CN103773966B - The extraction and application method of neodymium iron boron waste material - Google Patents
The extraction and application method of neodymium iron boron waste material Download PDFInfo
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- 239000002699 waste material Substances 0.000 title claims abstract description 51
- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 48
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000000605 extraction Methods 0.000 title claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 139
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 135
- 239000007788 liquid Substances 0.000 claims abstract description 128
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 110
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 43
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000001704 evaporation Methods 0.000 claims abstract description 37
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 37
- 230000008020 evaporation Effects 0.000 claims abstract description 33
- 230000003647 oxidation Effects 0.000 claims abstract description 31
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical group [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 28
- 229910000398 iron phosphate Inorganic materials 0.000 claims abstract description 24
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 19
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 19
- 238000003916 acid precipitation Methods 0.000 claims abstract description 17
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 15
- 238000001556 precipitation Methods 0.000 claims abstract description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 80
- 239000000706 filtrate Substances 0.000 claims description 80
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 60
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 52
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000003837 high-temperature calcination Methods 0.000 claims description 24
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 24
- 239000002002 slurry Substances 0.000 claims description 24
- 239000005696 Diammonium phosphate Substances 0.000 claims description 22
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 22
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 22
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 22
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000007791 liquid phase Substances 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 18
- 230000001590 oxidative effect Effects 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 230000007062 hydrolysis Effects 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 230000000887 hydrating effect Effects 0.000 claims description 6
- 239000012452 mother liquor Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 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 claims 1
- 238000011084 recovery Methods 0.000 abstract description 14
- RKLPWYXSIBFAJB-UHFFFAOYSA-N [Nd].[Pr] Chemical compound [Nd].[Pr] RKLPWYXSIBFAJB-UHFFFAOYSA-N 0.000 abstract description 10
- 102000004316 Oxidoreductases Human genes 0.000 abstract 2
- 108090000854 Oxidoreductases Proteins 0.000 abstract 2
- 239000002244 precipitate Substances 0.000 abstract 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 30
- 150000002910 rare earth metals Chemical class 0.000 description 25
- 238000000227 grinding Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- PYEJXBWRVNYIFO-UHFFFAOYSA-H C(C(=O)[O-])(=O)[O-].[Nd+3].[Pr+3].C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-] Chemical compound C(C(=O)[O-])(=O)[O-].[Nd+3].[Pr+3].C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-] PYEJXBWRVNYIFO-UHFFFAOYSA-H 0.000 description 8
- 239000004566 building material Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000003337 fertilizer Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 239000005955 Ferric phosphate Substances 0.000 description 4
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229940032958 ferric phosphate Drugs 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 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 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 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
- 230000005389 magnetism Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 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)
- Fertilizers (AREA)
Abstract
An extraction and application method for neodymium iron boron waste material, comprises following order step: dissolving with hydrochloric acid; A solid-liquid separation; Oxalic acid precipitation; Secondary solid-liquid separation; Hydrolyzing process; Three solid-liquid separation; Acid, oxidation operation; Tertiary iron phosphate precipitates; Four solid-liquid separation; Evaporation concentration; Five solid-liquid separation.Red iron oxide and oxidation Praseodymium neodymium is obtained by dissolving with hydrochloric acid, solid-liquid separation, oxalic acid precipitation and a secondary solid-liquid separation process; Red iron oxide and tertiary iron phosphate is obtained by dissolving with hydrochloric acid, solid-liquid separation, oxalic acid precipitation, secondary solid-liquid separation, hydrolyzing process, three solid-liquid separation, acid oxidase operation, tertiary iron phosphate precipitation and four solid-liquid separation process; Ammonium chloride is obtained by dissolving with hydrochloric acid, solid-liquid separation, oxalic acid precipitation, secondary solid-liquid separation, hydrolyzing process, three solid-liquid separation, acid oxidase operation, tertiary iron phosphate precipitation, four solid-liquid separation, evaporation concentration and five solid-liquid separation.It has the rate of recovery and the feature such as purity is high, environment friendly and pollution-free, cost recovery is low.
Description
Technical field
The invention belongs to the technical field of rare earth resources recycling, specifically a kind of extraction and application method of neodymium iron boron waste material.
Background technology
Neodymium iron boron is rear earth element nd, Boron, praseodymium etc. and the alloy of ferric oxide, is a kind of permanent magnet material with high remanent magnetism, high-coercive force, high energy product, is applied widely in modern industry and electronic technology.In the process of producing Nd-Fe-B permanent magnetic element, because the shape size of various element is different, the precision processing such as blank neodymium iron boron needs to carry out cutting, cut, mill, inevitably processing waste material will be produced in this precision processing process, according to statistics, neodymium iron boron waste material accounts for about 20% of blank total amount, and this is for the huge neodymium iron boron of demand, and the neodymium iron boron waste material amount of generation is very huge.
Due to the composition of neodymium iron boron waste material and the composition of finished product Nd-Fe-Bo permanent magnet material basically identical, containing rare earth composition about 30%, iron about 60 ~ 65%; In the rare earth composition of about 30%, praseodymium is about 20 ~ 25%, neodymium is about 75 ~ 80%, and different according to the performance of each element, and each neodymium iron boron waste material also has a small amount of rare earth element such as dysprosium, terbium, Gadolinium, lanthanum, cerium, samarium.In order to effectively utilize rare earth resources, in industry, usually can carry out extraction and application process to neodymium iron boron waste material, to extract rare earth element rare in neodymium iron boron waste material.
What traditional neodymium iron boron waste material extraction and application process mainly adopted is the technological measures such as calcining, grinding.Its Problems existing is: 1. resource consumption is high, the rate of recovery is low, significantly adds Separation and Recovery cost, extremely impracticable; 2. the rare earth element quality that obtains of Separation and Recovery is lower, and industrially recycling can affect the performance quality of finished product Nd-Fe-Bo permanent magnet material; 3. extraction and application measure is imperfect, only separation and Extraction rare earth element, other material contained by neodymium iron boron waste material, such as metallic compound (red iron oxide, tertiary iron phosphate), ammonium chloride etc., no longer separation and Extraction, direct discharge, not only causes severe environmental pollution, and further increases the Separation and Recovery cost of rare earth element.
In view of traditional neodymium iron boron waste material extraction and application technology Problems existing, in recent years, in succession occurred various novelty, unique separation and recovery technology in industry, these technology are appeared in the newspapers repeatly on public publication, but occur so far there are no identical with content of the present invention or akin technology.
Summary of the invention
The object of the invention is to: for above-mentioned the deficiencies in the prior art, provide a kind of low in resources consumption, the rate of recovery is high, reclaim that purity is high, the extraction and application method of Separation and Recovery is complete, environment friendly and pollution-free, byproduct use value is high, Separation and Recovery cost is low, reliable and practical neodymium iron boron waste material.
The technical solution used in the present invention is, a kind of extraction and application method of neodymium iron boron waste material, comprises following order step:
A. dissolving with hydrochloric acid: add in neodymium iron boron waste material concentration be 15 ~ 25% hydrochloric acid carry out acidolysis, the pH value of acidolysis terminal is 1.5 ~ 2.5, and the mass ratio of hydrochloric acid and neodymium iron boron waste material is 2:1, acidolysis temperature >=90 DEG C, the acidolysis time is 2 ~ 3 hours, and neodymium iron boron waste material is fully dissolved by hydrochloric acid;
B. a solid-liquid separation: the solution of steps A is carried out solid-liquid separation, obtains a filter residue, and a filter residue is after the high-temperature calcination of 400 ~ 600 DEG C, repeating step A, B, obtain secondary filter residue after repeating step A, B, this secondary filter residue is red iron oxide, sells directly; The filtrate obtained after solid-liquid separation enters oxalic acid precipitation step;
C. oxalic acid precipitation: the filtrate of step B is warming up to 60 ~ 90 DEG C, adds oxalic acid in filtrate, the mass ratio of oxalic acid and filtrate middle-weight rare earths total amount is 1.1 ~ 1.2:1, at least reacts after 25 minutes, leaves standstill 3 ~ 4 hours;
D. two solid-liquid separation: the solution of step C is carried out solid-liquid separation, the solid matter obtained carries out drying after washing, roasting, and maturing temperature is 850 ~ 1000 DEG C, and roasting time is 2 ~ 4 hours, obtains the oxidation Praseodymium neodymium that purity reaches more than 98%; Obtain liquid phase substance after solid-liquid separation and enter hydrolyzing process;
E. hydrolyzing process: add reduced iron powder in the liquid phase substance of step D, in reduced iron powder and liquid phase substance, the mass ratio of iron protochloride is 0.01 ~ 0.02:1, the pH value of solution is made to be 5 ~ 7, be hydrolyzed, hydrolysis temperature is 90 ~ 95 DEG C, hydrolysis time is 4 ~ 6 hours, and the metallic impurity in solution beyond iron are fully hydrolyzed;
F. three solid-liquid separation: the hydrating solution of step e is carried out solid-liquid separation, the filter residue obtained is repeating step A, B after the high-temperature calcination of 400 ~ 600 DEG C, and obtaining secondary filter residue after repeating step A, B is red iron oxide, sells directly; The filtrate that solid-liquid separation obtains enters acid, oxidation operation;
G. acid, oxidation operation: add in the filtrate of step F concentration be 85% industrial phosphoric acid carry out acidifying, in industrial phosphoric acid and filtrate, the mass ratio of iron protochloride is 1:3.5; In souring soln, add hydrogen peroxide be oxidized, in hydrogen peroxide and souring soln, the mass ratio of iron protochloride is 0.66 ~ 0.68:1, and oxidizing temperature is 40 ~ 60 DEG C, and oxidization time is 40 ~ 60 minutes;
H. tertiary iron phosphate precipitation: add diammonium phosphate and react in the oxidizing solution of step G, in diammonium phosphate and oxidizing solution, the mass ratio of iron protochloride is 0.8 ~ 1.2:1, and temperature of reaction is 40 ~ 60 DEG C, and the reaction times is 50 ~ 60 minutes; After question response completes, with ammoniacal liquor, the pH value of reaction soln is adjusted to 1.5 ~ 2.5, obtains tertiary iron phosphate precipitation;
I. four solid-liquid separation: step H is obtained product and carry out solid-liquid separation, the filter cake furnishing concentration obtained is the slurry of 50%, under whipped state, the industrial phosphoric acid that concentration is 85% is added in slurries, the mass ratio of industrial phosphoric acid and slurries is 0.04:1, the concentration of phosphoric acid in slurries is made to be 0.5 mol/L, be warming up to 60 ~ 90 DEG C, react 30 ~ 60 minutes, after question response completes, with ammoniacal liquor, the pH value of reaction soln is adjusted to 2.5 ~ 3.5, again reaction soln is filtered, the filter cake formed is dried after washing under the condition of 60 ~ 90 DEG C, obtain ferrophosphorus than the battery-grade iron phosphate for 1:0.97 ~ 1.02, the filtrate that solid-liquid separation and washing, filtration obtain enters evaporation concentration operation respectively,
J. evaporation concentration: carry out evaporation concentration by after twice filtrate mixing of step I, make filtrate be evaporated to hypersaturated state, after evaporation gas is condensed into water, cause dissolving with hydrochloric acid and/or solid-liquid separation process; Supersaturated solution is cooled to normal temperature, obtains ammonium chloride crystals;
K. five solid-liquid separation: the crystal solution obtained by step J carries out centrifugation, obtains ammonium chloride, sell directly; Be separated the mother liquor that obtains to be back to step J and to carry out repeated evaporation and concentrate.
Further, the hydrochloric acid in steps A is obtained through deionized water or distilled water diluting by the technical hydrochloric acid of concentration 32%.
Further, the oxalic acid in step C is the industrial ethanedioic acid of content 99.6%.
Further, reduced iron powder iron level >=98% in step e.
Further, the hydrogen peroxide in step G is the industrial hydrogen peroxide of massfraction > 25%.
Further, the diammonium phosphate in step H is industrial phosphoric acid two ammonium of content > 98%.
Further, the ammoniacal liquor in step H, I is the industrial ammonia of content > 25%.
Further, the separating device of a described solid-liquid separation, secondary solid-liquid separation, three solid-liquid separation, four solid-liquid separation employings is respectively plate-and-frame filter press.
The invention has the beneficial effects as follows: aforesaid method passes through dissolving with hydrochloric acid, oxalic acid precipitation, hydrolysis, a series of complete operation such as evaporation concentration, effectively, reliably rare in Separation and Recovery neodymium iron boron waste material, highly purified rare earth element-praseodymium neodymium, metallic compound (the red iron oxide that simultaneously Separation and Recovery use value is high, tertiary iron phosphate) and byproduct ammonium chloride, turn waste into wealth, avoid a large amount of consumption of neodymium iron boron waste material resource, waste and environmental pollution, significantly improve the rate of recovery, and then significantly reduce the Separation and Recovery cost of neodymium iron boron waste material, environment friendly and pollution-free, reliable and practical, manufacturing enterprise's high financial profit.
Accompanying drawing explanation
Fig. 1 is a kind of process flow sheet of the present invention.
Embodiment
See Fig. 1: below in conjunction with drawings and Examples, the present invention is further illustrated.
embodiment 1
The present invention includes following order step:
A. dissolving with hydrochloric acid: add in 1 ton of neodymium iron boron waste material (total amount of rare earth is about 25%) concentration be 20% hydrochloric acid carry out acidolysis, this hydrochloric acid is diluted through deionized water by the technical hydrochloric acid of concentration 32% and obtains, the mass ratio of hydrochloric acid and neodymium iron boron waste material is 2:1, acidolysis temperature is 95 DEG C, the acidolysis time is 3 hours, neodymium iron boron waste material is fully dissolved by hydrochloric acid, and the pH value of acidolysis reaction terminal is 2;
B. a solid-liquid separation: the solution of steps A is carried out solid-liquid separation by plate-and-frame filter press, obtain about 150kg(total amount of rare earth and be about 8%) a filter residue, a filter residue is through 450 DEG C of high-temperature calcinations, filter residue is substantially oxidized, to reduce the consumption of hydrochloric acid, the filter residue of high-temperature calcination oxidation is after grinding, repeating step A, B, the secondary filter residue of about 138kg is obtained after repeating step A, B, this secondary filter residue is red iron oxide, with deionized water wash 3 times, after pressing dry, sell, for building materials, coating etc. directly; The filtrate that obtains after solid-liquid separation (namely filter residue is separated to be separated with secondary filter residue and obtains) for total amount of rare earth be about 70g/L, volume is about 3.4m
3filtrate, filtrate enters oxalic acid precipitation step;
C. oxalic acid precipitation: the filtrate of step B is warming up to 80 DEG C, under whipped state, adds oxalic acid in filtrate, this oxalic acid is the industrial ethanedioic acid of content 99.6%, and the mass ratio of oxalic acid and filtrate middle-weight rare earths total amount is 1.14:1, and namely oxalic acid adds and is about 271kg, react after 30 minutes, leave standstill 3 hours;
D. two solid-liquid separation: the solution temperature of step C is down to 35 DEG C, then carries out solid-liquid separation by plate-and-frame filter press, the solid matter (i.e. praseodymium oxalate neodymium) obtained, after deionized water wash 3 times, obtains the solid matter of about 582kg; Solid matter is carried out dry, roasting, maturing temperature is 900 DEG C, and roasting time is 3 hours, makes praseodymium oxalate neodymium fully oxidized, obtains the oxidation Praseodymium neodymium that purity reaches 99.12% and is about 237kg; Obtain liquid phase substance after solid-liquid separation and enter hydrolyzing process;
E. hydrolyzing process: add reduced iron powder in the liquid phase substance of step D, this reduced iron powder iron level >=98%, in reduced iron powder and liquid phase substance, the mass ratio of iron protochloride is 0.015:1, namely the add-on of reduced iron powder is about 21kg, the reaction of intensification Accelerating reduction iron powder and free acid, makes the pH value of solution be 5, be hydrolyzed, hydrolysis temperature is 91 DEG C, and hydrolysis time is 5 hours, and the metallic impurity in solution beyond iron are fully hydrolyzed;
F. three solid-liquid separation: the hydrating solution of step e is carried out solid-liquid separation by plate-and-frame filter press, the filter residue obtained is about 50kg(because of other metallic impurity in solution and is fully hydrolyzed, in the filter residue obtained, the overwhelming majority is ironic hydroxide), these filter residues are through 450 DEG C of high-temperature calcinations, filter residue is substantially oxidized, to reduce the consumption of hydrochloric acid, the filter residue of high-temperature calcination oxidation is after grinding, repeating step A, B, repeating step A, obtaining secondary filter residue after B is red iron oxide, with deionized water, red iron oxide is washed 3 times, press dry rear to sell directly outward, for building materials, coating etc., repeating step A, B obtain the filtrate 0.45m that total amount of rare earth is about 25g/L
3, these filtrates enter step C, and after the oxalic acid reaction adding about 13kg, obtain by step D the oxidation Praseodymium neodymium 10.5kg that purity reaches 99.13%, so far, the rare earth reclaimed altogether is about 247.5kg, the filtrate that solid-liquid separation obtains enters acid, oxidation operation,
G. acid, oxidation operation: add in the filtrate of step F concentration be 85% industrial phosphoric acid carry out acidifying, in industrial phosphoric acid and filtrate, the mass ratio of iron protochloride is 1:3.5, and namely the add-on of industrial phosphoric acid is about 395kg; The hydrogen peroxide that adds that is slow in souring soln, that continue is oxidized, this hydrogen peroxide is the industrial hydrogen peroxide of massfraction > 25%, in whole oxidising process, the temperature of solution should control to be 40 DEG C, prevent decomposing hydrogen dioxide solution from causing waste, in hydrogen peroxide and souring soln, the mass ratio of iron protochloride is 0.66:1, namely the add-on of hydrogen peroxide is about 913kg, and oxidization time is 45 minutes;
H. tertiary iron phosphate precipitation: add diammonium phosphate and react in the oxidizing solution of step G, this diammonium phosphate is industrial phosphoric acid two ammonium of content > 98%, in diammonium phosphate and oxidizing solution, the mass ratio of iron protochloride is 0.829:1, namely the add-on of diammonium phosphate is about 1147kg, temperature of reaction is 40 DEG C, and the reaction times is 60 minutes; After question response completes, with ammoniacal liquor, the pH value of reaction soln is adjusted to 2.5, this ammoniacal liquor is the industrial ammonia of content > 25%, obtains tertiary iron phosphate precipitation;
I. four solid-liquid separation: step H is obtained product and carry out solid-liquid separation by plate-and-frame filter press, the filter cake furnishing concentration obtained is the slurry of 50%, under whipped state, the industrial phosphoric acid that concentration is 85% is added in slurries, the mass ratio of industrial phosphoric acid and slurries is about 0.04:1, the concentration of phosphoric acid in slurries is made to adjust to 0.5 mol/L, be warming up to 90 DEG C, react 40 minutes, after question response completes, with ammoniacal liquor, the pH value of reaction soln is adjusted to 3.5, this ammoniacal liquor is the industrial ammonia of content > 25%, again reaction soln is filtered by plate-and-frame filter press, the filter cake formed washs 3 times again, through 75 DEG C of oven dry, obtain ferrophosphorus than the battery-grade iron phosphate about 2.03 tons for 1:0.985, for productions such as ferric phosphate lithium cells, the filtrate that solid-liquid separation and washing, filtration obtain enters evaporation concentration operation respectively,
J. evaporation concentration: carry out evaporation concentration by after twice filtrate mixing of step I, filtrate is made to be evaporated to hypersaturated state, in whole evaporating concentration process, carry out under low temperature (but at least should guarantee that filtrate is evaporated to hypersaturated state) negative pressure as far as possible, decompose to prevent ammonium chloride, evaporation is after gas is condensed into water, cause respectively dissolving with hydrochloric acid operation, solid-liquid separation process, secondary solid-liquid separation process, three solid-liquid separation process and four solid-liquid separation process washing, size mixing and carry out water cycle; Under whipped state (about 32 revs/min), supersaturated solution is cooled to normal temperature, obtains ammonium chloride crystals;
K. five solid-liquid separation: the crystal solution obtained by step J carries out centrifugation by separating centrifuge, obtains the ammonium chloride of about 600kg, sell, for fertilizer and production of compound fertilizer etc. directly; Be separated mother liquor (about 1.4 m obtained
3) be back to step J and carry out repeated evaporation and concentrate, stop the discharge of ammonium nitrogen.
Filter residue in the present invention's solid-liquid separation and three solid-liquid separation process together can carry out high-temperature calcination.
embodiment 2
The present invention includes following order step:
A. dissolving with hydrochloric acid: add in 1 ton of neodymium iron boron waste material (total amount of rare earth is about 25%) concentration be 20% hydrochloric acid carry out acidolysis, this hydrochloric acid is diluted through deionized water by the technical hydrochloric acid of concentration 32% and obtains, the mass ratio of hydrochloric acid and neodymium iron boron waste material is 2:1, acidolysis temperature is 100 DEG C, the acidolysis time is 2.5 hours, neodymium iron boron waste material is fully dissolved by hydrochloric acid, and the pH value of acidolysis reaction terminal is 1.8;
B. a solid-liquid separation: the solution of steps A is carried out solid-liquid separation by plate-and-frame filter press, obtain about 150kg(total amount of rare earth and be about 8%) a filter residue, a filter residue is through 550 DEG C of high-temperature calcinations, filter residue is substantially oxidized, to reduce the consumption of hydrochloric acid, the filter residue of high-temperature calcination oxidation is after grinding, repeating step A, B, the secondary filter residue of about 138kg is obtained after repeating step A, B, this secondary filter residue is red iron oxide, with deionized water wash 3 times, after pressing dry, sell, for building materials, coating etc. directly; The filtrate that obtains after solid-liquid separation (namely filter residue is separated to be separated with secondary filter residue and obtains) for total amount of rare earth be about 70g/L, volume is about 3.4m
3filtrate, filtrate enters oxalic acid precipitation step;
C. oxalic acid precipitation: the filtrate of step B is warming up to 85 DEG C, under whipped state, adds oxalic acid in filtrate, this oxalic acid is the industrial ethanedioic acid of content 99.6%, and the mass ratio of oxalic acid and filtrate middle-weight rare earths total amount is 1.15:1, and namely oxalic acid adds and is about 274kg, react after 35 minutes, leave standstill 3 hours;
D. two solid-liquid separation: the solution temperature of step C is down to 30 DEG C, then carries out solid-liquid separation by plate-and-frame filter press, the solid matter (i.e. praseodymium oxalate neodymium) obtained, after deionized water wash 3 times, obtains the solid matter of about 582kg; Solid matter is carried out dry, roasting, maturing temperature is 900 DEG C, and roasting time is 3 hours, makes praseodymium oxalate neodymium fully oxidized, obtains the oxidation Praseodymium neodymium that purity reaches 99.12% and is about 237kg; Obtain liquid phase substance after solid-liquid separation and enter hydrolyzing process;
E. hydrolyzing process: add reduced iron powder in the liquid phase substance of step D, this reduced iron powder iron level >=98%, in reduced iron powder and liquid phase substance, the mass ratio of iron protochloride is 0.016:1, namely the add-on of reduced iron powder is about 22kg, the reaction of intensification Accelerating reduction iron powder and free acid, makes the pH value of solution be 5, be hydrolyzed, hydrolysis temperature is 95 DEG C, and hydrolysis time is 5 hours, and the metallic impurity in solution beyond iron are fully hydrolyzed;
F. three solid-liquid separation: the hydrating solution of step e is carried out solid-liquid separation by plate-and-frame filter press, the filter residue obtained is about 50kg(because of other metallic impurity in solution and is fully hydrolyzed, in the filter residue obtained, the overwhelming majority is ironic hydroxide), these filter residues are through 550 DEG C of high-temperature calcinations, filter residue is substantially oxidized, to reduce the consumption of hydrochloric acid, the filter residue of high-temperature calcination oxidation is after grinding, repeating step A, B, repeating step A, obtaining secondary filter residue after B is red iron oxide, with deionized water, red iron oxide is washed 3 times, press dry rear to sell directly outward, for building materials, coating etc., repeating step A, B obtain the filtrate 0.45m that total amount of rare earth is about 25g/L
3, these filtrates enter step C, and after the oxalic acid reaction adding about 13kg, obtain by step D the oxidation Praseodymium neodymium 10.5kg that purity reaches 99.13%, so far, the rare earth reclaimed altogether is about 247.5kg, the filtrate that solid-liquid separation obtains enters acid, oxidation operation,
G. acid, oxidation operation: add in the filtrate of step F concentration be 85% industrial phosphoric acid carry out acidifying, in industrial phosphoric acid and filtrate, the mass ratio of iron protochloride is 1:3.5, and namely the add-on of industrial phosphoric acid is about 395kg; The hydrogen peroxide that adds that is slow in souring soln, that continue is oxidized, this hydrogen peroxide is the industrial hydrogen peroxide of massfraction > 25%, in whole oxidising process, the temperature of solution should control to be 45 DEG C, prevent decomposing hydrogen dioxide solution from causing waste, in hydrogen peroxide and souring soln, the mass ratio of iron protochloride is 0.665:1, namely the add-on of hydrogen peroxide is about 920kg, and oxidization time is 45 minutes;
H. tertiary iron phosphate precipitation: add diammonium phosphate and react in the oxidizing solution of step G, this diammonium phosphate is industrial phosphoric acid two ammonium of content > 98%, in diammonium phosphate and oxidizing solution, the mass ratio of iron protochloride is 0.85:1, namely the add-on of diammonium phosphate is about 1176kg, temperature of reaction is 45 DEG C, and the reaction times is 60 minutes; After question response completes, with ammoniacal liquor, the pH value of reaction soln is adjusted to 2.5, this ammoniacal liquor is the industrial ammonia of content > 25%, obtains tertiary iron phosphate precipitation;
I. four solid-liquid separation: step H is obtained product and carry out solid-liquid separation by plate-and-frame filter press, the filter cake furnishing concentration obtained is the slurry of 50%, under whipped state, the industrial phosphoric acid that concentration is 85% is added in slurries, the mass ratio of industrial phosphoric acid and slurries is about 0.04:1, the concentration of phosphoric acid in slurries is made to adjust to 0.5 mol/L, be warming up to 90 DEG C, react 45 minutes, after question response completes, with ammoniacal liquor, the pH value of reaction soln is adjusted to 3.5, this ammoniacal liquor is the industrial ammonia of content > 25%, again reaction soln is filtered by plate-and-frame filter press, the filter cake formed washs 3 times again, through 85 DEG C of oven dry, obtain ferrophosphorus than the battery-grade iron phosphate about 2.03 tons for 1:0.985, for productions such as ferric phosphate lithium cells, the filtrate that solid-liquid separation and washing, filtration obtain enters evaporation concentration operation respectively,
J. evaporation concentration: carry out evaporation concentration by after twice filtrate mixing of step I, filtrate is made to be evaporated to hypersaturated state, in whole evaporating concentration process, carry out under low temperature (but at least should guarantee that filtrate is evaporated to hypersaturated state) negative pressure as far as possible, decompose to prevent ammonium chloride, evaporation is after gas is condensed into water, cause respectively dissolving with hydrochloric acid operation, solid-liquid separation process, secondary solid-liquid separation process, three solid-liquid separation process and four solid-liquid separation process washing, size mixing and carry out water cycle; Under whipped state (about 32 revs/min), supersaturated solution is cooled to normal temperature, obtains ammonium chloride crystals;
K. five solid-liquid separation: the crystal solution obtained by step J carries out centrifugation by separating centrifuge, obtains the ammonium chloride of about 600kg, sell, for fertilizer and production of compound fertilizer etc. directly; Be separated mother liquor (about 1.4 m obtained
3) be back to step J and carry out repeated evaporation and concentrate, stop the discharge of ammonium nitrogen.
Filter residue in the present invention's solid-liquid separation and three solid-liquid separation process together can carry out high-temperature calcination.
embodiment 3
The present invention includes following order step:
A. dissolving with hydrochloric acid: add in 1 ton of neodymium iron boron waste material (total amount of rare earth is about 25%) concentration be 23% hydrochloric acid carry out acidolysis, this hydrochloric acid is diluted through deionized water by the technical hydrochloric acid of concentration 32% and obtains, the mass ratio of hydrochloric acid and neodymium iron boron waste material is 2:1, acidolysis temperature is 105 DEG C, the acidolysis time is 2.5 hours, neodymium iron boron waste material is fully dissolved by hydrochloric acid, and the pH value of acidolysis reaction terminal is 1.6;
B. a solid-liquid separation: the solution of steps A is carried out solid-liquid separation by plate-and-frame filter press, obtain about 150kg(total amount of rare earth and be about 8%) a filter residue, a filter residue is through 600 DEG C of high-temperature calcinations, filter residue is substantially oxidized, to reduce the consumption of hydrochloric acid, the filter residue of high-temperature calcination oxidation is after grinding, repeating step A, B, the secondary filter residue of about 138kg is obtained after repeating step A, B, this secondary filter residue is red iron oxide, with deionized water wash 3 times, after pressing dry, sell, for building materials, coating etc. directly; The filtrate that obtains after solid-liquid separation (namely filter residue is separated to be separated with secondary filter residue and obtains) for total amount of rare earth be about 70g/L, volume is about 3.4m
3filtrate, filtrate enters oxalic acid precipitation step;
C. oxalic acid precipitation: the filtrate of step B is warming up to 90 DEG C, under whipped state, adds oxalic acid in filtrate, this oxalic acid is the industrial ethanedioic acid of content 99.6%, and the mass ratio of oxalic acid and filtrate middle-weight rare earths total amount is 1.17:1, and namely oxalic acid adds and is about 278kg, react after 40 minutes, leave standstill 3.5 hours;
D. two solid-liquid separation: the solution temperature of step C is down to 28 DEG C, then carries out solid-liquid separation by plate-and-frame filter press, the solid matter (i.e. praseodymium oxalate neodymium) obtained, after deionized water wash 3 times, obtains the solid matter of about 582kg; Solid matter is carried out dry, roasting, maturing temperature is 980 DEG C, and roasting time is 3.5 hours, makes praseodymium oxalate neodymium fully oxidized, obtains the oxidation Praseodymium neodymium that purity reaches 99.12% and is about 237kg; Obtain liquid phase substance after solid-liquid separation and enter hydrolyzing process;
E. hydrolyzing process: add reduced iron powder in the liquid phase substance of step D, this reduced iron powder iron level >=98%, in reduced iron powder and liquid phase substance, the mass ratio of iron protochloride is 0.014:1, namely the add-on of reduced iron powder is about 19.4kg, the reaction of intensification Accelerating reduction iron powder and free acid, makes the pH value of solution be 5.5, be hydrolyzed, hydrolysis temperature is 93 DEG C, and hydrolysis time is 6 hours, and the metallic impurity in solution beyond iron are fully hydrolyzed;
F. three solid-liquid separation: the hydrating solution of step e is carried out solid-liquid separation by plate-and-frame filter press, the filter residue obtained is about 50kg(because of other metallic impurity in solution and is fully hydrolyzed, in the filter residue obtained, the overwhelming majority is ironic hydroxide), these filter residues are through 600 DEG C of high-temperature calcinations, filter residue is substantially oxidized, to reduce the consumption of hydrochloric acid, the filter residue of high-temperature calcination oxidation is after grinding, repeating step A, B, repeating step A, obtaining secondary filter residue after B is red iron oxide, with deionized water, red iron oxide is washed 3 times, press dry rear to sell directly outward, for building materials, coating etc., repeating step A, B obtain the filtrate 0.45m that total amount of rare earth is about 25g/L
3, these filtrates enter step C, and after the oxalic acid reaction adding about 13.2kg, obtain by step D the oxidation Praseodymium neodymium 10.5kg that purity reaches 99.13%, so far, the rare earth reclaimed altogether is about 247.5kg, the filtrate that solid-liquid separation obtains enters acid, oxidation operation,
G. acid, oxidation operation: add in the filtrate of step F concentration be 85% industrial phosphoric acid carry out acidifying, in industrial phosphoric acid and filtrate, the mass ratio of iron protochloride is 1:3.5, and namely the add-on of industrial phosphoric acid is about 395kg; The hydrogen peroxide that adds that is slow in souring soln, that continue is oxidized, this hydrogen peroxide is the industrial hydrogen peroxide of massfraction > 25%, in whole oxidising process, the temperature of solution should control to be 50 DEG C, prevent decomposing hydrogen dioxide solution from causing waste, in hydrogen peroxide and souring soln, the mass ratio of iron protochloride is 0.67:1, namely the add-on of hydrogen peroxide is about 927kg, and oxidization time is 55 minutes;
H. tertiary iron phosphate precipitation: add diammonium phosphate and react in the oxidizing solution of step G, this diammonium phosphate is industrial phosphoric acid two ammonium of content > 98%, in diammonium phosphate and oxidizing solution, the mass ratio of iron protochloride is 1:1, namely the add-on of diammonium phosphate is about 1590kg, temperature of reaction is 55 DEG C, and the reaction times is 50 minutes; After question response completes, with ammoniacal liquor, the pH value of reaction soln is adjusted to 2.0, this ammoniacal liquor is the industrial ammonia of content > 25%, obtains tertiary iron phosphate precipitation;
I. four solid-liquid separation: step H is obtained product and carry out solid-liquid separation by plate-and-frame filter press, the filter cake furnishing concentration obtained is the slurry of 50%, under whipped state, the industrial phosphoric acid that concentration is 85% is added in slurries, the mass ratio of industrial phosphoric acid and slurries is about 0.04:1, the concentration of phosphoric acid in slurries is made to adjust to 0.5 mol/L, be warming up to 80 DEG C, react 50 minutes, after question response completes, with ammoniacal liquor, the pH value of reaction soln is adjusted to 3.0, this ammoniacal liquor is the industrial ammonia of content > 25%, again reaction soln is filtered by plate-and-frame filter press, the filter cake formed washs 3 times again, through 90 DEG C of oven dry, obtain ferrophosphorus than the battery-grade iron phosphate about 2.03 tons for 1:0.985, for productions such as ferric phosphate lithium cells, the filtrate that solid-liquid separation and washing, filtration obtain enters evaporation concentration operation respectively,
J. evaporation concentration: carry out evaporation concentration by after twice filtrate mixing of step I, filtrate is made to be evaporated to hypersaturated state, in whole evaporating concentration process, carry out under low temperature (but at least should guarantee that filtrate is evaporated to hypersaturated state) negative pressure as far as possible, decompose to prevent ammonium chloride, evaporation is after gas is condensed into water, cause respectively dissolving with hydrochloric acid operation, solid-liquid separation process, secondary solid-liquid separation process, three solid-liquid separation process and four solid-liquid separation process washing, size mixing and carry out water cycle; Under whipped state (about 32 revs/min), supersaturated solution is cooled to normal temperature, obtains ammonium chloride crystals;
K. five solid-liquid separation: the crystal solution obtained by step J carries out centrifugation by separating centrifuge, obtains the ammonium chloride of about 600kg, sell, for fertilizer and production of compound fertilizer etc. directly; Be separated mother liquor (about 1.4 m obtained
3) be back to step J and carry out repeated evaporation and concentrate, stop the discharge of ammonium nitrogen.
Filter residue in the present invention's solid-liquid separation and three solid-liquid separation process together can carry out high-temperature calcination.
embodiment 4
The present invention includes following order step:
A. dissolving with hydrochloric acid: add in 1 ton of neodymium iron boron waste material (total amount of rare earth is about 25%) concentration be 16% hydrochloric acid carry out acidolysis, this hydrochloric acid is diluted through deionized water by the technical hydrochloric acid of concentration 32% and obtains, the mass ratio of hydrochloric acid and neodymium iron boron waste material is 2:1, acidolysis temperature is 110 DEG C, the acidolysis time is 3 hours, neodymium iron boron waste material is fully dissolved by hydrochloric acid, and the pH value of acidolysis reaction terminal is 2.5;
B. a solid-liquid separation: the solution of steps A is carried out solid-liquid separation by plate-and-frame filter press, obtain about 150kg(total amount of rare earth and be about 8%) a filter residue, a filter residue is through 500 DEG C of high-temperature calcinations, filter residue is substantially oxidized, to reduce the consumption of hydrochloric acid, the filter residue of high-temperature calcination oxidation is after grinding, repeating step A, B, the secondary filter residue of about 138kg is obtained after repeating step A, B, this secondary filter residue is red iron oxide, with deionized water wash 3 times, after pressing dry, sell, for building materials, coating etc. directly; The filtrate that obtains after solid-liquid separation (namely filter residue is separated to be separated with secondary filter residue and obtains) for total amount of rare earth be about 70g/L, volume is about 3.4m
3filtrate, filtrate enters oxalic acid precipitation step;
C. oxalic acid precipitation: the filtrate of step B is warming up to 70 DEG C, under whipped state, adds oxalic acid in filtrate, this oxalic acid is the industrial ethanedioic acid of content 99.6%, and the mass ratio of oxalic acid and filtrate middle-weight rare earths total amount is 1.18:1, and namely oxalic acid adds and is about 280kg, react after 40 minutes, leave standstill 4 hours;
D. two solid-liquid separation: the solution temperature of step C is down to 25 DEG C, then carries out solid-liquid separation by plate-and-frame filter press, the solid matter (i.e. praseodymium oxalate neodymium) obtained, after deionized water wash 3 times, obtains the solid matter of about 583kg; Solid matter is carried out dry, roasting, maturing temperature is 950 DEG C, and roasting time is 2.5 hours, makes praseodymium oxalate neodymium fully oxidized, obtains the oxidation Praseodymium neodymium that purity reaches 99.12% and is about 237kg; Obtain liquid phase substance after solid-liquid separation and enter hydrolyzing process;
E. hydrolyzing process: add reduced iron powder in the liquid phase substance of step D, this reduced iron powder iron level >=98%, in reduced iron powder and liquid phase substance, the mass ratio of iron protochloride is 0.018:1, namely the add-on of reduced iron powder is about 25kg, the reaction of intensification Accelerating reduction iron powder and free acid, makes the pH value of solution be 6, be hydrolyzed, hydrolysis temperature is 95 DEG C, and hydrolysis time is 4.5 hours, and the metallic impurity in solution beyond iron are fully hydrolyzed;
F. three solid-liquid separation: the hydrating solution of step e is carried out solid-liquid separation by plate-and-frame filter press, the filter residue obtained is about 50kg(because of other metallic impurity in solution and is fully hydrolyzed, in the filter residue obtained, the overwhelming majority is ironic hydroxide), these filter residues are through 500 DEG C of high-temperature calcinations, filter residue is substantially oxidized, to reduce the consumption of hydrochloric acid, the filter residue of high-temperature calcination oxidation is after grinding, repeating step A, B, repeating step A, obtaining secondary filter residue after B is red iron oxide, with deionized water, red iron oxide is washed 3 times, press dry rear to sell directly outward, for building materials, coating etc., repeating step A, B obtain the filtrate 0.45m that total amount of rare earth is about 25g/L
3, these filtrates enter step C, and after the oxalic acid reaction adding about 13.3kg, obtain by step D the oxidation Praseodymium neodymium 11kg that purity reaches 99.13%, so far, the rare earth reclaimed altogether is about 248kg, the filtrate that solid-liquid separation obtains enters acid, oxidation operation,
G. acid, oxidation operation: add in the filtrate of step F concentration be 85% industrial phosphoric acid carry out acidifying, in industrial phosphoric acid and filtrate, the mass ratio of iron protochloride is 1:3.5, and namely the add-on of industrial phosphoric acid is about 395kg; The hydrogen peroxide that adds that is slow in souring soln, that continue is oxidized, this hydrogen peroxide is the industrial hydrogen peroxide of massfraction > 25%, in whole oxidising process, the temperature of solution should control to be 55 DEG C, prevent decomposing hydrogen dioxide solution from causing waste, in hydrogen peroxide and souring soln, the mass ratio of iron protochloride is 0.68:1, namely the add-on of hydrogen peroxide is about 940kg, and oxidization time is 50 minutes;
H. tertiary iron phosphate precipitation: add diammonium phosphate and react in the oxidizing solution of step G, this diammonium phosphate is industrial phosphoric acid two ammonium of content > 98%, in diammonium phosphate and oxidizing solution, the mass ratio of iron protochloride is 0.9:1, namely the add-on of diammonium phosphate is about 1245kg, temperature of reaction is 55 DEG C, and the reaction times is 55 minutes; After question response completes, with ammoniacal liquor, the pH value of reaction soln is adjusted to 1.8, this ammoniacal liquor is the industrial ammonia of content > 25%, obtains tertiary iron phosphate precipitation;
I. four solid-liquid separation: step H is obtained product and carry out solid-liquid separation by plate-and-frame filter press, the filter cake furnishing concentration obtained is the slurry of 50%, under whipped state, the industrial phosphoric acid that concentration is 85% is added in slurries, the mass ratio of industrial phosphoric acid and slurries is about 0.04:1, the concentration of phosphoric acid in slurries is made to adjust to 0.5 mol/L, be warming up to 70 DEG C, react 60 minutes, after question response completes, with ammoniacal liquor, the pH value of reaction soln is adjusted to 2.5, this ammoniacal liquor is the industrial ammonia of content > 25%, again reaction soln is filtered by plate-and-frame filter press, the filter cake formed washs 3 times again, through 90 DEG C of oven dry, obtain ferrophosphorus than the battery-grade iron phosphate about 2.03 tons for 1:0.985, for productions such as ferric phosphate lithium cells, the filtrate that solid-liquid separation and washing, filtration obtain enters evaporation concentration operation respectively,
J. evaporation concentration: carry out evaporation concentration by after twice filtrate mixing of step I, filtrate is made to be evaporated to hypersaturated state, in whole evaporating concentration process, carry out under low temperature (but at least should guarantee that filtrate is evaporated to hypersaturated state) negative pressure as far as possible, decompose to prevent ammonium chloride, evaporation is after gas is condensed into water, cause respectively dissolving with hydrochloric acid operation, solid-liquid separation process, secondary solid-liquid separation process, three solid-liquid separation process and four solid-liquid separation process washing, size mixing and carry out water cycle; Under whipped state (about 32 revs/min), supersaturated solution is cooled to normal temperature, obtains ammonium chloride crystals;
K. five solid-liquid separation: the crystal solution obtained by step J carries out centrifugation by separating centrifuge, obtains the ammonium chloride of about 600kg, sell, for fertilizer and production of compound fertilizer etc. directly; Be separated mother liquor (about 1.4 m obtained
3) be back to step J and carry out repeated evaporation and concentrate, stop the discharge of ammonium nitrogen.
Filter residue in the present invention's solid-liquid separation and three solid-liquid separation process together can carry out high-temperature calcination.
Claims (8)
1. an extraction and application method for neodymium iron boron waste material, comprises following order step:
A. dissolving with hydrochloric acid: add in neodymium iron boron waste material concentration be 15 ~ 25% hydrochloric acid carry out acidolysis, the pH value of acidolysis terminal is 1.5 ~ 2.5, and the mass ratio of hydrochloric acid and neodymium iron boron waste material is 2:1, acidolysis temperature >=90 DEG C, the acidolysis time is 2 ~ 3 hours, and neodymium iron boron waste material is fully dissolved by hydrochloric acid;
B. a solid-liquid separation: the solution of steps A is carried out solid-liquid separation, obtains a filter residue, and a filter residue is after the high-temperature calcination of 400 ~ 600 DEG C, repeating step A, B, obtain secondary filter residue after repeating step A, B, this secondary filter residue is red iron oxide, sells directly; The filtrate obtained after solid-liquid separation enters oxalic acid precipitation step;
C. oxalic acid precipitation: the filtrate of step B is warming up to 60 ~ 90 DEG C, adds oxalic acid in filtrate, the mass ratio of oxalic acid and filtrate middle-weight rare earths total amount is 1.1 ~ 1.2:1, at least reacts after 25 minutes, leaves standstill 3 ~ 4 hours;
D. two solid-liquid separation: the solution of step C is carried out solid-liquid separation, the solid matter obtained carries out drying after washing, roasting, and maturing temperature is 850 ~ 1000 DEG C, and roasting time is 2 ~ 4 hours, obtains the praseodymium neodymium oxide that purity reaches more than 98%; Obtain liquid phase substance after solid-liquid separation and enter hydrolyzing process;
E. hydrolyzing process: add reduced iron powder in the liquid phase substance of step D, in reduced iron powder and liquid phase substance, the mass ratio of iron protochloride is 0.01 ~ 0.02:1, the pH value of solution is made to be 5 ~ 7, be hydrolyzed, hydrolysis temperature is 90 ~ 95 DEG C, hydrolysis time is 4 ~ 6 hours, and the metallic impurity in solution beyond iron are fully hydrolyzed;
F. three solid-liquid separation: the hydrating solution of step e is carried out solid-liquid separation, the filter residue obtained is repeating step A, B after the high-temperature calcination of 400 ~ 600 DEG C, and obtaining secondary filter residue after repeating step A, B is red iron oxide, sells directly; The filtrate that solid-liquid separation obtains enters acid, oxidation operation;
G. acid, oxidation operation: add in the filtrate of step F concentration be 85% industrial phosphoric acid carry out acidifying, in industrial phosphoric acid and filtrate, the mass ratio of iron protochloride is 1:3.5; In souring soln, add hydrogen peroxide be oxidized, in hydrogen peroxide and souring soln, the mass ratio of iron protochloride is 0.66 ~ 0.68:1, and oxidizing temperature is 40 ~ 60 DEG C, and oxidization time is 40 ~ 60 minutes;
H. tertiary iron phosphate precipitation: add diammonium phosphate and react in the oxidizing solution of step G, in diammonium phosphate and oxidizing solution, the mass ratio of iron protochloride is 0.8 ~ 1.2:1, and temperature of reaction is 40 ~ 60 DEG C, and the reaction times is 50 ~ 60 minutes; After question response completes, with ammoniacal liquor, the pH value of reaction soln is adjusted to 1.5 ~ 2.5, obtains tertiary iron phosphate precipitation;
I. four solid-liquid separation: step H is obtained product and carry out solid-liquid separation, the filter cake furnishing concentration obtained is the slurry of 50%, under whipped state, the industrial phosphoric acid that concentration is 85% is added in slurries, the mass ratio of industrial phosphoric acid and slurries is 0.04:1, the concentration of phosphoric acid in slurries is made to be 0.5 mol/L, be warming up to 60 ~ 90 DEG C, react 30 ~ 60 minutes, after question response completes, with ammoniacal liquor, the pH value of reaction soln is adjusted to 2.5 ~ 3.5, again reaction soln is filtered, the filter cake formed is dried after washing under the condition of 60 ~ 90 DEG C, obtain ferrophosphorus than the battery-grade iron phosphate for 1:0.97 ~ 1.02, the filtrate that solid-liquid separation and washing, filtration obtain enters evaporation concentration operation respectively,
J. evaporation concentration: carry out evaporation concentration by after twice filtrate mixing of step I, make filtrate be evaporated to hypersaturated state, after evaporation gas is condensed into water, cause dissolving with hydrochloric acid and/or solid-liquid separation process; Supersaturated solution is cooled to normal temperature, obtains ammonium chloride crystals;
K. five solid-liquid separation: the crystal solution obtained by step J carries out centrifugation, obtains ammonium chloride, sell directly; Be separated the mother liquor that obtains to be back to step J and to carry out repeated evaporation and concentrate.
2. the extraction and application method of neodymium iron boron waste material according to claim 1, is characterized in that: the hydrochloric acid in steps A is obtained through deionized water or distilled water diluting by the technical hydrochloric acid of concentration 32%.
3. the extraction and application method of neodymium iron boron waste material according to claim 1, is characterized in that: the oxalic acid in step C is the industrial ethanedioic acid of content 99.6%.
4. the extraction and application method of neodymium iron boron waste material according to claim 1, is characterized in that: reduced iron powder iron level >=98% in step e.
5. the extraction and application method of neodymium iron boron waste material according to claim 1, is characterized in that: the hydrogen peroxide in step G is the industrial hydrogen peroxide of massfraction > 25%.
6. the extraction and application method of neodymium iron boron waste material according to claim 1, is characterized in that: the diammonium phosphate in step H is industrial phosphoric acid two ammonium of content > 98%.
7. the extraction and application method of neodymium iron boron waste material according to claim 1, is characterized in that: the ammoniacal liquor in step H, I is the industrial ammonia of content > 25%.
8. the extraction and application method of neodymium iron boron waste material according to claim 1, is characterized in that: the separating device that a described solid-liquid separation, secondary solid-liquid separation, three solid-liquid separation, four solid-liquid separation adopt is respectively plate-and-frame filter press.
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| CN201410073670.6A CN103773966B (en) | 2014-03-03 | 2014-03-03 | The extraction and application method of neodymium iron boron waste material |
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| CN105238929B (en) * | 2014-10-06 | 2017-07-04 | 永州市零陵远达新材料有限公司 | A kind of recovery of waste and old Nd-Fe-B permanent magnet material middle rare earth and utilization |
| US10351931B2 (en) | 2015-01-15 | 2019-07-16 | Worcester Polytechnic Institute | Separation of recycled rare earths |
| CN105002366B (en) * | 2015-07-14 | 2017-11-17 | 中稀天马新材料科技股份有限公司 | A kind of method of the recovering rare earth from neutralization slag caused by neodymium iron boron waste material recovering rare earth process |
| CN105087967A (en) * | 2015-08-30 | 2015-11-25 | 常州市鼎日环保科技有限公司 | Device for recycling rare earth elements in neodymium iron boron waste materials |
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| CN106319575B (en) * | 2016-11-02 | 2018-04-17 | 江西理工大学 | A kind of method of neodymium iron boron greasy filth waste material electrolytic preparation Nd Fe B alloys |
| CN107317029B (en) * | 2017-06-22 | 2019-11-08 | 赣州有色冶金研究所 | A kind of preparation method of ferric phosphate |
| CN107794373B (en) * | 2017-11-06 | 2019-01-22 | 孙东江 | The integrated conduct method of the useless magnetic material of neodymium iron boron |
| CN111575509A (en) * | 2020-05-22 | 2020-08-25 | 包头稀土研究院 | Method for recovering rare earth elements from neodymium iron boron magnet waste and application |
| CN111549230B (en) * | 2020-05-22 | 2022-04-01 | 包头稀土研究院 | Treatment method of neodymium iron boron waste |
| CN111485110A (en) * | 2020-06-05 | 2020-08-04 | 中国林业科学研究院林产化学工业研究所 | Method for improving utilization rate of valuable elements in rare earth |
| CN114572936B (en) * | 2022-03-01 | 2023-03-24 | 中稀天马新材料科技股份有限公司 | Method for recycling hydrochloric acid in process of extracting rare earth oxide from neodymium iron boron oxide material |
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