CN103667716B - A kind of at C2H2O4-NH3The method simultaneously reclaiming neodymium, praseodymium, dysprosium, cobalt, ferrum under system from neodymium iron boron greasy filth - Google Patents
A kind of at C2H2O4-NH3The method simultaneously reclaiming neodymium, praseodymium, dysprosium, cobalt, ferrum under system from neodymium iron boron greasy filth Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 61
- 229910052779 Neodymium Inorganic materials 0.000 title claims abstract description 56
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052777 Praseodymium Inorganic materials 0.000 title claims abstract description 53
- 229910052692 Dysprosium Inorganic materials 0.000 title claims abstract description 52
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 52
- 239000010941 cobalt Substances 0.000 title claims abstract description 52
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 52
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 title claims abstract description 52
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 title claims abstract description 47
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 39
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 40
- 238000001556 precipitation Methods 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 230000008929 regeneration Effects 0.000 claims description 9
- 238000011069 regeneration method Methods 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000011084 recovery Methods 0.000 abstract description 18
- 238000005516 engineering process Methods 0.000 abstract description 12
- 239000002699 waste material Substances 0.000 abstract description 8
- 238000004088 simulation Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000000047 product Substances 0.000 description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- -1 ferroboron Substances 0.000 description 13
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 10
- 229910052761 rare earth metal Inorganic materials 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000013461 design Methods 0.000 description 6
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 4
- 239000006247 magnetic powder Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000010303 mechanochemical reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000007500 overflow downdraw method Methods 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 229910001004 magnetic alloy Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
A kind of at C2H2O4-NH3The method simultaneously reclaiming neodymium, praseodymium, dysprosium, cobalt, ferrum under system from neodymium iron boron greasy filth, belongs to neodymium iron boron greasy filth recovery technology field.C2H2O4-NH3System thermodynamic study and simulation, set up thermodynamical model, it is determined that technique applicatory and technological parameter.And at C2H2O4-NH3Regulate and choose twice pH under system and be: (0.5～2.5)-9 carries out " coordinating-precipitation ", can reach to reclaim the effect of neodymium, praseodymium, dysprosium, cobalt, ferrum simultaneously.This flow process can effectively shorten early stage Process Exploration, simple to operate, concise in technology, effectively reduces waste discharge, and realizes the full recovery of neodymium in neodymium iron boron greasy filth, praseodymium, dysprosium, cobalt, ferrum.Wherein, response rate >=99% of neodymium；Response rate >=99% of praseodymium；Response rate >=79% of cobalt；Response rate >=99% of dysprosium；Response rate >=99% of ferrum.
Description
Technical field
The present invention relates to a kind of at C2H2O4-NH3The method extracting neodymium, praseodymium, dysprosium, cobalt, ferrum under system from neodymium iron boron greasy filth, belongs to neodymium iron boron greasy filth recovery technology field.
Background technology
Nineteen eighty-three with American scientist, Japan has almost found that its huge magnetic energy product has refreshed existing permanent magnet material record, causes the change that permanent magnet material market, the world is huge with since (third generation) RE permanent magnetic alloy that neodymium iron boron is matrix simultaneously.The exploitation of domestic neodymium iron boron is very fast, and the yearly productive capacity of the nearly various schools of thinkers enterprise in the whole nation reaches nearly more than 100,000 ton.It is well known that in the production process of NdFeB material, have many leftover pieces, defect ware and cut the waste material got off, total losses are up to more than 30%, therefore, strengthen research and production that neodymium iron boron waste material reclaims, have important realistic meaning.
Along with from neodymium iron boron waste material, the technology of recovering rare earth is increasingly mature, increasing businessman sees abundant profit therein.According to data, being with in Zhejiang and Guangdong one, the big and small producer reclaiming neodymium iron boron waste material just has several thousand.And this wherein just has black workshop, the underground much not having qualification of production, they will obtain the greasy filth after the neodymium iron boron waste material of coming, particularly polishing and line cutting, be only carry out coarse oxidizing roasting, then through the flow process such as acid-soluble, thus extracting central rare earth element.Owing to these businessmans had not both had production permit, also without regular production flow process.In this way not only significant wastage to rare earth resources, but also local environment can be formed huge pollution.
For the object of study neodymium iron boron greasy filth of this patent, the NdFeB magnetic powder how again preparing regeneration from neodymium iron boron greasy filth is the research core of this problem.Have bibliographical information, have people just to utilize Fe-Pr and Fe-Nd rapid quenching technique successfully to prepare magnetic is long-pending can the Hard Magnetic phase of up to 40KOe.Domestic Xiao Yao good fortune and Zhou Shouzeng et al. once used reduction-diffusion process successfully to produce out neodymium iron boron.The method by by NdO powder, Fe powder, Ca powder mixing compressing after, at 860 DEG C-1180 DEG C, carry out vat blue RS, be shaped again afterwards, sinter, it is thus achieved that magnetic energy product (BH) max=200-238KJ/m3NdFeB alloy.Sun Guangfei, Chen Jufang have also prepared NdFeB alloy by using reduction fusion method.Reduction fusion method is to reduce Neodymium chloride by calcium metal, and the neodymium metal being then reduced under the high temperature conditions merges with alloy element Fe, boron and prepares NdFeB alloy.And AngshumanPal, AlexanderGabay, GeorgeC.Hadjipanayis et al. is once by preparing NdFeB alloy and rich neodymium phase by Dineodymium trioxide powder, ferroboron, calcium powder ball milling, heat-treating methods, and wherein the coercivity of NdFeB alloy is more than 12KOe.Also someone passes through successfully to have prepared that NdFeB is nanocrystalline and nanometer sheet by adding surfactant in high-energy ball milling.Therefore, preparing NdFeB alloy by this method of Mechano-chemical Synthesizing is be worth using for reference.
The applicant intend adopting solid liquid phase-solid phase in NdFeB greasy filth-physical method for separation greasy filth acid-soluble-neodymium ferrum co-precipitation-high-temperature calcination-mechanochemical reaction synthesis NdFeB magnetic powder technique, with the acid-soluble sedimentation method, the sulfuric acid double salt sedimentation method, full extraction these compared by the method for Separation-purification, either directly through solid liquid phase-solid phase in NdFeB greasy filth-physical method for separation greasy filth acid-soluble-neodymium ferrum co-precipitation-high-temperature calcination-mechanochemical reaction synthesis NdFeB magnetic powder technique prepares the method for NdFeB alloy and can reduce cost further, reduce numerous and diverse chemical process, human resources and material resources are saved, decrease the discharge of waste water and waste liquid simultaneously, and realize reclaiming and recycling economy truly of full element.
Possessing the element of recyclable reproduction value in neodymium iron boron greasy filth containing neodymium, praseodymium, dysprosium, cobalt, ferrum these five kinds, will prepare neodymium iron boron regeneration magnetic powder, high-recovery is settled out neodymium simultaneously, praseodymium, dysprosium, cobalt, ferrum become crucial.
Summary of the invention
In this patent, would first, through neodymium, praseodymium, dysprosium, cobalt, these five kinds of elements of ferrum by calculating simulation, set up thermodynamical model, determined and optimize the optimal parameter of neodymium, praseodymium, dysprosium, cobalt, optimised process that ferrum reclaims simultaneously and technique by thermodynamical model.
It is contemplated that at C2H2O4-NH3The thermodynamical model of neodymium, praseodymium, dysprosium, cobalt, five kinds of elements of ferrum is set up under system, the result using for reference simulation determines that cooperation-depositing technology that neodymium, praseodymium, dysprosium, cobalt, ferrum reclaim selects, the process program being determined by reclaims the compound of neodymium, praseodymium, dysprosium, cobalt, these five kinds of elements of ferrum simultaneously, reclaims product and can be used for regenerating the preparation of neodymium iron boron.
Present invention determine that at C2H2O4-NH3First the method simultaneously reclaiming neodymium, praseodymium, dysprosium, cobalt, iron process under system from neodymium iron boron greasy filth, be the technical scheme is that, by searching each element at C2H2O4-NH3Contingent complex reaction and reaction equilibrium constant under system, set up thermodynamical model (preferably by MATLAB software for calculation)；Then, the thermodynamical model by having been built up is determined and is reclaimed the selection of parameter in neodymium, praseodymium, dysprosium, cobalt, the technique of ferrum and technique: at C2H2O4-NH3Under system, it is determined that technique is: neodymium iron boron greasy filth distillation, acid-soluble, oxidation, coordinate precipitate to obtain product.
The foundation of above-mentioned thermodynamical model (i.e. thermodynamical model after sedimentation equilibrium) comprises the following steps: first, consult at C2H2O4-NH3The equilibrium constant of neodymium, praseodymium, dysprosium, cobalt, the contingent reaction of ferrum and each reaction under system, can be obtained equation by the ionization equilibrium of water:
[H+]=10-pH(1-1)
[OH-]=Kw*10pH(1-2)
At C2H2O4In-OH system, the free metal ion concentration in solution is:
[Nd3+]=min{(Kspnac/[C2O4 2-]3)1/2,Kspnh/[OH-]3}(1-3)
[Pr3+]==min{(Ksppac/[C2O4 2-]3)1/2,KsppH/[OH-]3}(1-4)
[Dy3+]=min{(Kspdac/[C2O4 2-]3)1/2,Kspdh/[OH-]3}(1-5)
[Fe3+]=Kspf3h/[OH-]3(1-6)
[Fe2+]=min{Kspf2ac/[C2O4 2-],Kspf3h/[OH-]2}(1-7)
[Co2+]=Kspch/[OH-]2(1-8)
[H2C2O4]=[C2O4 2-]+[HC2O4 -]+[C2H2O4](1-9)
[H2C2O4]=[C2O4 2-]{1+10-pH/Kaac2+10-2pH/(Kaac2*Kaac1)}(1-10)
Owing to each metal ion is with [OH-]、[NH3]、[C2O4 2-] there is complex reaction, therefore obtain the total concentration of each metal ion in solution according to mass conservation law:
[Nd]=[Nd3+]+[Nd(OH)2+]+[Nd(C2O4)+]+[Nd(C2O4)2 -]+
[Nd(C2O4)3 3-]
=[Nd3+]+Knh*[Nd3+]*[OH-]+Knac11*[Nd3+]*[C2O4 2-]
+Knac12*[Nd3+]*[C2O4 2-]2+Knac13*[Nd3+]*[C2O4 2-]3(1-11)
[Pr]=[Pr3+]+[Pr(OH)2+]+[Pr(C2O4)+]+[Pr(C2O4)2 -]
+[Pr(C2O4)3 3-](1-12)
[Dy]=[Dy3+]+[Dy(OH)2+]+[Dy(C2O4)+]+[Dy(C2O4)2 -]+
[Dy(C2O4)3 3-](1-13)
[Fe2]=[Fe2+]+[Fe(OH)+]+[Fe(OH)2 0]+[Fe(OH)3 -]+[Fe(OH)4 2-]
+[Fe(C2O4)0]+[Fe(C2O4)2 2-]+[Fe(C2O4)3 4-]+[Fe(NH3)2+]
+[Fe(NH3)2 2+]+[Fe(NH3)4 2+]
=[Fe2+]{1+Kf2h1*[OH-]+Kf2h2*[OH-]2+Kf2h3*[OH-]3+Kf2h4*[OH-]4
+Knac11*[C2O4 2-]+Knac12*[C2O4 2-]2+Knac13*[C2O4 2-]3
+Kf2am11*[NH3]+Kf2am12*[NH3]2+Kf2am14*[NH3]4}
(1-14)
[Fe3]=[Fe3+]+[Fe(OH)2+]+[Fe(OH)2 +]+[Fe(OH)3 0]+[Fe(OH)4 2-]
=[Fe3+]{1+Kf3h1*[OH-]+Kf3h2*[OH-]2+Kf3h3*[OH-]3}
(1-15)
[Co]=[Co2+]+[Co(OH)+]+[Co(OH)2 0]+[Co(OH)3 -]+[Co(OH)4 2-]
+2*[Co2(OH)3 3-]+4*[Co4(OH)4 4-]+[Co(NH3)]
+[Co(NH3)2+]+[Co(NH3)2 2+]+[Co(NH3)3 2+]+[Co(NH3)4 2+]
+[Co(NH3)5 2+]+[Co(NH3)6 2+]
=[Co2+]{1+Kch1*[OH-]+Kch2*[OH-]2+Kch3*[OH-]3
+Kch4*[OH-]4+2*Kch21*[Co2+]*[OH-]+4*Kch44*[Co2+]3*[OH-]4
+Kcam11*[NH3]+Kcam12*[NH3]2+Kcam13*[NH3]3
+Kcam14*[NH3]4+Kcam15*[NH3]5+Kcam16*[NH3]6}(1-16)
[NH4 +]=Kam*[NH3]*[H+](1-17)
[N]=[NH3]+[NH4 +]+[Fe(NH3)2+]+[Fe(NH3)2 2+]+[Fe(NH3)4 2+
+[Co(NH3)]+[Co(NH3)2+]+[Co(NH3)2 2+]+[Co(NH3)3 2+]+
[Co(NH3)4 2+]+[Co(NH3)5 2+]+[Co(NH3)6 2+](1-18)
Parameter in table 1 is used for above-mentioned (1-1)-(1-18) formula, by converting [OH-] amount, be based upon C by chemical equilibrium, mass balance, charge conservation2H2O4-NH3Thermodynamical model under system.
Optimization model is calculated by MATLAB assembler language:
x=0:0.5:14;
u=0.1
p=u./(1+10.^(1.23-x)+10.^(5.42-2.*x))
P=1./(1+10.^(9.244-x))
a=min(2*sqrt(10^(-27.68)./p.^3),10.^(20.5-3*x))
b=10.^(11.69-2.*x);
c=10.^(3.45-3.*x);
w=10.^(13.77-2*x);
e=min(2*sqrt(10^(-27.68)./p.^3),10.^(21.17-3*x));
i=min(2*sqrt(10^(-28.8)./p.^3),10.^(21.85-3*x));
j=a.*[1+10^7.21.*p+10^11.5.*p.^2+10^14.*p.^3+10.^(x-8.5)];
g=b.*[1+10^2.9.*p+10^4.52.*p.^2+10^5.22.*p.^3+10.^(x-8.44)+10.^(2*x-18.23)+10.^(3*x-32.33)+10.^(4*x-47.72)+10^1.4.*P+10^2.2.*P.^2+10^3.74.*P.^4];
h=c.*[1+10^9.4.*p+10^16.2.*p.^2+10^20.2.*p.^3+10.^(x-2.13)+10.^(2*x-6.83)+10.^(3*x-12.33)];
q=w.*(1+10.^(x-10.7)+10.^(2.*x-18.8)+10.^(3.*x-31.5)+10.^(4.*x-45.8)+2.*10.^(x-11.3).*w+4.*10.^(4.*x-30.4).^(w.^3)+10^4.79.^p+10^6.7.*p.^2+10^9.7.*p.^3+10^2.11.^P+10^3.74.*P.^2+10^4.99.*P.^3+10^5.55.*P.^4+10^5.73.*P.^5+10^5.11.*P.^6);
r=e.*(1+10^7.21.*p+10^10.5.*p.^2+10^14.*p.^3+10.^(x-9.7));
l=i.*(1+10^7.21.*p+10^11.9.*p.^2+10^14.*p.^3+10.^(x-8.8));
y=log10(j);
m=log10(g);
n=log10(h);
o=log10(q)
t=log10(r)
z=log10(l)
plot(x,y,x,m,x,n,x,o,x,t,x,z)
Wherein, x represents pH value；U represents total oxalic acid [H2C2O4] concentration；pRepresent C in solution2O4 2-Concentration；A, b, c, w, e, i represent the free metal ion concentration value of [Nd], [Fe2], [Fe3], [Co], [Dy], [Pr] respectively；P represents free state [NH3] value；J, g, h, q, r, l represent remaining total concentration in [Nd], [Fe2], [Fe3], [Co], [Dy], [Pr] solution respectively；What y, m, n, o, t, z then represented respectively is remaining total concentration denary logarithm value in [Nd], [Fe2], [Fe3], [Co], [Dy], [Pr] solution.
It is a kind of at C that the present invention adopts said method to determine2H2O4-NH3The method simultaneously reclaiming neodymium, praseodymium, dysprosium, cobalt, ferrum under system from neodymium iron boron greasy filth, it is characterised in that comprise the following steps: after neodymium iron boron greasy filth is carried out distillation pretreatment, take hydrochloric acid and pretreated neodymium iron boron greasy filth is dissolved and filters, add H2O2, stir fully oxidized after, add NH4OH regulates pH=0.5-2.5, and adds C2H2O4Solution, after being sufficiently stirred for, adds NH again4It is 9 that OH regulates pH, the precipitation obtained is filtered, washs three times, dries, namely obtains the product of the neodymium iron boron that can be used for preparation regeneration.
Above-mentioned preferably every 5g is by hydrochloric acid 75ml, 3mlH of neodymium iron boron greasy filth correspondence 4mol/L2O2、NH4The concentration of OH is the C of 1mol/L, 1mol/L2H2O4Solution 32ml.
3 valency iron ions should be selected as far as possible, and by model can be seen that neodymium, praseodymium, dysprosium rare-earth salts optimum recovery pH value should in 0.5～2.5, and the recovery of ferrum and cobalt should be at a high ph, therefore, this patent design technology regulates pH by twice and completes, best precipitation neodymium, praseodymium, dysprosium, cobalt, ferrum pH scope in (0.5～2.5)-9, and should can pass through that a step process obtains neodymium, praseodymium, dysprosium, cobalt, ferrum coordinate precipitated product.Response rate >=99% of neodymium；Response rate >=99% of praseodymium；Response rate >=79% of cobalt；Response rate >=99% of dysprosium；Response rate >=99% of ferrum.
The beneficial effects of the present invention is:
(1) the early stage complexity exploration simultaneously reclaiming neodymium, praseodymium, dysprosium, cobalt, five kinds of elements of ferrum is overcome, it is provided that the analogy method of a kind of simplicity.
(2) make valuable element in neodymium iron boron greasy filth be obtained for good recovery, decrease the waste of element；Being reclaimed by one-time process, make recovery multiple element need repeatedly the present situation of technique get a new look and optimize, simple to operate, method is feasible.
Accompanying drawing explanation
Fig. 1 C2H2O4-NH3The impact that in system, neodymium, ferrum, cobalt, praseodymium, dysprosium concentration are changed by pH value；
Fig. 2 C2H2O4-NH3Neodymium in system, ferrum, cobalt, praseodymium, dysprosium the response rate with the change of pH value.
Detailed description of the invention
Below in conjunction with example, the present invention is further described.
Embodiment 1
Table 1 " C2H2O4-NH3 " main chemical reactions that relates in system and equilibrium constant
| NO. | Reactions | logK | NO. | Reactions | logK |
| 1 | H2O=H++OH— | logKw=-14 | 25 | Fe2++4OH—=Fe(OH)4 2— | logKf2h4=18.58 |
| 2 | Co2++OH—=Co(OH)+ | logKch1=3.3 | 26 | Fe3++OH—=Fe(OH)2+ | logKf3h1=11.87 |
| 3 | Co2++2OH—=Co(OH)2 0 | logKch2=9.2 | 27 | Fe3++2OH—=Fe(OH)2 + | logKf3h2=21.17 |
| 4 | Co2++3OH—=Co(OH)3 - | logKch3=10.5 | 28 | Fe3++3OH—=Fe(OH)3 0 | logKf3h3=29.67 |
| 5 | Co2++4OH—=Co(OH)4 2- | logKch4=10.2 | 29 | Co2++NH3=Co(NH3)2+ | logKcam11=2.11 |
| 6 | 2Co2++OH—=Co2(OH)3+ | logKch21=2.7 | 30 | Co2++2NH3=Co(NH3)2 2+ | logKcam12=3.74 |
| 7 | 4Co2++4OH—=Co4(OH)4 4+ | logKch44=25.6 | 31 | Co2++3NH3=Co(NH3)3 2+ | logKcam13=4.79 |
| 8 | Fe2++OH—=Fe(OH)+ | logKf2h1=5.56 | 32 | Co2++4NH3=Co(NH3)4 2+ | logKcam14=5.55 |
| 9 | Fe2++2OH—=Fe(OH)2 0 | logKf2h2=9.77 | 33 | Co2++5NH3=Co(NH3)5 2+ | logKcam15=5.73 |
| 10 | Fe2++3OH—=Fe(OH)3 — | logKf2h3=9.67 | 34 | Co2++6NH3=Co(NH3)6 2+ | logKcam16=5.11 |
| 11 | Nd+OH—=Nd(OH)2+ | logKnh=5.5 | 35 | Fe2++NH3=Fe(NH3)2+ | logKf2am11=1.4 |
| 12 | Pr+OH—=Pr(OH)2+ | logKpH=4.3 | 36 | Fe2++2NH3=Fe(NH3)2 2+ | logKf2am12=2.2 |
| 13 | Dy+OH—=Dy(OH)2+ | logKdh=5.2 | 37 | Fe2++4NH3=Fe(NH3)4 2+ | logKf2am13=3.74 |
| 14 | Co(OH)2(s)=Co2++2OH— | logKspch=-14.23 | 38 | Fe C2O4(s)=Fe2++C2O4 2— | logKspf2ac=-6.5 |
| 15 | Fe(OH)2(s)=Fe2++2OH— | logKspf2h=-16.31 | 39 | Fe2++C2O4 2—=Fe(C2O4)0 | logKf2ac11=2.9 |
| 16 | Fe(OH)3(s)=Fe3++3OH— | logKspf3h=-38.55 | 40 | Fe2++2C2O2—=Fe(C2O4)2 2— | logKf2ac12=4.52 |
| 17 | Nd(OH)3(s)=Nd3++3OH— | logKspnh=-21.49 | 41 | Fe2++3C2O4 2-=Fe(C2O4)3 4— | logKf2ac13=5.22 |
| 18 | Pr(OH)3(s)=Pr3++3OH— | logKsppH=-21.17 | 42 | Fe3++C2O4 2—=Fe(C2O4)+ | logKf3ac11=9.4 |
| 19 | Dy(OH)3(s)=Dy3++3OH— | logKspdh=-21.85 | 43 | Fe3++2C2O4 2—=Fe(C2O4)2 — | logKf3ac12=16.2 |
| 20 | Nd+OH—=Nd(OH)2+ | logKnh=5.5 | 44 | Fe3++3C2O4 2-=Fe(C2O4)3 3— | logKf3ac13=20.2 |
| 21 | NH3+H+=NH4 + | logKam=9.246 | 45 | H2C2O4=H++H C2O4 — | logKac1=1.23 |
| 22 | Nd2(C2O4)3(s)=2Nd2++3C2O4 2— | logKspdac=-27.68 | 46 | H C2O4 —=H++C2O4 2— | logKac2=-5.42 |
| 23 | Nd3++C2O4 2—=Nd(C2O4)+ | logKnac11=7.21 | 47 | Co2++C2O4 2—=Co(C2O4)0 | logKcac11=4.79 |
| 24 | Nd3++2C2O4 2—=Nd(C2O4)2 — | logKnac12=11.5 | 48 | Co2++2C2O4 2—=Co(C2O4)2 2— | logKcac12=6.7 |
| 25 | Nd3++3C2O4 2—=Nd(C2O4)3 3— | logKnac13=17 | 49 | Co2++3C2O4 2—=Co(C2O4)3 4— | logKcac13=9.7 |
In theory part: first, consult at C2H2O4-NH3The equilibrium constant of neodymium, praseodymium, dysprosium, cobalt, the contingent reaction of ferrum and each reaction under system, as shown in table 1.It is based upon C by chemical equilibrium, mass balance, charge conservation2H2O4-NH3Thermodynamical model under system, can be obtained equation by the ionization equilibrium of water:
[H+]=10-pH(1-1)
[OH-]=Kw*10pH(1-2)
At C2H2O4In-OH system, the free metal ion concentration in solution is:
[Nd3+]=min{(Kspnac/[C2O4 2-]3)1/2,Kspnh/[OH-]3}(1-3)
[Pr3+]==min{(Ksppac/[C2O4 2-]3)1/2,KsppH/[OH-]3}(1-4)
[Dy3+]=min{(Kspdac/[C2O4 2-]3)1/2,Kspdh/[OH-]3}(1-5)
[Fe3+]=Kspf3h/[OH-]3(1-6)
[Fe2+]=min{Kspf2ac/[C2O4 2-],Kspf3h/[OH-]2}(1-7)
[Co2+]=Kspch/[OH-]2(1-8)
[H2C2O4]=[C2O4 2-]+[HC2O4 -]+[C2H2O4](1-9)
[H2C2O4]=[C2O4 2-]{1+10-pH/Kaac2+10-2pH/(Kaac2*Kaac1)}(1-10)
Owing to each metal ion is with [OH-]、[NH3]、[C2O4 2-] there is complex reaction, therefore obtain the total concentration of each metal ion in solution according to mass conservation law:
[Nd]=[Nd3+]+[Nd(OH)2+]+[Nd(C2O4)+]+[Nd(C2O4)2 -]+
[Nd(C2O4)3 3-]
=[Nd3+]+Knh*[Nd3+]*[OH-]+Knac11*[Nd3+]*[C2O4 2-]
+Knac12*[Nd3+]*[C2O4 2-]2+Knac13*[Nd3+]*[C2O4 2-]3(1-11)
[Pr]=[Pr3+]+[Pr(OH)2+]+[Pr(C2O4)+]+[Pr(C2O4)2 -]
+[Pr(C2O4)3 3-](1-12)
[Dy]=[Dy3+]+[Dy(OH)2+]+[Dy(C2O4)+]+[Dy(C2O4)2 -]+
[Dy(C2O4)3 3-](1-13)
[Fe2]=[Fe2+]+[Fe(OH)+]+[Fe(OH)2 0]+[Fe(OH)3 -]+[Fe(OH)4 2-]
+[Fe(C2O4)0]+[Fe(C2O4)2 2-]+[Fe(C2O4)3 4-]+[Fe(NH3)2+]
+[Fe(NH3)2 2+]+[Fe(NH3)4 2+]
=[Fe2+]{1+Kf2h1*[OH-]+Kf2h2*[OH-]2+Kf2h3*[OH-]3+Kf2h4*[OH-]4
+Knac11*[C2O4 2-]+Knac12*[C2O4 2-]2+Knac13*[C2O4 2-]3
+Kf2am11*[NH3]+Kf2am12*[NH3]2+Kf2am14*[NH3]4}
(1-14)
[Fe3]=[Fe3+]+[Fe(OH)2+]+[Fe(OH)2 +]+[Fe(OH)3 0]+[Fe(OH)4 2-]
=[Fe3+]{1+Kf3h1*[OH-]+Kf3h2*[OH-]2+Kf3h3*[OH-]3}
(1-15)
[Co]=[Co2+]+[Co(OH)+]+[Co(OH)2 0]+[Co(OH)3 -]+[Co(OH)4 2-]
+2*[Co2(OH)3 3-]+4*[Co4(OH)4 4-]+[Co(NH3)]
+[Co(NH3)2+]+[Co(NH3)2 2+]+[Co(NH3)3 2+]+[Co(NH3)4 2+]
+[Co(NH3)5 2+]+[Co(NH3)6 2+]
=[Co2+]{1+Kch1*[OH-]+Kch2*[OH-]2+Kch3*[OH-]3
+Kch4*[OH-]4+2*Kch21*[Co2+]*[OH-]+4*Kch44*[Co2+]3*[OH-]4
+Kcam11*[NH3]+Kcam12*[NH3]2+Kcam13*[NH3]3
+Kcam14*[NH3]4+Kcam15*[NH3]5+Kcam16*[NH3]6}(1-16)
[NH4 +]=Kam*[NH3]*[H+](1-17)
[N]=[NH3]+[NH4 +]+[Fe(NH3)2+]+[Fe(NH3)2 2+]+[Fe(NH3)4 2+
+[Co(NH3)]+[Co(NH3)2+]+[Co(NH3)2 2+]+[Co(NH3)3 2+]+
[Co(NH3)4 2+]+[Co(NH3)5 2+]+[Co(NH3)6 2+](1-18)
Simultaneous formula (1-1)～(1-18), and the numerical value in table 1 is brought into (1-1)～(1-18), it is convertible into MATLAB assembler language:
x=0:0.5:14;
u=0.1
p=u./(1+10.^(1.23-x)+10.^(5.42-2.*x))
P=1./(1+10.^(9.244-x))
a=min(2*sqrt(10^(-27.68)./p.^3),10.^(20.5-3*x))
b=10.^(11.69-2.*x);
c=10.^(3.45-3.*x);
w=10.^(13.77-2*x);
e=min(2*sqrt(10^(-27.68)./p.^3),10.^(21.17-3*x));
i=min(2*sqrt(10^(-28.8)./p.^3),10.^(21.85-3*x));
j=a.*[1+10^7.21.*p+10^11.5.*p.^2+10^14.*p.^3+10.^(x-8.5)];
g=b.*[1+10^2.9.*p+10^4.52.*p.^2+10^5.22.*p.^3+10.^(x-8.44)+10.^(2*x-18.23)+10.^(3*x-32.33)+10.^(4*x-47.72)+10^1.4.*P+10^2.2.*P.^2+10^3.74.*P.^4];
h=c.*[1+10^9.4.*p+10^16.2.*p.^2+10^20.2.*p.^3+10.^(x-2.13)+10.^(2*x-6.83)+10.^(3*x-12.33)];
q=w.*(1+10.^(x-10.7)+10.^(2.*x-18.8)+10.^(3.*x-31.5)+10.^(4.*x-45.8)+2.*10.^(x-11.3).*w+4.*10.^(4.*x-30.4).^(w.^3)+10^4.79.^p+10^6.7.*p.^2+10^9.7.*p.^3+10^2.11.^P+10^3.74.*P.^2+10^4.99.*P.^3+10^5.55.*P.^4+10^5.73.*P.^5+10^5.11.*P.^6);
r=e.*(1+10^7.21.*p+10^10.5.*p.^2+10^14.*p.^3+10.^(x-9.7));
l=i.*(1+10^7.21.*p+10^11.9.*p.^2+10^14.*p.^3+10.^(x-8.8));
y=log10(j);
m=log10(g);
n=log10(h);
o=log10(q)
t=log10(r)
z=log10(l)
plot(x,y,x,m,x,n,x,o,x,t,x,z)
Wherein, x represents pH value；U represents total oxalic acid [H2C2O4] concentration；P represents C in solution2O4 2-Concentration；A, b, c, w, e, i represent the free metal ion concentration value of [Nd], [Fe2], [Fe3], [Co], [Dy], [Pr] respectively；P represents free state [NH3] value；J, g, h, q, r, l represent remaining total concentration in [Nd], [Fe2], [Fe3], [Co], [Dy], [Pr] solution respectively；What y, m, n, o, t, z then represented respectively is remaining total concentration denary logarithm value in [Nd], [Fe2], [Fe3], [Co], [Dy], [Pr] solution.Namely lg [ME]-pH thermodynamical model (Fig. 1) is obtained by changing the value of pH.
As shown in Figure 1.According to Fig. 1, it is believed that 3 valency iron ions should be selected as far as possible, and can be seen that neodymium, praseodymium, dysprosium rare-earth salts optimum recovery pH value should in 0.5～2.5, and the recovery of ferrum and cobalt should be at a high ph, therefore, this patent design technology regulates pH by twice and completes, best precipitation neodymium, praseodymium, dysprosium, cobalt, ferrum pH scope in (0.5～2.5)-9, and should can pass through that a step process obtains neodymium, praseodymium, dysprosium, cobalt, ferrum coordinate precipitated product.
At experimental section: taking after the neodymium iron boron greasy filth of five parts of respectively 5g carries out distillation pretreatment, pretreated neodymium iron boron greasy filth is dissolved and filters by the hydrochloric acid 75ml taking 4mol/L respectively, and addition 3ml content is the H of 30%.wt2O2, stir fully oxidized after, add 1mol/L NH4OH regulates pH=0.5, and adds the C of 1mol/L2H2O4Solution 32ml, after being sufficiently stirred for, adds the NH of 1mol/L again4OH regulates pH=9, the precipitation obtained is filtered, washs three times, dries, namely obtains the product of the neodymium iron boron that can be used for preparation regeneration.Take supernatant and carry out ICP-OES test, it is thus achieved that result as shown in Figure 2: the response rate of neodymium is: 99%；The response rate of ferrum is: 99%；The response rate of cobalt is: 79%；The response rate of praseodymium is: 99%；The response rate of dysprosium is: 99%.
Embodiment 2
Table 1 " C2H2O4-NH3 " main chemical reactions that relates in system and equilibrium constant
In theory part: first, consult at C2H2O4-NH3The equilibrium constant of neodymium, praseodymium, dysprosium, cobalt, the contingent reaction of ferrum and each reaction under system, as shown in table 1.It is based upon C by chemical equilibrium, mass balance, charge conservation2H2O4-NH3Thermodynamical model under system, as shown in Figure 1.According to Fig. 1, it is believed that 3 valency iron ions should be selected as far as possible, and can be seen that neodymium, praseodymium, dysprosium rare-earth salts optimum recovery pH value should in 0.5～2.5, and the recovery of ferrum and cobalt should be at a high ph, therefore, this patent design technology regulates pH by twice and completes, best precipitation neodymium, praseodymium, dysprosium, cobalt, ferrum pH scope in (0.5～2.5)-9, and should can pass through that a step process obtains neodymium, praseodymium, dysprosium, cobalt, ferrum coordinate precipitated product.
At experimental section: taking after the neodymium iron boron greasy filth of five parts of respectively 5g carries out distillation pretreatment, pretreated neodymium iron boron greasy filth is dissolved and filters by the hydrochloric acid 75ml taking 4mol/L respectively, and addition 3ml content is the H of 30%.wt2O2, stir fully oxidized after, add 1mol/L NH4OH regulates pH=1, and adds the C of 1mol/L2H2O4Solution 32ml, after being sufficiently stirred for, adds the NH of 1mol/L again4OH regulates pH=9, the precipitation obtained is filtered, washs three times, dries, namely obtains the product of the neodymium iron boron that can be used for preparation regeneration.Take supernatant and carry out ICP-OES test, it is thus achieved that result as shown in Figure 2: the response rate of neodymium is: 99%；The response rate of ferrum is: 99%；The response rate of cobalt is: 79%；The response rate of praseodymium is: 99%；The response rate of dysprosium is: 99%.
Embodiment 3
Table 1 " C2H2O4-NH3 " main chemical reactions that relates in system and equilibrium constant
In theory part: first, consult at C2H2O4-NH3The equilibrium constant of neodymium, praseodymium, dysprosium, cobalt, the contingent reaction of ferrum and each reaction under system, as shown in table 1.It is based upon C by chemical equilibrium, mass balance, charge conservation2H2O4-NH3Thermodynamical model under system, as shown in Figure 1.According to Fig. 1, it is believed that 3 valency iron ions should be selected as far as possible, and can be seen that neodymium, praseodymium, dysprosium rare-earth salts optimum recovery pH value should in 0.5～2.5, and the recovery of ferrum and cobalt should be at a high ph, therefore, this patent design technology regulates pH by twice and completes, best precipitation neodymium, praseodymium, dysprosium, cobalt, ferrum pH scope in (0.5～2.5)-9, and should can pass through that a step process obtains neodymium, praseodymium, dysprosium, cobalt, ferrum coordinate precipitated product.
At experimental section: taking after the neodymium iron boron greasy filth of five parts of respectively 5g carries out distillation pretreatment, pretreated neodymium iron boron greasy filth is dissolved and filters by the hydrochloric acid 75ml taking 4mol/L respectively, and addition 3ml content is the H of 30%.wt2O2, stir fully oxidized after, add 1mol/L NH4OH regulates pH=1.5, and adds the C of 1mol/L2H2O4Solution 32ml, after being sufficiently stirred for, adds the NH of 1mol/L again4OH regulates pH=9, the precipitation obtained is filtered, washs three times, dries, namely obtains the product of the neodymium iron boron that can be used for preparation regeneration.Take supernatant and carry out ICP-OES test, it is thus achieved that result as shown in Figure 2: the response rate of neodymium is: 99%；The response rate of ferrum is: 99%；The response rate of cobalt is: 78%；The response rate of praseodymium is: 99%；The response rate of dysprosium is: 99%.
Embodiment 4
Table 1 " C2H2O4-NH3 " main chemical reactions that relates in system and equilibrium constant
In theory part: first, consult at C2H2O4-NH3The equilibrium constant of neodymium, praseodymium, dysprosium, cobalt, the contingent reaction of ferrum and each reaction under system, as shown in table 1.It is based upon C by chemical equilibrium, mass balance, charge conservation2H2O4-NH3Thermodynamical model under system, as shown in Figure 1.According to Fig. 1, it is believed that 3 valency iron ions should be selected as far as possible, and can be seen that neodymium, praseodymium, dysprosium rare-earth salts optimum recovery pH value should in 0.5～2.5, and the recovery of ferrum and cobalt should be at a high ph, therefore, this patent design technology regulates pH by twice and completes, best precipitation neodymium, praseodymium, dysprosium, cobalt, ferrum pH scope in (0.5～2.5)-9, and should can pass through that a step process obtains neodymium, praseodymium, dysprosium, cobalt, ferrum coordinate precipitated product.
At experimental section: taking after the neodymium iron boron greasy filth of five parts of respectively 5g carries out distillation pretreatment, pretreated neodymium iron boron greasy filth is dissolved and filters by the hydrochloric acid 75ml taking 4mol/L respectively, and addition 3ml content is the H of 30%.wt2O2, stir fully oxidized after, add 1mol/L NH4OH regulates pH=2, and adds the C of 1mol/L2H2O4Solution 32ml, after being sufficiently stirred for, adds the NH of 1mol/L again4OH regulates pH=9, the precipitation obtained is filtered, washs three times, dries, namely obtains the product of the neodymium iron boron that can be used for preparation regeneration.Take supernatant and carry out ICP-OES test, it is thus achieved that result as shown in Figure 2: the response rate of neodymium is: 99%；The response rate of ferrum is: 99%；The response rate of cobalt is: 85%；The response rate of praseodymium is: 99%；The response rate of dysprosium is: 99%.
Embodiment 5
Table 1 " C2H2O4-NH3 " main chemical reactions that relates in system and equilibrium constant
In theory part: first, consult at C2H2O4-NH3The equilibrium constant of neodymium, praseodymium, dysprosium, cobalt, the contingent reaction of ferrum and each reaction under system, as shown in table 1.It is based upon C by chemical equilibrium, mass balance, charge conservation2H2O4-NH3Thermodynamical model under system, as shown in Figure 1.According to Fig. 1, it is believed that 3 valency iron ions should be selected as far as possible, and can be seen that neodymium, praseodymium, dysprosium rare-earth salts optimum recovery pH value should in 0.5～2.5, and the recovery of ferrum and cobalt should be at a high ph, therefore, this patent design technology regulates pH by twice and completes, best precipitation neodymium, praseodymium, dysprosium, cobalt, ferrum pH scope in (0.5～2.5)-9, and should can pass through that a step process obtains neodymium, praseodymium, dysprosium, cobalt, ferrum coordinate precipitated product.
At experimental section: taking after the neodymium iron boron greasy filth of five parts of respectively 5g carries out distillation pretreatment, pretreated neodymium iron boron greasy filth is dissolved and filters by the hydrochloric acid 75ml taking 4mol/L respectively, and addition 3ml content is the H of 30%.wt2O2, stir fully oxidized after, add 1mol/L NH4OH regulates pH=2.5, and adds the C of 1mol/L2H2O4Solution 32ml, after being sufficiently stirred for, adds the NH of 1mol/L again4OH regulates pH=9, the precipitation obtained is filtered, washs three times, dries, namely obtains the product of the neodymium iron boron that can be used for preparation regeneration.Take supernatant and carry out ICP-OES test, it is thus achieved that result as shown in Figure 2: the response rate of neodymium is: 99%；The response rate of ferrum is: 99%；The response rate of cobalt is: 87%；The response rate of praseodymium is: 99%；The response rate of dysprosium is: 99%.
Claims (1)
1. one kind at C2H2O4-NH3The method simultaneously reclaiming neodymium, praseodymium, dysprosium, cobalt, ferrum under system from neodymium iron boron greasy filth, it is characterised in that comprise the following steps: after neodymium iron boron greasy filth is carried out distillation pretreatment, take hydrochloric acid and pretreated neodymium iron boron greasy filth is dissolved and filters, add H2O2, stir fully oxidized after, add NH4OH regulates pH=0.5-2.5, and adds C2H2O4Solution, after being sufficiently stirred for, adds NH again4It is 9 that OH regulates pH, the precipitation obtained is filtered, washs three times, dries, and namely obtains and can be used for preparation the regeneration neodymium of neodymium iron boron, praseodymium, dysprosium, cobalt, ferrum；
Every 5g is by hydrochloric acid 75ml, 3mlH of neodymium iron boron greasy filth correspondence 4mol/L2O2、NH4The concentration of OH is the C of 1mol/L, 1mol/L2H2O4Solution 32ml.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206755A (en) * | 2011-03-06 | 2011-10-05 | 林剑 | Method for separating and recovering valuable elements from neodymium-iron-boron wastes |
| CN103343233A (en) * | 2013-07-19 | 2013-10-09 | 北京工业大学 | Method for recovering neodymium and iron from neodymium iron boron oil sludge |
| CN103343234A (en) * | 2013-07-19 | 2013-10-09 | 北京工业大学 | Method for preparing neodymium and iron oxides by using neodymium iron boron oil sludge through regeneration and co-precipitation |
| CN103343235A (en) * | 2013-07-19 | 2013-10-09 | 北京工业大学 | Method for recovering neodymium and iron from neodymium iron boron oil sludge through two-step co-precipitation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102206755A (en) * | 2011-03-06 | 2011-10-05 | 林剑 | Method for separating and recovering valuable elements from neodymium-iron-boron wastes |
| CN103343233A (en) * | 2013-07-19 | 2013-10-09 | 北京工业大学 | Method for recovering neodymium and iron from neodymium iron boron oil sludge |
| CN103343234A (en) * | 2013-07-19 | 2013-10-09 | 北京工业大学 | Method for preparing neodymium and iron oxides by using neodymium iron boron oil sludge through regeneration and co-precipitation |
| CN103343235A (en) * | 2013-07-19 | 2013-10-09 | 北京工业大学 | Method for recovering neodymium and iron from neodymium iron boron oil sludge through two-step co-precipitation |
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