CN104480316A - Simple and convenientindustrial method for recovering Co element from NdFeBmagnetwaste materials - Google Patents
Simple and convenientindustrial method for recovering Co element from NdFeBmagnetwaste materials Download PDFInfo
- Publication number
- CN104480316A CN104480316A CN201410813573.6A CN201410813573A CN104480316A CN 104480316 A CN104480316 A CN 104480316A CN 201410813573 A CN201410813573 A CN 201410813573A CN 104480316 A CN104480316 A CN 104480316A
- Authority
- CN
- China
- Prior art keywords
- oxidation
- leach liquor
- iron boron
- neodymium iron
- waste material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a simple and convenientindustrial method for recovering the Co element from NdFeBmagnetwaste materials. The simple and convenientindustrial method comprises the steps as follows: material oxidation, preferential dissolution leaching, oxidation hydrolysis, Co element recovery, compound preparation and the like. According to the technical route design, the variable valence characteristic of the Co element and stability difference of bivalent Co and trivalent Co are combined skillfully. According to the method, flow matching and technology integration between the Co recovery process link and the conventional rare earth recovery assembly line in the domestic NdFeBwaste material recovery industry can be realized; in the aspect of technical target, the same principle is followed, the Co element is effectively entrapped and recovered at the front end of the whole flow based on the process steps includingmaterial oxidation, preferential dissolution leaching and oxidation hydrolysis, meanwhile, interference of a leachatesystemby Fe and Co elements in the follow-up procedure is avoided, and a rare earth extraction separation process is realized.
Description
Technical field
The invention belongs to the technical field of waste resource comprehensive utilization, relate to rare earth resources recovery and utilization technology, be specifically related to a kind of easy method of neodymium iron boron waste material being carried out to pre-treatment-Ore Leaching.
Background technology
Nd-Fe-Bo permanent magnet material (NdFeB) is the permanent magnet material that magnetic property is the strongest up to now found in 1982, has been widely used in the fields such as computer, medical device, communication device, electron device, magnetic machinery.Current domestic neodymium iron boron industry oneself reach annual ten ton scales, and still in continuous growth.With regard to chemical component, in neodymium iron boron magnetic materials, about 30% is rare earth element (wherein more than 90% is Nd), and 65 ~ 69% is Fe element, separately contains the B element of 1.1 ~ 1.2%.Large quantity research shows, in NdFeB magnetic material, being added with of Co element helps weaken principal phase Nd
2fe
14the magnetic coupling interaction of B crystal grain point, increases micro-magnetic parameter α k value, finally causes the coercive force of NdFeB alloy to promote.In recent years, in NdFeB permanent magnet material is produced, add a certain amount of Co element to improve magnet coercive force, become the general choice of a neodymium iron boron magnetic materials industry.The Co element addition in cobalt neodymium iron boron magnetic materials that contains common in current industry, generally between 1.8 ~ 5.6%, more has Co constituent content in some high cobalt type products to reach more than 6%.
From the production process of Nd-Fe-Bo permanent magnet material, each link of its process for processing all inevitably produces waste material or waste product, and the generation ratio of waste material reaches more than 30%; Current domestic neodymium iron boron waste material generation has reached annual more than 30,000 tons.Neodymium iron boron waste material, with regard to its chemical composition, is basically identical with magnetic material finished product.In neodymium iron boron waste material, the ree content such as Nd enriches, and therefore, the resource utilization of neodymium iron boron waste material reclaims industry and receives technology and developing rapidly in recent years.At present, it is nearly all reclaim extraction rare earth element wherein as industry goal that domestic neodymium iron boron waste material reclaims industry, and main processing method adopts hydrometallurgical processes.
As everyone knows, cobalt is a kind of extremely important strategy metal, and its physics, chemical property are excellent, is the important source material of producing refractory alloy, Wimet, anti-corrosion alloy, magneticalloy and various cobalt salt.And China's cobalt ore resource famine, the overwhelming majority is associated resources, all reclaims as mine byproduct; In the more good mining areas of current exploitation, mineral deposit is only 0.02 ~ 0.18% containing cobalt grade.The extraction of cobalt element is originally just very difficult, if cobalt master metal is extracted from the heavy metal smelting processes such as ambrose alloy and reclaim from chemical system and obtain.Along with the year consumption of domestic cobalt increases year by year, the cobalt raw material (copper nickel sulfide mineral, cobalt iron concentrate, smaltite, cobaltiferous waste material etc.) of the domestic current overwhelming majority needs dependence on import.
As third generation rare earth permanent-magnetic material, compare first-generation rare earth permanent-magnetic material (RECo
5), s-generation rare earth permanent-magnetic material (RE
2tM
17), in Nd-Fe-Bo permanent magnet material, the massfraction of contained cobalt element significantly reduces.But to compare in the heavy metal smelting processes such as ambrose alloy the melting waste slags such as converter slag, with regard to cobalt element content, neodymium iron boron waste material has more recycling undoubtedly and is worth.On the other hand, domestic neodymium iron boron magnetic materials production capacity exceedes 50% of the whole world for a long time, and annual neodymium iron boron magnetic materials output is very huge, conservative estimation, and the cobalt element comprised in all kinds of neodymium iron boron waste material has also reached at hundreds of tons/year according to simple substance Co meter.Therefore, neodymium iron boron magnetic materials waste material should as the important secondary resource of a class cobalt element, to the Co element of neodymium iron boron waste material in addition comprehensive reutilization, lacks situation to a certain extent have positive effect for alleviation China cobalt resource.
The industrial technology focus that neodymium iron boron waste material is recycled is how to recycle rare earth element wherein all the time.For many years, many researchers are also had in succession to carry out the research work of Call Provision and other valuable metals from neodymium iron boron waste material.Existing research work is following process program mainly:
(1) remaining liquid deironing postprecipitation Call Provision: adopt sulfuric acid decomposition neodymium iron boron waste material, by oxalic acid precipitation or double salt precipitation recovering rare earth; Yellow modumite method deironing, carbon ammonium precipitation or sulfide precipitation Call Provision is passed through in liquid more than after recovering rare earth.Main literature: the people such as Zhang Wanyan, the condition test [J] of recovering rare earth and cobalt oxide from neodymium iron boron waste material, Jiangxi nonferrous metal, 2001,15 (4): 23; Chen Wei equality people, recovery research [J] of cobalt in NdFeB waste material, rare metal and Wimet, 2006,34 (2): 55; The people such as Chen Dongying, sulfurization-precipitation method extracts cobalt [J], Jiangxi nonferrous metal, 2007,21 (3): 17 from liquid more than waste and old neodymium iron boron recovering rare earth.
(2) extracting and separating cobalt after remaining liquid deironing: the people such as Xu Tao have reported by the complete molten neodymium iron boron waste material of sulfuric acid, more than after recovering rare earth in liquid, after yellow modumite method deironing, extract Call Provision further by extracting and separating.
chen Yun's brocadereport by the complete molten neodymium iron boron waste material of concentrated hydrochloric acid Deng people, extracted deironing in advance, in deironing raffinate, carried out RE extraction point with P507, in raffinate, sunk cobalt and obtain cobaltous carbonate by carbonate.Concrete document: the people such as Xu Tao, the recovery [J] of neodymium, dysprosium and cobalt in neodymium iron boron waste material, rare earth, 2004,25 (2): 31;
chen Yun's brocadedeng people, the rare earth in full extraction process recovery neodymium iron boron waste material and cobalt [J], Chinese Resources fully utilizes, 2004,6:10.
(3) extracting and separating cobalt in excellent molten leach liquor: domestic patent " a kind of method of Separation and Recovery valuable element from neodymium iron boron waste material " (patent No.: ZL201110058039.5) has been reported and carried out excellent dissolving into out by hydrochloric acid, passes through P for leach liquor
507carry out being separated of rare earth element and cobalt in extraction system, in cobalt pregnant solution, add sodium bicarbonate precipitation Call Provision.
Be conceived to Co element retrieve see, above-mentioned several process program Co element extraction link is all the remaining liquid and the raffinate that come from precipitation or extraction process, from operational path, the extraction link of Co element is in the rear section of processing step, so all also exist, technological process is tediously long, cost recovery is too high, economic benefit is difficult to the drawbacks such as embodiment.Also Just because of this, the various technical schemes that in above-mentioned neodymium iron boron waste material, Co element reclaims are failed to reclaim industry with rare earth element always and are really combined.At present, recycle in neodymium iron boron waste material to Co element, this remains an industry blank at home.
Summary of the invention
The object of the invention is to, in conjunction with the rare earth recovery process generally adopted in Present Domestic neodymium iron boron waste material comprehensive utilization industry, disclose a kind of simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material.Based on technical scheme of the present invention, the process procedure that Co reclaims can be mated and Integration ofTechnology with realization flow between domestic existing neodymium iron boron waste material recovering rare earth device line.
In order to the technical scheme of the present invention of statement clearly, first set forth the excellent molten extract technology of hydrochloric acid of the domestic neodymium iron boron waste material recovering rare earth element generally adopted at present.
It is the industrialization technology generally adopted at present that the resource utilization adopting the excellent molten technique of hydrochloric acid to carry out neodymium iron boron waste material reclaims.Its technological principle is: neodymium iron boron waste material is disposed through peroxidation, simple substance element in alloying constituent (each rare earth element, Fe and Addition ofelements Co, Al etc.) is converted into oxide compound, the hydrochloric acid of about 2.5N concentration is adopted to carry out excellent molten decomposition, the component things such as REO can preferentially be leached by hydrochloric acid and enter into leach liquor system, and Fe
2o
3excellent molten waste residue can be entered into Deng component thing.Then, reclaim rare earth element based on above-mentioned leach liquor through extracting and separating, and excellent molten waste residue can as a class " secondary processes waste ".
In order to the technical scheme of the present invention of statement clearly, in following analysis elaboration neodymium iron boron waste material system, Co element is in each link whereabouts situation of the excellent molten extract technology of above-mentioned hydrochloric acid.
According to the excellent molten extract technology of the domestic hydrochloric acid generally adopted at present, it is with high oxide (Co that the Co element in waste material system to dispose after link more than 75% through peroxidation
2o
3) form existence.Due to Co
3+ion has very strong oxidizing property, cannot directly with Co in water solution system
3+form exists.Therefore, Co element all will be converted into CoCl in acidleach link
2, then Co element can with CoCl after solid-liquid separation
2form enters into leach liquor.
Main component based on the excellent molten leach liquor of technique gained of the excellent molten leaching of hydrochloric acid is rare earth chloride (RECl
3), and comprise non-rare earth class ion Fe
2+, Co
2+, Al
3+and a small amount of Fe
3+.According to the processing requirement of recovering rare earth element, usually before rare earth extraction point, purification and impurity removal means are adopted to remove non-rare earth class ion in leach liquor further.Now the most frequently used purifying and impurity-removing method has two kinds:
(1) oxidizing water solution: by Fe
2+be oxidized to Fe
3+, with FeOOH or Fe (OH)
3precipitate morphology filtering;
(2) deironing is extracted: before carrying out the separation of rare earth extraction, first carry out extraction deironing to leach liquor system, conventional extraction agent mainly amine extractant, as N
235, N
503deng.In extraction deironing link, first by Fe
2+be converted into Fe
3+, with HFeCl
4form extracts into organic phase.
In purification and impurity removal link, a small amount of Co element is inevitably with Co (OH)
2precipitated form enters into precipitation slag, or with [H
2(CoCl
2)] form is extracted into organic phase.According to our actual tests, when carrying out purification and impurity removal by oxidizing water solution, Co element in the rate of loss of this link below 3%.According to existing reported in literature, at [Cl
-] concentration is when being less than 100g/L, Co element is extracted hardly; In actual production process, when carrying out purification and impurity removal by extraction deironing, in organic phase, Co element loss rate is below 0.3%.In other words, according to commonly using purification and impurity removal technique at present, Co element is less in this link rate of loss, and the Co element derived from neodymium iron boron waste material still mainly remains among leach liquor.
To sum up, according to the excellent molten extract technology of the domestic hydrochloric acid generally adopted and purification and impurity removal technique at present, in neodymium iron boron waste material system, Co element is after excellent molten, the purification and impurity removal of persalt, mainly remains with CoCl
2form is present in leach liquor.Co element will enter into the follow-up extracting and separating stage with leach liquor system, and along with extraction point RE process, final Co major part remains in raffinate or washing lotion.
The object of the present invention is achieved like this: a kind of simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material, it is characterized in that the method comprises following several step:
(1) material oxidation: neodymium iron boron waste material is carried out material oxidation; The oxidation of described material adopt in air natural oxidation, roasting oxidation one or both;
(2) excellent molten leaching: the material after oxidation calcination is added hydrochloric acid and carries out excellent molten leaching, carries out solid-liquid separation to leaching product, obtains excellent molten leach liquor and excellent molten waste residue after separation; The volumetric molar concentration of described hydrochloric acid is between 1.5N ~ 7N;
(3) oxydrolysis: carry out oxydrolysis in excellent molten leach liquor, adopts one of two kinds of methods below:
Single stage method:
In excellent molten leach liquor, add oxygenant A carry out oxydrolysis, solid-liquid separation is carried out to oxydrolysis product and obtains leach liquor A and oxidation precipitation slag A; Described oxygenant A is one or more mixtures in hypochlorite, ferrate, ozone, chlorine, peroxydisulfate, peroxy-monosulfate; According to theoretical equivalence divalence Fe in excellent molten leach liquor, Co element being all oxidized to trivalent Fe, Co element requisite oxygen agent, oxygenant A add-on is 100 ~ 180% of theoretical equivalence value;
Two-step approach:
First in excellent molten leach liquor, add oxygenant B carries out once oxidation hydrolysis, carries out solid-liquid separation obtain leach liquor B and oxidation precipitation slag B to oxydrolysis product; Described oxygenant B is one or more mixtures in oxymuriate, hydrogen peroxide, potassium permanganate, potassium bichromate, bromate, nitric acid, bromine water, oxygen; According to divalence Fe element in excellent molten leach liquor is all oxidized to the theoretical equivalence of trivalent Fe element requisite oxygen agent, oxygenant B add-on is 100 ~ 150% of theoretical equivalence value;
In leach liquor B, add oxygenant C again carry out secondary oxidation hydrolysis, solid-liquid separation is carried out to oxydrolysis product and obtains leach liquor C and oxidation precipitation slag C; Described oxygenant C is one or more mixtures in hypochlorite, ferrate, ozone, chlorine, peroxydisulfate, peroxy-monosulfate; According to theoretical equivalence divalence Co element in leach liquor B being all oxidized to trivalent Co element requisite oxygen agent, oxygenant C add-on is 100 ~ 160% of theoretical equivalence value;
(4) cobalt element reclaims and compound preparation: according to different oxydrolysis methods, and cobalt element reclaims and compound preparation adopts the following two kinds method respectively:
Method one: for one-pot oxidation hydrolysis gained oxidation precipitation slag A, add after sulfuric acid carries out heating for dissolving, adopt the deironing of ihleite method, after filtering scum, one or more mixtures added in filtrate in oxalic acid, oxalate, carbonate, supercarbonate, mineral alkali carry out precipitation and obtain CoC
2o
4, CoCO
3, Co (OH)
2in one or more mixtures, then obtain the oxide compound of cobalt through roasting;
Method two: for two-step approach oxydrolysis gained oxidation precipitation slag C, obtain Co (OH) after carrying out pickling, washing, drying
3; In oxidation precipitation slag C, add hydrochloric acid or sulfuric acid carries out heating for dissolving, one or more mixtures added in oxalic acid, oxalate, carbonate, supercarbonate, mineral alkali carry out precipitation and obtain CoC
2o
4, CoCO
3, Co (OH)
2in one or more mixtures, then obtain the oxide compound of cobalt through roasting.
Further, the mixture of one or more among the grinding powder produced in the ultrafine powder that the slag that step (1) described neodymium iron boron waste material produces for Nd-Fe-Bo permanent magnet material machining link scrap stock, vacuum melting produce, pulverizing process produce, bruting process, defective permanent magnet waste product.
In order to improve the changing effect of material oxidation, further, step (1) had also carried out physical pulverization or chemically fragmenting process to neodymium iron boron waste material before neodymium iron boron waste material carries out oxidizing roasting; Material oxidation adopts roasting oxidation, and maturing temperature is 600 DEG C ~ 1100 DEG C.
In order to improve the effect of excellent molten leaching, further, the material of step (2) after oxidation calcination to add before hydrochloric acid carries out excellent molten leaching and also pulverizes the material after oxidation calcination; Adding while hydrochloric acid carries out excellent molten leaching, in material system, also with the addition of one or both mixtures in sulfuric acid, nitric acid, the addition of sulfuric acid, nitric acid by H ionic equivalent than being no more than 10% of hydrochloric acid total amount.
As preferably:
Further, the volumetric molar concentration of step (2) described hydrochloric acid is between 2.0N ~ 5.0N; Described excellent molten extraction temperature is more than 70 DEG C, and the pH value of excellent molten leaching terminal controls between 1.0 ~ 2.5.
Further, the described oxygenant A of step (3) is the one in hypochlorite, ferrate, ozone, chlorine; According to theoretical equivalence divalence Fe in excellent molten leach liquor, Co element being all oxidized to trivalent Fe, Co element requisite oxygen agent, oxygenant A add-on is 105 ~ 120% of theoretical equivalence value.
Further, the described oxygenant B of step (3) is the one in oxymuriate, hydrogen peroxide; According to divalence Fe element in excellent molten leach liquor is all oxidized to the theoretical equivalence of trivalent Fe element requisite oxygen agent, oxygenant B add-on is 105 ~ 120% of theoretical equivalence value.
Further, the described oxygenant C of step (3) is the one in hypochlorite, ferrate, ozone, chlorine; According to theoretical equivalence divalence Co element in leach liquor B being all oxidized to trivalent Co element requisite oxygen agent, oxygenant C add-on is 105 ~ 120% of theoretical equivalence value.
Further, the deironing of step (4) described ihleite method is being heated to by solution after more than 90 DEG C, is adding NaCO in the solution
3, one in NaOH, by the Fe in solution
3+be converted into NaFe
3(SO
4)
2(OH)
6the sodium ihleite alum throw out of structure and reach deironing object.
Further, step (4) described pickling adopts the dilute hydrochloric acid of massfraction below 5% or dilute sulphuric acid to wash material.
Further, the terminal point determining of the described one-pot oxidation hydrolysis of step (3) is Co element residual concentration below control 0.4mg/L in the liquid-phase system of foundation leach liquor; In described two-step approach, the terminal point determining of once oxidation hydrolysis is that in the liquid-phase system of foundation leach liquor, Fe element residual concentration controls at below 0.2mg/L; In described two-step approach, the terminal point determining of secondary oxidation hydrolysis is that in the liquid-phase system of foundation leach liquor, Co element residual concentration controls at below 0.4mg/L.
Further, the described excellent molten waste residue main component of step (2) is Fe
2o
3, the main component of step (3) described oxidation precipitation slag B is Fe (OH)
3or FeOOH, all for the production of iron oxide red and ferrite magnetic material; Step (3) described leach liquor A and leach liquor C mainly becomes rare earth chloride, for passing through extracting and separating recovering rare earth element.
Know-why of the present invention is:
1, the present invention carries out material oxidation to neodymium iron boron waste material, and to make valuable metal in material fully be converted into metal oxide, wherein Co element is converted into divalence and cobaltic oxide compound in this link; In general, under preferred processing condition, Co element 95% can be converted into metal oxide after material oxidation link, and wherein more than 65 ~ 90% is with high oxide (Co
2o
3) form existence.Chemically in characteristic, be metal oxide by the Co cycling of elements in material, the acidleach rate of Co element can be improved.
2, according to the excellent molten extract technology generally adopted in current industry, in excellent molten acidleach link, the Co element more than 97% massfraction in material can enter among leach liquor system.In view of Co
3+ion has very strong oxidisability, Co element in leach liquor system all with CoCl
2form exists, simultaneously and be stored in leach liquor system and have rare earth ion, Fe
2+, Co
2+, Al
3+and a small amount of Fe
3+(main component wherein in system is rare earth ion).
3, the present invention carries out oxydrolysis to excellent molten leach liquor, Co element oxide is trivalent cobalt and with Co (OH) in this link
3sedimentary form " retains " from leach liquor system; By oxydrolysis, Fe, Co element in excellent molten leach liquor will enter into oxidation precipitation slag, and this also just can meet the processing requirement that follow-up rare earth extraction is separated simultaneously.
To Co (OH)
2with Co (OH)
3dissociation constant contrasted, its pKa value is respectively 14.8 and 43.8, and both gaps are extremely obvious; Therefore, after Co element is oxidized to trivalent from divalence, be easier to the precipitation of hydroxide obtaining Co element from leach liquor system, thus reach the technical purpose retaining and reclaim Co element.From electropotential, E
0(Fe
3+/ Fe
2+)=0.77V, E
0(Co
3+/ Co
2+)=1.83V, positive trivalent cobalt ion Co
3+oxidisability much larger than positive trivalent Fe
3+ion, both gaps are obvious; In other words, divalence cobalt oxidation is that the contrast of trivalent cobalt is ferrous oxidising for ferric iron, from the selection of oxygenant, is then the oxygenant needing selective oxidizing stronger.According to known achievement in research, because the oxidisability of trivalent cobalt ion is very strong, oxidizing potential is very high, and can precipitate hydrolysis under very low pH, and pH just can precipitate hydrolysis about 0.5; And divalent cobalt ion just can precipitate hydrolysis at about pH6.
According to the technology of the present invention, one-step technology have employed the strong oxidizer (i.e. oxygenant A) that divalence cobalt element in excellent molten leach liquor can be oxidized to trivalent cobalt element, and in gained oxidation precipitation slag A, main component is Fe (OH)
3with Co (OH)
3.Generally, with neodymium iron boron waste material rare earth elements total amount, rare earth element is lost in accounting in oxidation precipitation slag A below 0.2%.In view of excellent molten leaching link has retained most Fe elements, generally, Co (OH) in oxidation precipitation slag A
3shared massfraction is between 30 ~ 80%; With Co element total amount in neodymium iron boron waste material, by oxidation precipitation slag A with Co (OH)
3form reclaims Co element accounting more than 95%.
According to the technology of the present invention, first two-step process have employed and ferrous iron element oxide in excellent molten leach liquor can be ferric iron element and the oxygenant (i.e. oxygenant B) being not enough to divalence cobalt element to be oxidized to trivalent cobalt element, and in gained oxidation precipitation slag B, main component is Fe (OH)
3or FeOOH; Generally, with Co element total amount in neodymium iron boron waste material, the accounting of Co element loss in oxidation precipitation slag B below 2%, and in leach liquor B Fe element residual concentration at below 0.2mg/L%.
According to the technology of the present invention, two-step process is follow-up have employed the strong oxidizer (i.e. oxygenant C) that divalence cobalt element in leach liquor B can be oxidized to trivalent cobalt element, and in gained oxidation precipitation slag C, main component is Co (OH)
3.Generally, with Co element total amount in neodymium iron boron waste material, by oxidation precipitation slag C with Co (OH)
3form reclaims Co element accounting more than 94%.
Generally, adopt two-step process, with neodymium iron boron waste material rare earth elements total amount, rare earth element is lost in accounting in oxidation precipitation slag B and oxidation precipitation slag C below 0.3%.
According to the technology of the present invention, excellent molten leach liquor after oxydrolysis, under one-step technology in leach liquor system Fe, Co element total residual concentration at 0.1mg/L, under two-step process in leach liquor system Fe, Co element total residual concentration at below 0.06mg/L; Accordingly, from the angle of recovering rare earth element, the leach liquor system after oxydrolysis has reached the technical purpose of fully purification.
4, reclaim and compound preparation technology according to cobalt element of the present invention, carry out in the process of heating for dissolving at employing hydrochloric acid, sulfuric acid, Co (OH) in oxidation precipitation slag
3will with cobaltous CoCl
2, CoSO
4form is entered among solution system by dissolving, and then obtains a series of cobalt (II) compound through post precipitation process.
Compared with prior art, its advantage is in the present invention:
1, technological line design of the present invention, can reclaim realization flow between industry existing recovering rare earth device line by the process procedure that Co reclaims with domestic neodymium iron boron waste material and mate and Integration ofTechnology.In technical object, have followed identity principle, based on the processing step of material oxidation, excellent molten leaching and oxydrolysis, the effectively catching to Co element and recovery is achieved in the front end of whole flow process, also ensure that extracted liquid ties up to the interference that subsequent handling does not exist Fe, Co element, the technique being conducive to extracting point rare earth realizes simultaneously.
2, the characteristic of appraising at the current rate that cleverly Co element possessed of technical thought of the present invention, and the stability difference of divalence Co and trivalent Co combines; Also be because trivalent cobalt exists precipitation hydrolysis properties under very low pH, can be consistent with the acidic character of leach liquor system, eliminate the operation of regulation system pH, also omit corresponding acid, alkali consumption.
3, the ingenious difference that make use of between trivalent Co and trivalent Fe in oxidisability of technical thought of the present invention, thus select different oxygenants and oxidizing condition, the substep realizing Fe, Co element retains, thus the very easy technical purpose reaching recovery Co element.
4, due to the stability difference that the valence state of Co element causes, and cobaltic low ph value precipitation hydrolysis properties, loss can not be produced to the rare earth element existed a large amount of in leach liquor system from process implementation.Therefore, the technology of the present invention has good process controllability, from the processing condition and control overflow of each step, all have good Technological adaptability, thus ensure that Co element with Co (OH)
3what precipitate morphology was concentrated is retained among hydrolytic precipitation slag and is reclaimed, and in this link gained throw out, the rate of recovery of gained Co element can reach more than 94%, and the loss of rare earth element can control below 0.3%.
Accompanying drawing explanation
accompanying drawing 1for technical process of the present invention
figure.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further described.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
embodiment 1:
Get a collection of scrap stock deriving from Nd-Fe-Bo permanent magnet material machining link and produce.After testing, in above-mentioned every 100g neodymium iron boron waste material, metallic element comprises: rare earth element total amount 31.03g(wherein main component is Nd, separately comprises Pr, Dy, Gd), Fe constituent content 60.01g, Co constituent content 4.36g, Al constituent content 0.40g.
Get 1000Kg material in above-mentioned a collection of neodymium iron boron waste material, undertaken grinding below median size 300 order by ball mill, material after pulverizing is carried out oxidizing roasting (maturing temperature 700 DEG C in rotary kiln, roasting time 1 hour), with the hydrochloric acid of 2.7N concentration, (extraction temperature 85 DEG C is leached to the material after oxidizing roasting again, the pH value controlling to leach terminal is 2.0), the material after having leached obtains excellent molten leach liquor and excellent molten waste residue after press filtration is separated.According to purposes of statistical process, Yancheng consumption is about 1.8 cubic metres.
Detect excellent molten leach liquor, wherein Co constituent content is that 42.80Kg, Fe element remains total amount 51.78Kg, wherein two valency Fe element total amount 41.48Kg, trivalent Fe element total amount 10.30Kg.Calculate accordingly, the Co unit in neodymium iron boron waste material have 98.16% and enters into excellent molten leach liquor.
Excellent molten leach liquor is divided into two parts of equal deal.
Get the excellent molten leach liquor of a copy of it, carry out oxydrolysis by one-step technology.
Adopt ozonizer generates ozone to be used as oxygenant, in special ozone-oxidizing device, carry out oxydrolysis reaction by ozone, temperature of reaction controls at 40 DEG C; Sampling analysis when separating out without obvious sediment thing in question response system, stopped reaction when Co element residual concentration is less than 0.4mg/L in the liquid-phase system of leach liquor, carries out press filtration separation immediately, obtains the leach liquor after oxydrolysis and oxidation precipitation slag.According to purposes of statistical process, ozone usage is that 19.35Kg(closes 403.12mol); Calculating known theoretical equivalence divalence Fe in this portion of excellent molten leach liquor, Co element being all oxidized to oxidant, ozone needed for trivalent Fe, Co element is 366.54mol; The actual amount of oxidant, ozone is theoretical equivalence value 110%.
To oxidation precipitation slag sampling analysis, gross weight is 88.53Kg, and its major ingredient is Fe (OH)
3with Co (OH)
3, wherein Co (OH)
3weight is 38.93Kg, accounts for 43.97% of oxidation precipitation slag; Count, by oxidation precipitation slag with Co (OH) according to the Co element total amount 21.8Kg corresponding to waste material source
3it is 95.78% that form reclaims Co element accounting.
Analyze the content of rare earth in oxidation precipitation slag, its rare earth elements total amount closes 202g, and count according to the rare earth element total amount 155.15Kg corresponding to waste material source, the rare earth element accounting be lost in oxidation precipitation slag is 0.13%.
By above-mentioned oxidation precipitation slag with add 25% concentration sulfuric acid mix, be heated to 95 DEG C, after material dissolves completely, add a little hydrogen peroxide, carry out under the condition constantly stirred slowly and continuous print adds Na
2cO
3solution, when keeping system pH stable, constantly has sodium ihleite Precipitation; Treat to separate out without obvious sediment thing, and when occurring that pH value obviously rises, stop Na
2cO
3solution.Filtering separation is carried out to reaction mass, obtains sodium ihleite precipitation and filtrate.In filtrate, add precipitation agent sodium oxalate, collecting precipitation thing obtains cobalt oxalate product.Roasting is carried out to cobalt oxalate, according to the difference of maturing temperature, obtains the cobalt/cobalt oxide product of different valence state.
embodiment 2:
In Example 1, other a excellent molten leach liquor, carries out oxydrolysis by two-step process.
First the oxygenant adopting sodium chlorate to be hydrolyzed as once oxidation, is heated to 90 DEG C by excellent molten leach liquor, constantly adds sodium chlorate solution wherein, after precipitation starts appearance, slows down sodium chlorate solution and adds speed; Sampling analysis when separating out without obvious sediment thing in question response system, stopped reaction when Fe element residual concentration controls at below 0.2mg/L in the liquid-phase system of leach liquor, carry out press filtration separation immediately, obtain the leach liquor after once oxidation hydrolysis and once oxidation precipitation slag.According to purposes of statistical process, sodium chlorate consumption is that 7.10Kg(closes 66.67mol); Calculating known theoretical equivalence divalence Fe element in this portion of excellent molten leach liquor being all oxidized to trivalent Fe element requisite oxygen agent sodium chlorate is 61.73mol; The actual amount of oxygenant sodium chlorate is theoretical equivalence value 108%.
To once oxidation precipitation slag sampling analysis, gross weight is 81.69Kg, and its main component is FeOOH.Analyze the Co constituent content in once oxidation hydrolysis residue, wherein Co constituent content is 231g, and count according to the Co element total amount 21.8Kg corresponding to waste material source, the accounting of Co element loss in once oxidation precipitation slag is 1.06%.
Adopt the oxygenant that clorox is hydrolyzed as secondary oxidation again, add clorox in the leach liquor after once oxidation hydrolysis and carry out secondary oxidation hydrolysis, temperature of reaction controls at 45 DEG C; Sampling analysis when separating out without obvious sediment thing in question response system, stopped reaction when Co element residual concentration is less than 0.4mg/L in the liquid-phase system of leach liquor, carries out press filtration separation immediately, obtains the leach liquor after secondary oxidation hydrolysis and secondary oxidation precipitation slag.According to purposes of statistical process, clorox consumption is that 15.27Kg(closes 204.94mol); Calculating known theoretical equivalence divalence Co element in leach liquor after this part of once oxidation hydrolysis being all oxidized to oxidizing agent sodium hypochlorite needed for trivalent Co element is 181.36mol; The actual amount of oxidizing agent sodium hypochlorite is theoretical equivalence value 113%.
To secondary oxidation precipitation slag sampling analysis, gross weight is 39.13Kg, and its major ingredient is Co (OH)
3, wherein Co (OH)
3weight is 38.55Kg, accounts for 98.50% of secondary oxidation precipitation slag; Count, by secondary oxidation precipitation slag with Co (OH) according to the Co element total amount 21.8Kg corresponding to waste material source
3it is 94.86% that form reclaims Co element accounting.
Analyze the content of rare earth in once oxidation precipitation slag and secondary oxidation precipitation slag, its rare earth elements total amount closes 326g, and count according to the rare earth element total amount 155.15Kg corresponding to waste material source, the rare earth element accounting be lost in oxidation precipitation slag is 0.21%.
Above-mentioned secondary oxidation precipitation slag is divided into equal two parts.
A copy of it secondary oxidation precipitation slag dilute hydrochloric acid of 3% concentration carries out rinsing, then after washing with soft water, obtains Co (OH) after drying
3product.
By in other a oxidation precipitation slag with the mixed in hydrochloric acid of 2N concentration, be heated to 85 DEG C, after material dissolves completely, add precipitation agent bicarbonate of ammonia, collecting precipitation thing obtains cobaltous carbonate product.Roasting is carried out to cobaltous carbonate, according to the difference of maturing temperature, obtains the cobalt/cobalt oxide product of different valence state.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. from neodymium iron boron magnetic materials waste material, reclaim a simplified industrial method for Co element, it is characterized in that the method comprises following several step:
(1) material oxidation: neodymium iron boron waste material is carried out material oxidation; The oxidation of described material adopt in air natural oxidation, roasting oxidation one or both;
(2) excellent molten leaching: the material after oxidation calcination is added hydrochloric acid and carries out excellent molten leaching, carries out solid-liquid separation to leaching product, obtains excellent molten leach liquor and excellent molten waste residue after separation; The volumetric molar concentration of described hydrochloric acid is between 1.5N ~ 7N;
(3) oxydrolysis: carry out oxydrolysis in excellent molten leach liquor, adopts one of two kinds of methods below:
Single stage method:
In excellent molten leach liquor, add oxygenant A carry out oxydrolysis, solid-liquid separation is carried out to oxydrolysis product and obtains leach liquor A and oxidation precipitation slag A; Described oxygenant A is one or more mixtures in hypochlorite, ferrate, ozone, chlorine, peroxydisulfate, peroxy-monosulfate; According to theoretical equivalence divalence Fe in excellent molten leach liquor, Co element being all oxidized to trivalent Fe, Co element requisite oxygen agent, oxygenant A add-on is 100 ~ 180% of theoretical equivalence value;
Two-step approach:
First in excellent molten leach liquor, add oxygenant B carries out once oxidation hydrolysis, carries out solid-liquid separation obtain leach liquor B and oxidation precipitation slag B to oxydrolysis product; Described oxygenant B is one or more mixtures in oxymuriate, hydrogen peroxide, potassium permanganate, potassium bichromate, bromate, nitric acid, bromine water, oxygen; According to divalence Fe element in excellent molten leach liquor is all oxidized to the theoretical equivalence of trivalent Fe element requisite oxygen agent, oxygenant B add-on is 100 ~ 150% of theoretical equivalence value;
In leach liquor B, add oxygenant C again carry out secondary oxidation hydrolysis, solid-liquid separation is carried out to oxydrolysis product and obtains leach liquor C and oxidation precipitation slag C; Described oxygenant C is one or more mixtures in hypochlorite, ferrate, ozone, chlorine, peroxydisulfate, peroxy-monosulfate; According to theoretical equivalence divalence Co element in leach liquor B being all oxidized to trivalent Co element requisite oxygen agent, oxygenant C add-on is 100 ~ 160% of theoretical equivalence value;
(4) cobalt element reclaims and compound preparation: according to different oxydrolysis methods, and cobalt element reclaims and compound preparation adopts the following two kinds method respectively:
Method one: for one-pot oxidation hydrolysis gained oxidation precipitation slag A, add after sulfuric acid carries out heating for dissolving, adopt the deironing of ihleite method, after filtering scum, one or more mixtures added in filtrate in oxalic acid, oxalate, carbonate, supercarbonate, mineral alkali carry out precipitation and obtain CoC
2o
4, CoCO
3, Co (OH)
2in one or more mixtures, then obtain the oxide compound of cobalt through roasting;
Method two: for two-step approach oxydrolysis gained oxidation precipitation slag C, obtain Co (OH) after carrying out pickling, washing, drying
3; In oxidation precipitation slag C, add hydrochloric acid or sulfuric acid carries out heating for dissolving, one or more mixtures added in oxalic acid, oxalate, carbonate, supercarbonate, mineral alkali carry out precipitation and obtain CoC
2o
4, CoCO
3, Co (OH)
2in one or more mixtures, then obtain the oxide compound of cobalt through roasting.
2. the simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material according to claim 1, is characterized in that: the mixture of one or more among the grinding powder produced in the ultrafine powder that the slag that the scrap stock that step (1) described neodymium iron boron waste material produces for Nd-Fe-Bo permanent magnet material machining link, vacuum melting produce, pulverizing process produce, bruting process, defective permanent magnet waste product; Step (1) had also carried out physical pulverization or chemically fragmenting process to neodymium iron boron waste material before neodymium iron boron waste material carries out oxidizing roasting; Material oxidation adopts roasting oxidation, and maturing temperature is 600 DEG C ~ 1100 DEG C.
3. the simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material according to claim 1, is characterized in that: the material of step (2) after oxidation calcination adds before hydrochloric acid carries out excellent molten leaching also to be pulverized the material after oxidation calcination; Adding while hydrochloric acid carries out excellent molten leaching, in material system, also with the addition of one or both mixtures in sulfuric acid, nitric acid, the addition of sulfuric acid, nitric acid by H ionic equivalent than being no more than 10% of hydrochloric acid total amount; The volumetric molar concentration of step (2) described hydrochloric acid is between 2.0N ~ 5.0N; Described excellent molten extraction temperature is more than 70 DEG C, and the pH value of excellent molten leaching terminal controls between 1.0 ~ 2.5.
4. the simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material according to claim 1, is characterized in that: the described oxygenant A of step (3) is the one in hypochlorite, ferrate, ozone, chlorine; According to theoretical equivalence divalence Fe in excellent molten leach liquor, Co element being all oxidized to trivalent Fe, Co element requisite oxygen agent, oxygenant A add-on is 105 ~ 120% of theoretical equivalence value.
5. the simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material according to claim 1, is characterized in that: the described oxygenant B of step (3) is the one in oxymuriate, hydrogen peroxide; According to divalence Fe element in excellent molten leach liquor is all oxidized to the theoretical equivalence of trivalent Fe element requisite oxygen agent, oxygenant B add-on is 105 ~ 120% of theoretical equivalence value.
6. the simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material according to claim 1, is characterized in that: the described oxygenant C of step (3) is the one in hypochlorite, ferrate, ozone, chlorine; According to theoretical equivalence divalence Co element in leach liquor B being all oxidized to trivalent Co element requisite oxygen agent, oxygenant C add-on is 105 ~ 120% of theoretical equivalence value.
7. the simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material according to claim 1, is characterized in that: the deironing of step (4) described ihleite method is being heated to by solution after more than 90 DEG C, is adding NaCO in the solution
3, one in NaOH, by the Fe in solution
3+be converted into NaFe
3(SO
4)
2(OH)
6the sodium ihleite alum throw out of structure and reach deironing object.
8. the simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material according to claim 1, is characterized in that: step (4) described pickling adopts the dilute hydrochloric acid of massfraction below 5% or dilute sulphuric acid to wash material.
9. the simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material according to claim 1, is characterized in that: the terminal point determining of the described one-pot oxidation hydrolysis of step (3) is Co element residual concentration below control 0.4mg/L in the liquid-phase system of foundation leach liquor; In described two-step approach, the terminal point determining of once oxidation hydrolysis is that in the liquid-phase system of foundation leach liquor, Fe element residual concentration controls at below 0.2mg/L; In described two-step approach, the terminal point determining of secondary oxidation hydrolysis is that in the liquid-phase system of foundation leach liquor, Co element residual concentration controls at below 0.4mg/L.
10. the simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material according to claim 1, is characterized in that: the described excellent molten waste residue main component of step (2) is Fe
2o
3, the main component of step (3) described oxidation precipitation slag B is Fe (OH)
3or FeOOH, all for the production of iron oxide red and ferrite magnetic material; Step (3) described leach liquor A and leach liquor C mainly becomes rare earth chloride, for passing through extracting and separating recovering rare earth element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410813573.6A CN104480316B (en) | 2014-12-24 | 2014-12-24 | A kind of simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410813573.6A CN104480316B (en) | 2014-12-24 | 2014-12-24 | A kind of simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104480316A true CN104480316A (en) | 2015-04-01 |
| CN104480316B CN104480316B (en) | 2016-12-07 |
Family
ID=52754917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410813573.6A Active CN104480316B (en) | 2014-12-24 | 2014-12-24 | A kind of simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104480316B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105567999A (en) * | 2015-12-31 | 2016-05-11 | 郴州丰越环保科技有限公司 | Method for recycling valuable metal from zinc hydrometallurgy purified cobalt and nickel residues |
| CN105734296A (en) * | 2016-04-20 | 2016-07-06 | 南阳东方应用化工研究所 | Comprehensive utilization method of neodymium iron boron waste acid leaching slag |
| CN107794373A (en) * | 2017-11-06 | 2018-03-13 | 王志勇 | The integrated conduct method of the useless magnetic material of neodymium iron boron |
| CN108193051A (en) * | 2017-12-28 | 2018-06-22 | 长春工程学院 | A kind of neodymium iron boron powdered scrap room temperature wet method air, ozone secondary oxidation remove the device and method of iron |
| CN112575196A (en) * | 2020-12-24 | 2021-03-30 | 中国石油化工股份有限公司 | Method and equipment for extracting high-purity titanium liquid from olefin polymerization industrial waste acid residues |
| CN113652540A (en) * | 2021-07-15 | 2021-11-16 | 江西理工大学 | Method for selectively separating rare earth and comprehensively recovering iron from neodymium iron boron waste |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09217132A (en) * | 1996-02-13 | 1997-08-19 | Santoku Kinzoku Kogyo Kk | Method for recovering useful element from rare earth-iron alloy |
| CN102154558A (en) * | 2011-03-23 | 2011-08-17 | 连云港市兆昱新材料实业有限公司 | Method for recovering rare earth by segments from neodymium iron boron waste |
| CN102206755A (en) * | 2011-03-06 | 2011-10-05 | 林剑 | Method for separating and recovering valuable elements from neodymium-iron-boron wastes |
| CN102912134A (en) * | 2012-09-27 | 2013-02-06 | 信丰县包钢新利稀土有限责任公司 | Neodymium, iron and boron waste recycling process with approximately zero wastewater discharge |
| CN103555950A (en) * | 2013-10-12 | 2014-02-05 | 瑞科稀土冶金及功能材料国家工程研究中心有限公司 | Recycling method of samarium cobalt magnetic waste material |
| CN103725890A (en) * | 2014-01-07 | 2014-04-16 | 中南大学 | Method for recycling valuable metals step by step from zinc-manganese-cobalt-rich slag in multiplex control manner |
-
2014
- 2014-12-24 CN CN201410813573.6A patent/CN104480316B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09217132A (en) * | 1996-02-13 | 1997-08-19 | Santoku Kinzoku Kogyo Kk | Method for recovering useful element from rare earth-iron alloy |
| CN102206755A (en) * | 2011-03-06 | 2011-10-05 | 林剑 | Method for separating and recovering valuable elements from neodymium-iron-boron wastes |
| CN102154558A (en) * | 2011-03-23 | 2011-08-17 | 连云港市兆昱新材料实业有限公司 | Method for recovering rare earth by segments from neodymium iron boron waste |
| CN102912134A (en) * | 2012-09-27 | 2013-02-06 | 信丰县包钢新利稀土有限责任公司 | Neodymium, iron and boron waste recycling process with approximately zero wastewater discharge |
| CN103555950A (en) * | 2013-10-12 | 2014-02-05 | 瑞科稀土冶金及功能材料国家工程研究中心有限公司 | Recycling method of samarium cobalt magnetic waste material |
| CN103725890A (en) * | 2014-01-07 | 2014-04-16 | 中南大学 | Method for recycling valuable metals step by step from zinc-manganese-cobalt-rich slag in multiplex control manner |
Non-Patent Citations (2)
| Title |
|---|
| 克勒斯顿著，贾立德等译: "《电化学概论 下》", 30 November 1959 * |
| 株洲硬质合金厂著: "《硬质合金的生产》", 30 June 1974 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105567999A (en) * | 2015-12-31 | 2016-05-11 | 郴州丰越环保科技有限公司 | Method for recycling valuable metal from zinc hydrometallurgy purified cobalt and nickel residues |
| CN105734296A (en) * | 2016-04-20 | 2016-07-06 | 南阳东方应用化工研究所 | Comprehensive utilization method of neodymium iron boron waste acid leaching slag |
| CN107794373A (en) * | 2017-11-06 | 2018-03-13 | 王志勇 | The integrated conduct method of the useless magnetic material of neodymium iron boron |
| CN107794373B (en) * | 2017-11-06 | 2019-01-22 | 孙东江 | The integrated conduct method of the useless magnetic material of neodymium iron boron |
| CN108193051A (en) * | 2017-12-28 | 2018-06-22 | 长春工程学院 | A kind of neodymium iron boron powdered scrap room temperature wet method air, ozone secondary oxidation remove the device and method of iron |
| CN112575196A (en) * | 2020-12-24 | 2021-03-30 | 中国石油化工股份有限公司 | Method and equipment for extracting high-purity titanium liquid from olefin polymerization industrial waste acid residues |
| CN112575196B (en) * | 2020-12-24 | 2023-11-03 | 中国石油化工股份有限公司 | Method and equipment for extracting high-purity titanium liquid from olefin polymerization industrial waste acid sludge |
| CN113652540A (en) * | 2021-07-15 | 2021-11-16 | 江西理工大学 | Method for selectively separating rare earth and comprehensively recovering iron from neodymium iron boron waste |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104480316B (en) | 2016-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104593603A (en) | Simple and convenient chemical industry method for extracting and recovering cobalt from waste neodymium-iron-boron magnetic material | |
| CN104480316B (en) | A kind of simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material | |
| Liu et al. | High-efficiency simultaneous extraction of rare earth elements and iron from NdFeB waste by oxalic acid leaching | |
| Peelman et al. | Hydrometallurgical recovery of rare earth elements from mine tailings and WEEE | |
| CN102206755B (en) | Method for separating and recovering valuable elements from neodymium-iron-boron wastes | |
| CN106367622B (en) | It is a kind of using aluminum sulfate as the ion adsorption type re efficient green extracting method of leaching agent | |
| CN103540756B (en) | A kind of method processing waste and old neodymium iron boron material dissolution rare earth | |
| CN102230082B (en) | Method for recovering rare earth and niobium from rare metallic ores | |
| CN101463427A (en) | Method for recycling valuable metal from cobalt white alloy | |
| Chen et al. | Highly efficient recovery and purification of scandium from the waste sulfuric acid solution from titanium dioxide production by solvent extraction | |
| CN102312083A (en) | Method for extracting zinc indium and recovering iron from high-iron high indium zinc concentrate | |
| Liu et al. | A new process of extracting vanadium from stone coal | |
| CN102851496B (en) | Treatment method of high-indium high-iron zinc concentrate | |
| CN104278165A (en) | Method for recovering thorium, uranium and rare earth from monazite smelting acid-insoluble slag | |
| CN107299219B (en) | A kind of resource utilization method of electroplating sludge | |
| CN106834692A (en) | The comprehensive recovering process of valuable metal in a kind of zinc dust precipitation slag | |
| CN104388711A (en) | Method for recovering rare earth by leaching rare earth oxide molten slag | |
| CN102560109A (en) | Method for extracting copper, nickel and cobalt intermediate products from copper and cobalt ore at low cost | |
| CN105110300B (en) | The method that a kind of compound manganese ore of Containing Sulfur manganese extracts manganese and sulphur | |
| CN106906360A (en) | A kind of technique of synthetical recovery cupric cobalt sulfate slag | |
| CN110564961B (en) | Method for reducing leached hydrocobaltite | |
| CN106222417B (en) | A kind of method that neodymium iron boron waste material rare earth elements are leached using rare earth raffinate | |
| CN112342399A (en) | Method for simultaneously extracting vanadium, titanium and chromium from vanadium slag | |
| CN109777953B (en) | Low-grade oxidation and copper sulfide ore environment-friendly recovery process | |
| CN103553155A (en) | Method for treating laterite intermediate product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |