unit of the solid-to-liquid ratio being g/L;
preferably, the temperature for mixing the phosphate kaolin and the rare earth waste liquid is 20-30 ℃;
preferably, the mixing time of the phosphate kaolin and the rare earth waste liquid is 1-4h;
preferably, the phosphate kaolin is mixed with the rare earth waste liquid with stirring;
preferably, the stirring rate is 200-300r/min.
8. The method according to any one of claims 1 to 7, wherein the elution liquid used for the elution comprises an acidic solution;
preferably, the acidic solution comprises any one of hydrochloric acid, nitric acid or sulfuric acid, or a combination of at least two thereof;
preferably, the concentration of the acid solution is 0.1-0.4mol/L;
preferably, the elution time is 0.5-1h;
preferably, the temperature of the elution is 20-30 ℃.
9. The method according to any one of claims 1 to 8, wherein the temperature of the washing is 20 to 30 ℃;
preferably, the temperature of the drying is 60-80 ℃;
preferably, the drying time is 8-16h.
10. A method according to any of claims 1-9, characterized in that the method comprises the steps of:
mixing phosphate kaolin and rare earth waste liquid according to the solid-liquid ratio of (1-3) to 1g/L at 20-30 ℃ for 1-4h, and after solid-liquid separation, eluting by using an acid solution with the concentration of 0.1-0.4mol/L for 0.5-1h to complete the recovery of rare earth elements;
the concentration of rare earth elements in the rare earth waste liquid is 30-40mg/L, and the rare earth elements comprise any one or combination of at least two of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, yttrium or lutetium; the concentration of impurity elements in the rare earth waste liquid is 500-800mg/L, and the impurity elements comprise any one or the combination of at least two of calcium, magnesium or ammonia nitrogen;
the phosphate kaolin is prepared by mixing kaolin and phosphoric acid in a mass ratio of (5-20): 1, performing ball milling for min, and washing and drying the mixture; the ball milling speed is 200-400r/min.
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