CN115874069A - Method for leaching rare earth in neodymium iron boron waste iron tailings - Google Patents
Method for leaching rare earth in neodymium iron boron waste iron tailings Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 207
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 103
- 238000002386 leaching Methods 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 76
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 73
- 239000002699 waste material Substances 0.000 title claims abstract description 73
- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 64
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 64
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000002253 acid Substances 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 46
- 150000002505 iron Chemical class 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 238000000498 ball milling Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 238000004090 dissolution Methods 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 43
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 11
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 238000004137 mechanical activation Methods 0.000 abstract description 9
- 238000000605 extraction Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 239000002893 slag Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- DEGLFTVQHFLGRC-UHFFFAOYSA-N [B].[Fe].[Nd].[Fe] Chemical compound [B].[Fe].[Nd].[Fe] DEGLFTVQHFLGRC-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000011085 pressure filtration Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 2
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 229910052777 Praseodymium Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052776 Thorium Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 229910003440 dysprosium oxide Inorganic materials 0.000 description 1
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(iii) oxide Chemical compound O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910001938 gadolinium oxide Inorganic materials 0.000 description 1
- 229940075613 gadolinium oxide Drugs 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- KBLRIGLPGMRISA-UHFFFAOYSA-N neodymium(3+) oxygen(2-) praseodymium(3+) Chemical compound [O-2].[Pr+3].[Nd+3].[O-2].[O-2] KBLRIGLPGMRISA-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- -1 rare earth sulfate Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910003451 terbium oxide Inorganic materials 0.000 description 1
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 description 1
- VGBPIHVLVSGJGR-UHFFFAOYSA-N thorium(4+);tetranitrate Chemical compound [Th+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VGBPIHVLVSGJGR-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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 relates to a method for leaching rare earth in neodymium iron boron waste iron tailings, which comprises the following steps: (1) Drying the neodymium iron boron waste iron tailings to obtain iron tailing materials; (2) Carrying out dry ball milling on the iron tailing material obtained in the step (1), and separating ball materials to obtain an activated iron tailing material; (3) And (3) mixing acid liquor with the pH value of 1-3 with the activated iron tailing material obtained in the step (2), and performing solid-liquid separation to obtain leaching liquor containing rare earth and leaching residues. The invention combines mechanical activation and acid leaching, changes the chemical stability of the iron tailings by using the mechanical activation, ensures higher leaching rate of the rare earth elements under the condition of preferential dissolution of dilute acid by combining the reasonable pH value and preparation process parameters of the acid liquor, and can directly flow into the extraction separation process without an iron removal process for the obtained leaching solution containing the rare earth, thereby reducing the production cost.
Description
Technical Field
The invention relates to the technical field of industrial waste residue recovery, in particular to a method for leaching rare earth in neodymium iron boron waste iron tailings.
Background
The neodymium iron boron permanent magnet material is widely applied to the fields of new energy, consumer electronics, wind power generation and the like due to the characteristics of high coercive force, high magnetic energy product and the like. About 30% of waste materials are generated in the production process of the neodymium iron boron permanent magnet material, the waste materials contain about 1% of boron, 60-70% of iron, 20-30% of rare earth elements such as praseodymium, neodymium, dysprosium and the like, and a small amount of impurities such as silicon, aluminum, cobalt and the like, so that the recycling value is extremely high.
At present, the rare earth elements in the waste materials are generally recovered by adopting a hydrochloric acid optimum solution method in the industry, and the process route is as follows: oxidizing roasting, hydrochloric acid preferential dissolution, extraction separation and precipitation roasting. Wherein, the slag obtained after the treatment of the hydrochloric acid preferential dissolution working procedure is called iron tailings, the main component of which is ferric oxide, and the content of rare earth oxide is 0.3-2%. Although the rare earth grade is still superior to that of natural rare earth ore, because the residual rare earth in the iron tailings is not completely oxidized and the cladding effect caused by the existence of a large amount of chemically stable ferric oxide, the residual rare earth cannot be effectively extracted from the iron tailings simply through the preferential dissolution of hydrochloric acid, and therefore, the development of an efficient and low-cost method for extracting the rare earth in the iron tailings is the key for improving the recycling value of the iron tailings.
CN 105039727A discloses a process method for recovering rare earth from ultralow-content NdFeB waste residues, which comprises the following steps: mixing, stirring and filtering iron slag, an extracting agent and water to obtain a solid A1 and a liquid B1; mixing the solid A1 with water for washing, and mixing the washed liquid with the liquid B1 to form a liquid B2; subjecting the liquid B2 and the shrinkage enrichment agent to shrinkage enrichment and recovery to produce a solid A2 and a liquid B3; mixing and stirring the solid A2, a dissolving agent, water, an oxidant and a neutralizing agent respectively according to a sequence to obtain a solid A3 and a liquid B4; the liquid B4 enters the first line and/or the second line for extraction and separation; through the procedures of precipitation and ignition, praseodymium neodymium oxide, dysprosium oxide, gadolinium oxide, terbium oxide and the like are obtained. According to the method, the inorganic acid is used for extracting the rare earth in the iron tailings, so that although the rare earth can be dissolved out more effectively by increasing the acid concentration, a large amount of impurities such as iron and the like are dissolved out, the subsequent impurity removal cost is greatly increased, and the economic benefit is poor.
CN 103184343A discloses a method for recovering rare earth, thorium and iron from waste residue of rare earth acid process, which is characterized in that: taking waste residue generated by the rare earth acid method process as a raw material, and mixing the waste residue generated by the rare earth acid method process with HCl and H 2 SO 4 、HNO 3 Mixing one or more than one mixed acid solution, stirring and leaching at the temperature of 60 ℃ to boiling, filtering and washing a filter cake to obtain a leaching solution and secondary waste residues; extracting the leachate by primary amine, and back-extracting the leachate into thorium nitrate solution by nitric acid; adjusting pH of the thorium raffinate to 4.5-5.5 with alkali, and precipitating Fe (OH) 3 A by-product; the filtrate is a rare earth feed liquid product. However, the method directly adopts the acid leaching method to recover the rare earth, and the leaching rate of the rare earth still needs to be improved.
CN 105734296A discloses a comprehensive utilization method of neodymium iron boron waste acid leaching residue, which comprises the steps of sequentially carrying out sulfuric acid leaching, reduction, impurity removal and oxidation on iron tailings to prepare iron oxide red, filtering and washing to dissolve rare earth sulfate in acid leaching residue, and sending filtrate obtained after separation to a rare earth extraction process for preparing rare earth products. However, the ferric oxide in the invention is relatively stable, and the leaching rates of iron, cobalt and rare earth are relatively low and the cost is relatively high by adopting a conventional sulfuric acid leaching method.
Aiming at the defects of the prior art, the method for extracting rare earth from iron tailings with high rare earth leaching rate and low cost is needed.
Disclosure of Invention
The invention aims to provide a method for leaching rare earth in neodymium iron boron iron tailings, which combines mechanical activation and acid leaching and realizes efficient and low-cost leaching of rare earth in neodymium iron boron iron tailings by controlling the pH value of acid liquor and preparation process parameters.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for leaching rare earth in iron tailings of neodymium iron boron waste, which comprises the following steps:
(1) Drying the neodymium iron boron waste iron tailings to obtain iron tailings;
(2) Carrying out dry ball milling on the iron tailing material obtained in the step (1), and separating ball materials to obtain an activated iron tailing material;
(3) And (3) mixing acid liquor with the pH value of 1-3 with the activated iron tailing material obtained in the step (2), and performing solid-liquid separation to obtain rare earth-containing leaching liquor and leaching residues.
According to the method provided by the invention, the neodymium iron boron iron waste iron tailings are dried to remove moisture, and then the chemical stability of the neodymium iron boron iron waste tailings is destroyed through the physicochemical change generated in the mechanical activation process, so that rare earth can be effectively extracted under a milder condition in the subsequent acid leaching process, rare earth elements in the neodymium iron boron waste iron tailings are dissolved out by acid and enter a leachate in an ionic form, and iron oxide in the neodymium iron boron waste iron tailings basically does not react and remains in a slag phase. The method provided by the invention is efficient and low in cost, the utilization rate of the iron tailings of the neodymium iron boron iron waste is obviously improved, and the resource waste is avoided.
The pH value of the acid solution in the step (3) is 1-3, for example, 1, 1.5, 2, 2.5 or 3, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
In the invention, the pH value of the added acid liquor is controlled to be 1-3, so that the leaching effect of the rare earth can be ensured and a large amount of iron can be avoided dissolving out.
The leaching solution containing rare earth obtained in the step (3) can directly flow into an extraction separation process so as to further purify and produce rare earth products; the obtained leaching residue contains a large amount of valuable metals such as iron, cobalt and the like, and can be recycled.
Preferably, the neodymium iron boron waste iron tailings in the step (1) are obtained by performing acid dissolution treatment on neodymium iron boron waste.
Preferably, the content of the rare earth oxide in the neodymium iron boron waste iron tailings in the step (1) is more than or equal to 0.3%, for example, 0.3%, 0.5%, 0.6%, 0.8%, 1%, or 1.2%, but not limited to the recited values, and other values in the range of the values are also applicable.
The content of iron oxide in the neodymium iron boron waste iron tailings is 70-75%, the content of water is 13-15%, rare earth elements in contained rare earth oxides comprise lanthanum, cerium, praseodymium, neodymium, gadolinium and the like, and impurities comprise aluminum, silicon, calcium, chlorine, cobalt, copper, zinc, titanium, chromium and the like.
Preferably, the drying treatment in the step (1) is carried out until the neodymium iron boron waste iron tailings have constant weight.
The drying treatment adopts a heating drying method, and is a conventional technical means in the field.
Preferably, the mass ratio of the dry ball milled in the step (2) is 1 (2-60), and can be, for example, 1:2, 1:5, 1.
Preferably, the dry ball milling of step (2) is carried out in any one of a planetary ball mill, a roller ball mill or a stirred ball mill.
Preferably, the dry ball milling in step (2) is performed at 30-1000rpm, such as 30rpm, 100rpm, 300rpm, 500rpm, 800rpm or 1000rpm, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the dry ball milling time in step (2) is 0.5-50h, such as 0.5h, 5h, 10h, 20h, 30h, 40h or 50h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the solid-to-liquid ratio of the activated iron tailings to the acid liquor in the step (3) is 1g (1-10) mL, and may be, for example, 1g.
Preferably, the acid in the acid solution in the step (3) comprises an inorganic acid and/or an organic acid.
Preferably, the inorganic acid comprises hydrochloric acid and/or nitric acid.
Preferably, the organic acid comprises citric acid and/or lactic acid.
Preferably, the temperature of the mixing in step (3) is 20-100 ℃, for example 20 ℃, 40 ℃, 60 ℃, 80 ℃ or 100 ℃, but not limited to the recited values, and other values not recited in the numerical ranges are equally applicable.
Preferably, the mixing time in step (3) is 0.5 to 10 hours, for example, 0.5 hour, 3 hours, 5 hours, 8 hours or 10 hours, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
The mixing is continuous stirring.
Preferably, the solid-liquid separation method in step (3) includes any one or a combination of at least two of suction filtration, pressure filtration and centrifugation, and typical but non-limiting combinations include suction filtration and centrifugation, pressure filtration and centrifugation, or suction filtration, pressure filtration and centrifugation.
As a preferred technical scheme of the method, the method comprises the following steps:
(1) Drying the neodymium iron boron waste iron tailings until the weight of the neodymium iron boron waste iron tailings is constant, so as to obtain iron tailings;
the neodymium iron boron waste iron tailings are obtained by performing acid dissolution treatment on neodymium iron boron waste; the content of rare earth oxide in the neodymium iron boron waste iron tailings is more than or equal to 0.3%;
(2) Carrying out dry ball milling on the iron tailing material obtained in the step (1) for 0.5-50h at the rotating speed of 30-1000rpm, and separating a ball material to obtain an activated iron tailing material; the mass ratio of the material balls of the dry ball milling is 1 (2-60);
(3) Mixing acid liquor with the pH value of 1-3 and the activated iron tailing material obtained in the step (2) for 0.5-10h at 20-100 ℃, and performing solid-liquid separation to obtain rare earth-containing leachate and leaching residue; the solid-liquid ratio of the activated iron tailing material to the acid liquor is 1g (1-10) mL.
Compared with the prior art, the invention has the following beneficial effects:
according to the method for leaching rare earth from the iron tailings of the neodymium iron boron waste, provided by the invention, mechanical activation and acid leaching are combined, the chemical stability of the iron tailings is changed by using the mechanical activation effect, and the reasonable pH value and preparation process parameters of the acid liquor are combined, so that the leaching rate of rare earth elements is up to 85% under the condition of dilute acid preferential dissolution, the obtained leaching solution containing rare earth can directly flow into an extraction separation process without an iron removal process, and the production cost is greatly reduced; the method has the advantages of simple process, conventional equipment and higher economical and practical properties, and can be used for recycling industrial resources of the iron tailings.
Detailed Description
The technical solution of the present invention is further described below by way of specific 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.
In the embodiment provided by the invention, the neodymium iron boron waste iron tailings are obtained by acid dissolution treatment of neodymium iron boron waste; the chemical composition (mass percentage) of the neodymium iron boron waste iron tailings is that the content of ferric oxide is 73%, the content of rare earth oxide is 1%, the moisture content is 14%, and the balance is impurities.
Example 1
The embodiment provides a method for leaching rare earth in iron tailings of neodymium iron boron wastes, which comprises the following steps:
(1) Drying the neodymium iron boron waste iron tailings until the weight of the neodymium iron boron waste iron tailings is constant, so as to obtain iron tailings;
(2) Carrying out dry ball milling on the iron tailing obtained in the step (1) for 25 hours in a planetary ball mill at the rotating speed of 500rpm, and separating ball materials to obtain activated iron tailing; the mass ratio of the dry ball-milled material balls is 1;
(3) Mixing a hydrochloric acid solution with the pH value of 1 with the activated iron tailing material obtained in the step (2) for 3 hours at 90 ℃, and performing suction filtration to obtain a leaching solution containing rare earth and leaching residues; the solid-liquid ratio of the activated iron tailing material to the acid liquor is 1g.
Example 2
The embodiment provides a method for leaching rare earth in neodymium iron boron waste iron tailings, which comprises the following steps:
(1) Drying the neodymium iron boron waste iron tailings until the weight of the neodymium iron boron waste iron tailings is constant, so as to obtain iron tailings;
(2) Carrying out dry ball milling on the iron tailings obtained in the step (1) for 40h in a planetary ball mill at the rotating speed of 200rpm, and separating ball materials to obtain activated iron tailings; the mass ratio of the dry ball-milled material balls is 1;
(3) Mixing a hydrochloric acid solution with the pH value of 1 at 40 ℃ with the activated iron tailing material obtained in the step (2) for 8 hours, and performing suction filtration to obtain a leaching solution containing rare earth and leaching slag; the solid-liquid ratio of the activated iron tailing material to the acid liquid is 1g and 8mL.
Example 3
The embodiment provides a method for leaching rare earth in iron tailings of neodymium iron boron wastes, which comprises the following steps:
(1) Drying the neodymium iron boron waste iron tailings until the weight of the neodymium iron boron waste iron tailings is constant, so as to obtain iron tailings;
(2) Carrying out dry ball milling on the iron tailings obtained in the step (1) for 10 hours in a planetary ball mill at the rotating speed of 800rpm, and separating ball materials to obtain activated iron tailings; the mass ratio of the dry ball-milled material balls is 1;
(3) Mixing a hydrochloric acid solution with the pH value of 1 with the activated iron tailing material obtained in the step (2) for 5 hours at 70 ℃, and performing suction filtration to obtain a leaching solution containing rare earth and leaching residues; the solid-liquid ratio of the activated iron tailing to the acid liquor is 1g.
Example 4
The embodiment provides a method for leaching rare earth in iron tailings of neodymium iron boron wastes, which comprises the following steps:
(1) Drying the neodymium iron boron waste iron tailings to constant weight to obtain iron tailing materials;
(2) Carrying out dry ball milling on the iron tailings obtained in the step (1) for 50h in a roller ball mill at the rotating speed of 30rpm, and separating ball materials to obtain activated iron tailings; the mass ratio of the material balls subjected to dry ball milling is 1:2;
(3) Mixing a hydrochloric acid solution with the pH value of 1 at 20 ℃ with the activated iron tailing material obtained in the step (2) for 10 hours, and performing suction filtration to obtain a leaching solution containing rare earth and leaching slag; the solid-liquid ratio of the activated iron tailing to the acid liquor is 1g and 10mL.
Example 5
The embodiment provides a method for leaching rare earth in neodymium iron boron waste iron tailings, which comprises the following steps:
(1) Drying the neodymium iron boron waste iron tailings until the weight of the neodymium iron boron waste iron tailings is constant, so as to obtain iron tailings;
(2) Carrying out dry ball milling on the iron tailings obtained in the step (1) for 0.5h in a roller ball mill at the rotating speed of 1000rpm, and separating ball materials to obtain activated iron tailings; the mass ratio of the dry ball-milled material balls is 1;
(3) Mixing a hydrochloric acid solution with the pH value of 1 at 100 ℃ with the activated iron tailing material obtained in the step (2) for 0.5h, and performing suction filtration to obtain a leaching solution containing rare earth and leaching slag; the solid-liquid ratio of the activated iron tailing to the acid liquor is 1g.
Example 6
The embodiment provides a method for leaching rare earth from iron tailings of neodymium iron boron wastes, which is different from the embodiment 1 in that the method is the same as the embodiment 1 except that the pH value of the hydrochloric acid solution in the step (3) is adjusted to 3.
Example 7
The embodiment provides a method for leaching rare earth from iron tailings of neodymium iron boron wastes, which is different from the embodiment 1 in that the method is the same as the embodiment 1 except that the hydrochloric acid solution and other pH values in the step (3) are replaced by nitric acid solution.
Example 8
The embodiment provides a method for leaching rare earth from iron tailings of neodymium iron boron wastes, which is different from the embodiment 1 in that the method is the same as the embodiment 1 except that the hydrochloric acid solution and other pH values in the step (3) are replaced by citric acid solution.
Example 9
The embodiment provides a method for leaching rare earth from iron tailings of neodymium iron boron wastes, which is different from the embodiment 1 in that the method is the same as the embodiment 1 except that the hydrochloric acid solution and the like in the step (3) are replaced by a lactic acid solution.
Comparative example 1
The comparative example provides a method for leaching rare earth in iron tailings of neodymium iron boron wastes, which is different from the method in example 1 in that the step (2) is omitted, and the rest is the same as the method in example 1.
Comparative example 2
The comparative example provides a method for leaching rare earth from iron tailings of neodymium iron boron wastes, which is different from the method in the example 1 in that the method is the same as the method in the example 1 except that the pH value of the hydrochloric acid solution in the step (3) is adjusted to be 4.
Comparative example 3
The comparative example provides a method for leaching rare earth in iron tailings of neodymium iron boron wastes, which is different from the method in the example 1 in that the method is the same as the example 1 except that the hydrogen ion concentration of the hydrochloric acid solution in the step (3) is adjusted to be 1 mol/L.
The method for leaching rare earth in the neodymium iron boron waste iron tailings provided by the embodiments 1 to 9 and the comparative examples 1 to 3 is adopted to obtain leaching liquid containing rare earth and leaching slag, samples are measured and calculated according to JY/T0567-2020, the leaching rates of rare earth oxide and ferric oxide are obtained, and the obtained results are shown in Table 1.
TABLE 1
As can be seen from table 1, the method for leaching rare earth from neodymium iron boron waste iron tailings provided by the invention changes the chemical stability of the neodymium iron boron waste iron tailings by using the mechanical activation effect, enables the rare earth element to have higher leaching rate under the condition of dilute acid preferential dissolution, and enables the obtained leaching solution containing rare earth to directly flow into the extraction separation process without removing iron, thereby reducing the production cost;
compared with the example 6 and the comparative examples 2 and 3, the pH value of the hydrochloric acid solution has certain influence on the leaching effect of the rare earth oxide, the pH value of the hydrochloric acid solution is in a reasonable range, and a higher leaching rate can be obtained, when the pH value of the hydrochloric acid solution is lower than 1, the iron in the iron tailings can be greatly dissolved out, the impurity removal cost is increased, the pH value of the hydrochloric acid solution is too high, and the leaching rate of the rare earth oxide is remarkably reduced; as can be seen from the comparison between example 1 and examples 7-9, the adoption of nitric acid, citric acid and lactic acid as leaching agents can still effectively ensure that the rare earth oxide has higher leaching rate;
compared with the comparative example 1, the embodiment 1 shows that the chemical stability of the neodymium iron boron waste iron tailings is difficult to change without adopting a dry ball milling step, so that the leaching difficulty of rare earth is improved, and the leaching rate is obviously reduced.
In conclusion, the method for leaching rare earth from the iron tailings of the neodymium iron boron waste provided by the invention combines mechanical activation and acid leaching, changes the chemical stability of the iron tailings by using the mechanical activation effect, combines the reasonable pH value of the acid solution and the preparation process parameters, ensures that the leaching rate of rare earth elements reaches 85% under the condition of dilute acid preferential dissolution, and ensures that the obtained leaching solution containing rare earth can directly flow into the extraction separation process without an iron removal process, thereby greatly reducing the production cost; the method has the advantages of simple process, conventional equipment and higher economical and practical properties, and can be used for recycling industrial resources of the iron tailings.
The above description is only for the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.
Claims (10)
1. A method for leaching rare earth in neodymium iron boron waste iron tailings is characterized by comprising the following steps:
(1) Drying the neodymium iron boron waste iron tailings to obtain iron tailings;
(2) Carrying out dry ball milling on the iron tailing material obtained in the step (1), and separating ball materials to obtain an activated iron tailing material;
(3) And (3) mixing acid liquor with the pH value of 1-3 with the activated iron tailing material obtained in the step (2), and performing solid-liquid separation to obtain rare earth-containing leaching liquor and leaching residues.
2. The method according to claim 1, wherein the neodymium iron boron waste iron tailings obtained in the step (1) are neodymium iron boron waste materials which are subjected to acid dissolution treatment.
3. The method according to claim 1 or 2, wherein the content of the rare earth oxide in the neodymium iron boron waste iron tailings in the step (1) is more than or equal to 0.3%.
4. The method according to any one of claims 1 to 3, wherein the drying treatment in step (1) is carried out until the neodymium iron boron waste iron tailings are of constant weight.
5. The method according to any one of claims 1 to 4, wherein the mass ratio of the material balls of the dry ball milling in the step (2) is 1 (2-60);
preferably, the dry ball milling of step (2) is carried out in any one of a planetary ball mill, a roller ball mill or a stirred ball mill.
6. The method according to any one of claims 1 to 5, wherein the dry ball milling in step (2) is performed at a rotation speed of 30 to 1000rpm;
preferably, the time of the dry ball milling in the step (2) is 0.5-50h.
7. The method according to any one of claims 1 to 6, wherein the solid-to-liquid ratio of the activated iron tailings to the acid liquor in the step (3) is 1g (1-10) mL.
8. The process according to any one of claims 1 to 7, wherein the acid in the acid solution of step (3) comprises an inorganic acid and/or an organic acid;
preferably, the inorganic acid comprises hydrochloric acid and/or nitric acid;
preferably, the organic acid comprises citric acid and/or lactic acid.
9. The process according to any one of claims 1 to 8, wherein the temperature of the mixing in step (3) is 20 to 100 ℃;
preferably, the mixing time in step (3) is 0.5-10h.
10. A method according to any of claims 1-9, characterized in that the method comprises the steps of:
(1) Drying the neodymium iron boron waste iron tailings until the weight of the neodymium iron boron waste iron tailings is constant, so as to obtain iron tailings;
the neodymium iron boron waste iron tailings are obtained by performing acid dissolution treatment on neodymium iron boron waste; the content of rare earth oxide in the neodymium iron boron waste iron tailings is more than or equal to 0.3%;
(2) Carrying out dry ball milling on the iron tailing material obtained in the step (1) for 0.5-50h at the rotating speed of 30-1000rpm, and separating a ball material to obtain an activated iron tailing material; the mass ratio of the material balls of the dry ball milling is 1 (2-60);
(3) Mixing acid liquor with the pH value of 1-3 with the activated iron tailing material obtained in the step (2) for 0.5-10h at 20-100 ℃, and performing solid-liquid separation to obtain leaching liquor containing rare earth and leaching residues; the solid-to-liquid ratio of the activated iron tailing material to the acid liquor is 1g (1-10) mL.
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