CN104480316B - A kind of simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material - Google Patents
A kind of simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material Download PDFInfo
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Abstract
The invention discloses a kind of simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material, it includes that material oxidation, excellent molten leaching, oxydrolysis, cobalt element recovery and compound such as prepare at the step.The technology path design of the present invention, the characteristic of appraising at the current rate possessed by Co element cleverly, and the stability difference of bivalence Co and trivalent Co combine.According to the technology of the present invention, the process procedure that can be reclaimed by Co and domestic neodymium iron boron waste material reclaim and realize flow path match and Integration ofTechnology between industry existing recovering rare earth device line.In terms of technical goal, have followed identity principle, based on material oxidation, excellent molten leaching and the processing step of 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 subsequent handling and there is not the interference of Fe, Co element simultaneously, be conducive to the technique of extraction point rare earth to realize.
Description
Technical field
The invention belongs to the technical field of waste resource comprehensive utilization, relate to rare earth resources recovery and utilization technology, specifically relate to
And a kind of easy method that neodymium iron boron waste material is carried out pre-treatment-Ore Leaching.
Background technology
Nd-Fe-B permanent magnet material (NdFeB) is the permanent magnet material that the magnetic property up to now found for 1982 is the strongest, the most extensively
General it is applied to the fields such as computer, medical device, communication device, electronic device, magnetic machinery.Current domestic neodymium iron boron industry is own
Reach annual ten ton scales, and still constantly increasing.For chemical component, in neodymium iron boron magnetic materials, about 30% is rare earth
Element (wherein 90% is above Nd), and 65～69% is Fe element, another containing 1.1～the B element of 1.2%.Numerous studies show,
In NdFeB magnetic material, being added with of Co element helps weaken principal phase Nd2Fe14The magnetic coupling interaction of B crystal grain point, increases micro-magnetic parameter α k
Value, the coercivity ultimately resulting in NdFeB alloy promotes.In recent years, in NdFeB permanent magnet material produces, a certain amount of Co unit is added
Element, to improve magnet coercivity, has had become as the general choice of a neodymium iron boron magnetic materials industry.Common containing in industry at present
In cobalt neodymium iron boron magnetic materials, Co element addition is typically between 1.8～5.6%, more has Co constituent content in some high cobalt type products
More than 6% can be reached.
From the point of view of the production process of Nd-Fe-B permanent magnet material, each link of its production and processing all inevitably results from
Waste material or waste product, the generation ratio of waste material reaches more than 30%；Current domestic neodymium iron boron waste material generation amount has reached annual 30000 tons
Above.Neodymium iron boron waste material, for its chemical composition, is basically identical with magnetic material finished product.The rare earth such as Nd in neodymium iron boron waste material
Constituent content enriches, and therefore, the resource of neodymium iron boron waste material reclaims industry receipts technology and quickly grew in recent years.At present, domestic
It is nearly all to reclaim extraction rare earth element therein as industry goal, main process that neodymium iron boron waste material reclaims industry
It is to use hydrometallurgical processes.
It is known that cobalt is a kind of extremely important strategy metal, its physics, chemical property are excellent, are to produce resistance to heat seal
Gold, hard alloy, anti-corrosion alloy, magnetic alloy and the important source material of various cobalt salt.And China's cobalt ore resource famine, the most greatly
Majority is associated resources, all reclaims as mine side-product；Develop at present mineral deposit in preferable some mining areas containing cobalt product
Position is only 0.02～0.18%.The extraction of cobalt element is the most difficult, and cobalt metal is mainly from heavy metal smelting processes such as ambrose alloys
Middle extraction and from chemical system reclaim and obtain.Along with the year consumption figure of domestic cobalt increases year by year, the cobalt of the domestic current overwhelming majority
Raw material (copper nickel sulfide mineral, cobalt iron concentrate, smaltite, cobaltiferous waste material etc.) needs dependence on import.
As third generation rare earth permanent-magnetic material, compare first generation rare earth permanent-magnetic material (RECo5), second filial generation rare earth permanent magnet material
Material (RE2TM17For), in Nd-Fe-B permanent magnet material, the mass fraction of contained cobalt element is greatly reduced.But, compare ambrose alloy etc.
In heavy metal smelting process for the melting waste slag such as vessel slag, for cobalt element content, neodymium iron boron waste material the most more resource
Change value.On the other hand, domestic neodymium iron boron magnetic materials production capacity already exceedes the 50% of the whole world, annual neodymium iron boron magnetic materials yield
The hugest, conservative estimation, the cobalt element included in all kinds of neodymium iron boron waste materials has reached hundreds of the most according to simple substance Co meter
Ton/year.Therefore, neodymium iron boron magnetic materials waste material should be as the important secondary resource of a class cobalt element, the Co unit to neodymium iron boron waste material
Element in addition comprehensive reutilization, lacks situation and has positive effect for alleviating China's cobalt resource to a certain extent.
The industrial technology focus that neodymium iron boron waste material recycles is how to recycle rare earth element therein all the time.
For many years, many researchers are also had in succession to carry out grinding of from neodymium iron boron waste material Call Provision and other valuable metals
Study carefully work.Existing research work is mainly following process program:
(1) more than, liquid removes ferrum postprecipitation Call Provision: use sulfuric acid decomposition neodymium iron boron waste material, is sunk by oxalic acid precipitation or double salt
Shallow lake recovering rare earth；Remaining liquid after recovering rare earth is reclaimed except ferrum, carbon ammonium precipitation or sulfide precipitation by yellow modumite method
Cobalt.Main literature: Zhang Wanyan et al., the condition test [J] of recovering rare earth and cobalt oxide from neodymium iron boron waste material, Jiangxi Nonferrous gold
Belong to, 2001,15 (4): 23；Chen Wei equality people, recovery research [J] of cobalt in NdFeB waste material, rare metal and hard alloy,
2006,34 (2): 55；Chen Dongying et al., sulfurization-precipitation method extracts cobalt [J], Jiangxi from the remaining liquid of waste and old neodymium iron boron recovering rare earth
Non-ferrous metal, 2007,21 (3): 17.
(2) after more than, liquid removes ferrum, extract and separate cobalt: Xu Tao et al. has reported by the complete molten neodymium iron boron waste material of sulphuric acid, dilute reclaiming
In remaining liquid after soil, after removing ferrum by yellow modumite method, extract Call Provision by extract and separate further.Chen Yun's brocade et al. report
Having led by the complete molten neodymium iron boron waste material of concentrated hydrochloric acid, extraction is except ferrum in advance, carries out RE extraction point, in extraction with P507 in except ferrum raffinate
Remaining liquid sinks cobalt by carbonate and obtains cobalt carbonate.Concrete document: Xu Tao et al., in neodymium iron boron waste material, neodymium, dysprosium and cobalt returns
Receive [J], rare earth, 2004,25 (2): 31；Chen Yun's brocade et al., full extraction reclaims the rare earth in neodymium iron boron waste material and cobalt [J], in
State's comprehensive utilization of resources, 2004,6:10.
(3) extract and separate cobalt in excellent molten leachate: domestic patent " a kind of separation and recovery valuable element from neodymium iron boron waste material
Method " (patent No.: ZL201110058039.5) reported and carried out excellent dissolving into out by hydrochloric acid, passes through P for leachate507
Extraction system carries out the separation of rare earth element and cobalt, cobalt pregnant solution adds sodium bicarbonate precipitation Call Provision.
From the point of view of being conceived to the recovery of Co element, above-mentioned several process program Co element extraction links all come from precipitation or
The remaining liquid of person's extraction process and raffinate, from process route, after the extraction link of Co element is in processing step
Part, so all also existing, technical process is tediously long, cost recovery is too high, economic benefit is difficult to the drawbacks such as embodiment.Also just because of such as
This, the various technical schemes that in above-mentioned neodymium iron boron waste material, Co element reclaims fail to reclaim industry with rare earth element always and are really combined
Together.At present, in neodymium iron boron waste material recycling Co element, this remains an industry blank at home.
Summary of the invention
It is an object of the invention to combine commonly used rare earth in Present Domestic neodymium iron boron waste material comprehensive utilization industry return
Knock off skill, disclose a kind of simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material.Technology based on the present invention
Scheme, can realize flow process between process procedure and the domestic existing neodymium iron boron waste material recovering rare earth device line of Co recovery
Join and Integration ofTechnology.
In order to more clearly state technical scheme, first illustrate that the most domestic the commonly used neodymium iron boron gives up
The excellent molten extract technology of hydrochloric acid of material recovering rare earth element.
It is the most commonly used industrialization skill that the resource using the excellent molten technique of hydrochloric acid to carry out neodymium iron boron waste material reclaims
Art.Its technological principle is: neodymium iron boron waste material through peroxidating dispose, by simple substance element in alloying component (each rare earth element, Fe with
And addition element Co, Al etc.) it is converted into oxide, use the hydrochloric acid of about 2.5N concentration to carry out the component things such as excellent molten decomposition, REO
Can preferentially be leached by hydrochloric acid and enter into leachate system, and Fe2O3Excellent molten waste residue can be entered into Deng component thing.Then, based on upper
State leachate through extract and separate to reclaim rare earth element, and excellent molten waste residue can be as a class " secondary processes garbage ".
In order to more clearly state technical scheme, next analyze and illustrate Co unit in neodymium iron boron waste material system
Element is in each link whereabouts situation of the excellent molten extract technology of above-mentioned hydrochloric acid.
According to the most domestic the commonly used excellent molten extract technology of hydrochloric acid, the Co element in waste material system is at peroxidating
After putting link, 75% is above with high oxide (Co2O3) form existence.Due to Co3+Ion has very strong oxidizing property, water-soluble
Cannot be directly with Co in liquid system3+Form exists.Therefore, Co element will be completely converted into CoCl in acidleach link2, then through solid
After liquid separates, Co element can be with CoCl2Form enters in leachate.
The main component of the excellent molten leachate of technique gained based on the excellent molten leaching of hydrochloric acid is rare earth chloride (RECl3), and
Including non-rare earth class ion Fe2+、Co2+、Al3+And a small amount of Fe3+.According to the technological requirement of recovering rare earth element, generally exist
Purification and impurity removal means are used to remove non-terres rares ion in leachate further before rare earth extraction point.The most the most frequently used purification
Impurity-removing method has two kinds:
(1) oxydrolysis method: by Fe2+It is oxidized to Fe3+, with FeOOH or Fe (OH)3Precipitate morphology filter；
(2) extraction is except ferrum: before carrying out rare earth extraction separation, leachate system first carries out extraction except ferrum, conventional extraction
Agent is mainly amine extractant, such as N235、N503Deng.Save except iron hoop in extraction, first by Fe2+It is converted into Fe3+, with HFeCl4Form extracts
Enter organic facies.
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 [H2(CoCl2)] form is extracted into organic facies.According to our actual tests, carry out purification by oxydrolysis method and remove
In the case of miscellaneous, Co element in the loss rate of this link below 3%.According to existing reported in literature, at [Cl-] concentration is less than
During 100g/L, Co element is extracted hardly；In actual production process, in the case of carrying out purification and impurity removal by extraction except ferrum,
In organic facies, Co element loss rate is below 0.3%.In other words, according to the most conventional purification and impurity removal technique, Co element is in this link
Loss rate is less, and the Co element derived from neodymium iron boron waste material mainly remains among leachate.
To sum up, according to the current excellent molten extract technology of domestic commonly used hydrochloric acid and purification and impurity removal technique, neodymium iron boron gives up
In material system, Co element is after excellent molten, the purification and impurity removal of persalt, mainly remains with CoCl2Form is present in leachate.Co
Element will enter into the follow-up extract and separate stage with leachate system, and along with extraction point RE process, final Co major part remains in extraction
In remaining liquid or washing liquid.
The object of the present invention is achieved like this: a kind of simple industrial reclaiming Co element from neodymium iron boron magnetic materials waste material
Method, it is characterised in that the method includes following several step:
(1) material oxidation: neodymium iron boron waste material is carried out material oxidation；The oxidation of described material uses air autoxidation, roasting
Burn oxidation in one or both；
(2) excellent molten leaching: the material after oxidation calcination is added hydrochloric acid and carries out excellent molten leaching, carry out solid-liquid to leaching product
Separate, after separation, obtain excellent molten leachate and excellent molten waste residue；The molar concentration of described hydrochloric acid is between 1.5N～7N；
(3) oxydrolysis: to carrying out oxydrolysis in excellent molten leachate, one of employing following two method:
One-step method:
In excellent molten leachate, add oxidant A carry out oxydrolysis, oxydrolysis product is carried out solid-liquid separation and obtains
Leachate A and oxidation precipitation slag A；Described oxidant A is hypochlorite, ferrate, ozone, chlorine, peroxydisulfate, crosses one
One or more mixture in sulfate；According to bivalence Fe, Co element in excellent molten leachate are all oxidized to trivalent Fe, Co
The theoretical equivalence of element requisite oxygen agent, oxidant A addition is the 100～180% of theoretical equivalence value；
Two-step method:
In excellent molten leachate, first add oxidant B carry out once oxidation hydrolysis, oxydrolysis product is carried out solid-liquid and divides
From obtaining leachate B and oxidation precipitation slag B；Described oxidant B is chlorate, hydrogen peroxide, potassium permanganate, potassium dichromate, bromic acid
One or more mixture in salt, nitric acid, bromine water, oxygen；According to bivalence Fe element in excellent molten leachate is all oxidized to
The theoretical equivalence of trivalent Fe element requisite oxygen agent, oxidant B addition is the 100～150% of theoretical equivalence value；
In leachate B, add oxidant C again carry out secondary oxidation hydrolysis, oxydrolysis product is carried out solid-liquid separation and obtains
To leachate C and oxidation precipitation slag C；Described oxidant C is hypochlorite, ferrate, ozone, chlorine, peroxydisulfate, mistake
One or more mixture in one sulfate；According to bivalence Co element in leachate B is all oxidized to trivalent Co element institute
The theoretical equivalence of aerobic agent, oxidant C addition is the 100～160% of theoretical equivalence value；
(4) cobalt element reclaims and prepared by compound: according to different oxydrolysis methods, cobalt element reclaims and compound system
The standby the following two kinds method that is respectively adopted:
Method one: hydrolyze gained oxidation precipitation slag A for one-pot oxidation, after addition sulphuric acid carries out heating for dissolving, use
Ihleite method removes ferrum, after filtering scum, adds in oxalic acid, oxalates, carbonate, bicarbonate, inorganic base in filtrate
Plant or several mixture carries out precipitation and obtains CoC2O4、CoCO3、Co(OH)2In one or more mixture, more fired
Oxide to cobalt；
Method two: for two-step method oxydrolysis gained oxidation precipitation slag C, carries out pickling, washing, obtains Co after drying
(OH)3；In oxidation precipitation slag C, add hydrochloric acid or sulphuric acid carries out heating for dissolving, add oxalic acid, oxalates, carbonate, carbonic acid
One or more mixture in hydrogen salt, inorganic base carry out precipitation and obtain CoC2O4、CoCO3、Co(OH)2In one or more
Mixture, the more fired oxide obtaining cobalt.
Further, step (1) described neodymium iron boron waste material be Nd-Fe-B permanent magnet material machining link produce leftover pieces,
The grinding powder produced in slag, the micropowder of pulverizing process generation, bruting process produced by vacuum melting, defective permanent magnet
The mixture of one or more among waste product.
In order to improve material oxidation changing effect, further, step (1) neodymium iron boron waste material carry out oxidizing roasting it
Before also neodymium iron boron waste material carried out physical pulverization or chemically fragmenting processed；Material oxidation uses roasting oxidation, and sintering temperature is
600 DEG C～1100 DEG C.
In order to improve the effect of excellent molten leaching, further, the step (2) material after oxidation calcination adds hydrochloric acid and carries out excellent
Also the material after oxidation calcination is pulverized before molten leaching；While addition hydrochloric acid carries out excellent molten leaching, also at thing
Material system with the addition of one or both mixture in sulphuric acid, nitric acid, sulphuric acid, nitric acid addition based on H ionic equivalent ratio
Less than hydrochloric acid total amount 10%.
As preferably:
Further, the 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, the pH value of excellent molten leaching terminal controls between 1.0～2.5.
Further, step (3) described oxidant A is the one in hypochlorite, ferrate, ozone, chlorine；Foundation
Bivalence Fe, Co element in excellent molten leachate are all oxidized to trivalent Fe, the theoretical equivalence of Co element requisite oxygen agent, oxidant
A addition is the 105～120% of theoretical equivalence value.
Further, step (3) described oxidant B is the one in chlorate, hydrogen peroxide；According to by excellent molten leachate
Bivalence Fe element is all oxidized to the theoretical equivalence of trivalent Fe element requisite oxygen agent, and oxidant B addition is theoretical equivalence value
105～120%.
Further, step (3) described oxidant C is the one in hypochlorite, ferrate, ozone, chlorine；Foundation
Bivalence Co element in leachate B is all oxidized to the theoretical equivalence of trivalent Co element requisite oxygen agent, and oxidant C addition is
The 105～120% of theoretical equivalence value.
Further, step (4) described ihleite method is after solution is heated to more than 90 DEG C except ferrum, adds in the solution
Enter NaCO3, one in NaOH, by the Fe in solution3+It is converted into NaFe3(SO4)2(OH)6The sodium ihleite vitriol precipitate of structure
And reach except ferrum purpose.
Further, step (4) described pickling is to use mass fraction dilute hydrochloric acid below 5% or dilute sulfuric acid to thing
Material washs.
Further, the terminal point determining of step (3) described one-pot oxidation hydrolysis is based in the liquid-phase system of leachate
Co element residual concentration controls below 0.4mg/L；In described two-step method, the terminal point determining of once oxidation hydrolysis is based on leachate
Liquid-phase system in Fe element residual concentration control at below 0.2mg/L；In described two-step method, the terminal of secondary oxidation hydrolysis is sentenced
Surely it is based on Co element residual concentration in the liquid-phase system of leachate to control at below 0.4mg/L.
Further, the described excellent molten waste residue main component of step (2) is Fe2O3, step (3) described oxidation precipitation slag B's
It is mainly composed of Fe (OH)3Or FeOOH, is used to produce iron oxide red and ferrite magnetic material；Step (3) described leachate A
With leachate C mainly become rare earth chloride, for by extract and separate recovering rare earth element.
The know-why of the present invention is:
1, the present invention carries out material oxidation to neodymium iron boron waste material, so that valuable metal is fully converted into metal oxygen in material
Compound, wherein Co element is converted into bivalence and cobaltic oxide in this link；In general, in preferred process conditions
Under, Co element 95% can be converted into metal-oxide after material oxidation link, wherein 65～90% is above with high price oxidation
Thing (Co2O3) form existence.From the point of view of chemically in characteristic, it is metal-oxide by the Co cycling of elements in material, Co can be improved
The acidleach rate of element.
2, according to excellent molten extract technology commonly used in current industry, in excellent molten acidleach link, more than 97% matter in material
The Co element of amount mark can enter among leachate system.In view of Co3+Ion has the strongest oxidisability, and Co element is leaching
All with CoCl in liquid system2Form exists, simultaneously and be stored in leachate system and have rare earth ion, Fe2+、Co2+、Al3+And
A small amount of Fe3+(wherein the main component in system is rare earth ion).
3, the present invention carries out oxydrolysis to excellent molten leachate, is trivalent cobalt with Co in this link by Co element oxide
(OH)3Sedimentary form " retains " from leachate system；Fe, Co unit by oxydrolysis, in excellent molten leachate
Element will go in oxidation precipitation slag, and this most just can meet the technological requirement that follow-up rare earth extraction separates simultaneously.
To Co (OH)2With Co (OH)3Dissociation constant contrasted, its pKa value is respectively 14.8 and 43.8, both gaps
The most obvious；Therefore, by Co element after divalent oxygen turns to trivalent, it is easier to obtain the hydrogen-oxygen of Co element from leachate system
Compound precipitates, thus reaches to retain the technical purpose reclaiming Co element.From electrode potential, E0(Fe3+/Fe2+)=0.77V、
E0(Co3+/Co2+)=1.83V, positive trivalent cobalt ion Co3+Oxidisability much larger than positive trivalent Fe3+Ion, both gaps are obvious；Change
Yan Zhi, it is ferrous oxidising for ferric iron that bivalence cobalt oxide turns to the contrast of trivalent cobalt, from the selection of oxidant, is then to need choosing
Select the oxidant that oxidisability is higher.According to known achievement in research, because the oxidisability of trivalent cobalt ion is very strong, oxidizing potential is very
Height, and hydrolysis can be precipitated under the lowest pH, pH just can precipitate hydrolysis about 0.5；And divalent cobalt ion is at about pH6
Just can precipitate hydrolysis.
According to the technology of the present invention, one-step technology have employed and bivalence cobalt element in excellent molten leachate can be oxidized to trivalent
The strong oxidizer (i.e. oxidant A) of cobalt element, is mainly composed of Fe (OH) in gained oxidation precipitation slag A3With Co (OH)3.General feelings
Under condition, in terms of neodymium iron boron waste material rare earth elements total amount, the accounting that rare earth element is lost in oxidation precipitation slag A 0.2% with
Under.In view of excellent molten leaching link has retained the Fe element of the overwhelming majority, generally, Co (OH) in oxidation precipitation slag A3Institute
Account for mass fraction between 30～80%；In terms of Co element total amount in neodymium iron boron waste material, by oxidation precipitation slag A with Co (OH)3Shape
State reclaims Co element accounting more than 95%.
According to the technology of the present invention, two-step process is initially with being by ferrous iron element oxide in excellent molten leachate
Ferric iron element and be not enough to be oxidized to bivalence cobalt element the oxidant (i.e. oxidant B) of trivalent cobalt element, gained oxidation is heavy
Mud B is mainly composed of Fe (OH)3Or FeOOH；Generally, in terms of Co element total amount in neodymium iron boron waste material, Co
Element loss accounting in oxidation precipitation slag B below 2%, and in leachate B Fe element residual concentration 0.2mg/L% with
Under.
According to the technology of the present invention, bivalence cobalt element in leachate B can be oxidized to three by follow-up have employed of two-step process
The strong oxidizer (i.e. oxidant C) of valency cobalt element, is mainly composed of Co (OH) in gained oxidation precipitation slag C3.Generally,
In terms of Co element total amount in neodymium iron boron waste material, by oxidation precipitation slag C with Co (OH)3Form reclaim Co element accounting 94% with
On.
Generally, using two-step process, in terms of 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 is below 0.3%.
According to the technology of the present invention, excellent molten leachate after oxydrolysis, Fe in leachate system under one-step technology,
Co element total residual concentration under 0.1mg/L, two-step process in leachate system Fe, Co element total residual concentration exist
Below 0.06mg/L；Accordingly, from the angle of recovering rare earth element, the leachate system after oxidized hydrolysis has reached to fill
Divide the technical purpose purified.
4, reclaim and compound preparation technology according to the cobalt element of the present invention, carry out heating for dissolving using hydrochloric acid, sulphuric acid
During, Co (OH) in oxidation precipitation slag3Will be with cobaltous CoCl2、CoSO4Form be dissolved enter into solution system it
In, and then process through post precipitation and obtain a series of cobalt (II) compound.
The present invention compared with prior art, has an advantage in that:
1, the technology path design of the present invention, the process procedure that can be reclaimed by Co reclaims industry with domestic neodymium iron boron waste material
Flow path match and Integration ofTechnology is realized between existing recovering rare earth device line.In terms of technical goal, it then follows identity principle,
Based on material oxidation, excellent molten leaching and the processing step of oxydrolysis, achieve in the front end of whole flow process and Co element is had
Effect retains and reclaims, and also ensure that extracted liquid ties up to subsequent handling and there is not the interference of Fe, Co element simultaneously, is conducive to extraction point
The technique of rare earth realizes.
2, the characteristic of appraising at the current rate that Co element is possessed by the technical thought of the present invention cleverly, and bivalence Co and trivalent Co
Stability difference combines；It is also due to trivalent cobalt and under the lowest pH, there is precipitation hydrolysis properties, with leachate system
Acidic character can be consistent, eliminates 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 terms of oxidisability of the technical thought of the present invention, thus
Selecting different oxidants and oxidizing condition, the substep realizing Fe, Co element retains, thus the easiest having reached is reclaimed
The technical purpose of Co element.
4, the stability difference caused due to the valence state of Co element, and cobaltic low ph value precipitation hydrolysis properties,
From process implementation, the rare earth elements existed a large amount of in leachate system will not be produced loss.Therefore, the technology of the present invention
There is good process controllability, require to be respectively provided with good Technological adaptability from the process conditions of each step and control, from
And ensure that Co element with Co (OH)3Being retained in that precipitate morphology is concentrated is reclaimed, at this among hydrolytic precipitation slag
In link gained precipitate, the response rate of gained Co element can reach more than 94%, and the loss of rare earth element can control
Less than 0.3%.
Accompanying drawing explanation
Accompanying drawing 1 is the process chart of the present invention.
Detailed description of the invention
So that the purpose of the present invention, technical scheme and advantage are clearer, below in conjunction with embodiment to this
Bright further illustrate.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not used to limit this
Invention.
Embodiment 1:
Take a collection of leftover pieces deriving from Nd-Fe-B permanent magnet material machining link generation.After testing, above-mentioned every 100g neodymium
Ferrum boron metals from waste element includes: rare earth element total amount 31.03g(wherein main component is Nd, separately includes Pr, Dy, Gd), Fe
Constituent content 60.01g, Co constituent content 4.36g, Al constituent content 0.40g.
Take 1000Kg material in above-mentioned a collection of neodymium iron boron waste material, be ground being crushed to mean diameter 300 by ball mill
Below mesh, the material after pulverizing carries out oxidizing roasting (sintering temperature 700 DEG C, roasting time 1 hour) in rotary kiln, then uses
The hydrochloric acid of 2.7N concentration the material after oxidizing roasting is leached (extraction temperature 85 DEG C, control leach terminal pH value be
2.0) material after, having leached obtains excellent molten leachate and excellent molten waste residue after filter pressing separates.According to purposes of statistical process, Yancheng is used
Amount is about 1.8 cubic metres.
Detecting excellent molten leachate, wherein Co constituent content is that 42.80Kg, Fe element remains total amount 51.78Kg, its
In two valency Fe element total amounts 41.48Kg, trivalent Fe element total amount 10.30Kg.Calculating accordingly, the Co unit in neodymium iron boron waste material have
98.16% enters in excellent molten leachate.
Excellent molten leachate is divided into two parts of equal deal.
Take the excellent molten leachate of a copy of it, carry out oxydrolysis by one-step technology.
Use ozonator to produce ozone and be used as oxidant, carried out by ozone in special ozone-oxidizing device
Oxydrolysis reacts, and reaction temperature controls at 40 DEG C；Sample analysis when separating out without obvious sediment thing in question response system, works as leaching
In the liquid-phase system of liquid, Co element residual concentration is less than stopped reaction during 0.4mg/L, carries out filter pressing separation immediately, obtains aoxidizing water
Leachate after solution and oxidation precipitation slag.According to purposes of statistical process, ozone usage is that 19.35Kg(closes 403.12mol)；Calculate and understand
Needed for bivalence Fe in this portion of excellent molten leachate, Co element are all oxidized to trivalent Fe, Co element, the theory of oxidant, ozone is worked as
Amount is 366.54mol；The actual amount of oxidant, ozone is theoretical equivalence value 110%.
To oxidation precipitation slag sample analysis, gross weight is 88.53Kg, and its Main Ingredients and Appearance is Fe (OH)3With Co (OH)3, wherein
Co(OH)3Weight is 38.93Kg, accounts for the 43.97% of oxidation precipitation slag；According to Co element total amount 21.8Kg corresponding to waste material source
Meter, by oxidation precipitation slag with Co (OH)3It is 95.78% that form reclaims Co element accounting.
Analyzing the content of rare earth in oxidation precipitation slag, its rare earth elements total amount closes 202g, according to corresponding to waste material source
Rare earth element total amount 155.15Kg is counted, and it is 0.13% that rare earth element is lost in the accounting in oxidation precipitation slag.
Above-mentioned oxidation precipitation slag is mixed with the sulphuric acid being added 25% concentration, is heated to 95 DEG C, treat that material is completely dissolved
After, add a little hydrogen peroxide, under conditions of being stirred continuously, carry out slowly continuous print addition Na2CO3Solution, keeps system pH
In the case of value stabilization, constantly have sodium ihleite Precipitation；Treat to separate out without obvious sediment thing, and occur that pH value substantially rises
Time, stop Na2CO3Solution.Carry out reaction mass filtering and separate, obtain sodium ihleite precipitation and filtrate.Filtrate is added
Precipitant Disodium oxalate., collects precipitate and obtains cobalt oxalate product.Cobalt oxalate is carried out roasting, according to the difference of sintering temperature,
Cobalt/cobalt oxide product to different valence state.
Embodiment 2:
In Example 1, the most a excellent molten leachate, carries out oxydrolysis by two-step process.
The oxidant hydrolyzed as once oxidation initially with sodium chlorate, is heated to 90 DEG C by excellent molten leachate, wherein
It is continuously added sodium chlorate solution, after precipitation starts to occur, slows down sodium chlorate solution and add speed；Without substantially in question response system
Sample analysis when precipitate separates out, when in the liquid-phase system of leachate, Fe element residual concentration stops when controlling at below 0.2mg/L
Only reaction, carries out filter pressing separation immediately, obtains the leachate after once oxidation hydrolysis and once oxidation precipitation slag.Unite according to technique
Meter, sodium chlorate consumption is that 7.10Kg(closes 66.67mol)；Calculate and understand the whole oxygen of bivalence Fe element in this portion of excellent molten leachate
The theoretical equivalence turning to trivalent Fe element requisite oxygen agent sodium chlorate is 61.73mol；The actual amount of oxidant sodium chlorate is reason
Opinion equivalent value 108%.
To once oxidation precipitation slag sample analysis, gross weight is 81.69Kg, and it is mainly composed of FeOOH.Analyze an oxygen
Changing the Co constituent content in hydrolysis residue, wherein Co constituent content is 231g, according to the Co element total amount corresponding to waste material source
21.8Kg counts, and Co element loss accounting in once oxidation precipitation slag is 1.06%.
Use the oxidant that sodium hypochlorite hydrolyzes as secondary oxidation again, the leachate after once oxidation hydrolyzes adds
Sodium hypochlorite carries out secondary oxidation hydrolysis, and reaction temperature controls at 45 DEG C；Take when question response system separates out without obvious sediment thing
Sample is analyzed, the stopped reaction when Co element residual concentration is less than 0.4mg/L in the liquid-phase system of leachate, carries out filter pressing immediately and divides
From, obtain the leachate after secondary oxidation hydrolysis and secondary oxidation precipitation slag.According to purposes of statistical process, sodium hypochlorite consumption is
15.27Kg(close 204.94mol)；Calculate bivalence Co element in the leachate after understanding this part of once oxidation hydrolysis all to aoxidize
It is 181.36mol for the theoretical equivalence of oxidizing agent sodium hypochlorite needed for trivalent Co element；The actual amount of oxidizing agent sodium hypochlorite
For theoretical equivalence value 113%.
To secondary oxidation precipitation slag sample analysis, gross weight is 39.13Kg, and its Main Ingredients and Appearance is Co (OH)3, wherein Co
(OH)3Weight is 38.55Kg, accounts for the 98.50% of secondary oxidation precipitation slag；According to the Co element total amount corresponding to waste material source
21.8Kg counts, by secondary oxidation precipitation slag with Co (OH)3It is 94.86% that form reclaims Co element accounting.
Analyzing the content of rare earth in once oxidation precipitation slag and secondary oxidation precipitation slag, its rare earth elements total amount is closed
326g, according to the rare earth element total amount 155.15Kg meter corresponding to waste material source, rare earth element is lost in accounting in oxidation precipitation slag
Ratio is 0.21%.
Above-mentioned secondary oxidation precipitation slag is divided into equal two part.
A copy of it secondary oxidation precipitation slag dilute hydrochloric acid of 3% concentration rinses, then after washing with soft water, dry
Co (OH) is obtained after dry3Product.
By mixed in hydrochloric acid with 2N concentration in additionally a oxidation precipitation slag, it is heated to 85 DEG C, after material is completely dissolved,
Add precipitant ammonium hydrogen carbonate, collect precipitate and obtain cobalt carbonate product.Cobalt carbonate is carried out roasting, according to sintering temperature not
With, obtain the cobalt/cobalt oxide product of different valence state.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention
Any amendment, equivalent and the improvement etc. made within god and principle, should be included within the scope of the present invention.
Claims (10)
1. one kind from neodymium iron boron magnetic materials waste material reclaim Co element simplified industrial method, it is characterised in that the method include as
Under several steps:
(1) material oxidation: neodymium iron boron waste material is carried out material oxidation；The oxidation of described material uses air autoxidation, roasting oxygen
One or both in change；
(2) excellent molten leaching: the material after oxidation calcination is added hydrochloric acid and carries out excellent molten leaching, leaching product is carried out solid-liquid and divides
From, obtain excellent molten leachate and excellent molten waste residue after separation；The molar concentration of described hydrochloric acid is between 1.5N～7N；Excellent molten leaching is eventually
Point pH value controls between 2.0～2.5；
(3) oxydrolysis: excellent molten leachate is carried out oxydrolysis, one of employing following two method:
One-step method:
In excellent molten leachate, add oxidant A carry out oxydrolysis, oxydrolysis product is carried out solid-liquid separation and is leached
Liquid A and oxidation precipitation slag A；Described oxidant A is hypochlorite, ferrate, ozone, chlorine, peroxydisulfate, permonosulphuric acid
One or more mixture in salt；According to bivalence Fe, Co element in excellent molten leachate are all oxidized to trivalent Fe, Co element
The theoretical equivalence of requisite oxygen agent, oxidant A addition is the 100～180% of theoretical equivalence value；
Two-step method:
In excellent molten leachate, first add oxidant B carry out once oxidation hydrolysis, oxydrolysis product is carried out solid-liquid separation and obtains
To leachate B and oxidation precipitation slag B；Described oxidant B is chlorate, hydrogen peroxide, potassium permanganate, potassium dichromate, bromate, nitre
One or more mixture in acid, bromine water, oxygen；According to bivalence Fe element in excellent molten leachate is all oxidized to trivalent Fe
The theoretical equivalence of element requisite oxygen agent, oxidant B addition is the 100～150% of theoretical equivalence value；
In leachate B, add oxidant C again carry out secondary oxidation hydrolysis, oxydrolysis product is carried out solid-liquid separation and is soaked
Go out liquid C and oxidation precipitation slag C；Described oxidant C is hypochlorite, ferrate, ozone, chlorine, peroxydisulfate, crosses a sulfur
One or more mixture in hydrochlorate；According to bivalence Co element in leachate B is all oxidized to trivalent Co element requisite oxygen
The theoretical equivalence of agent, oxidant C addition is the 100～160% of theoretical equivalence value；
(4) cobalt element reclaims and prepared by compound: according to different oxydrolysis methods, and cobalt element reclaims and compound preparation point
Cai Yong the following two kinds method:
Method one: hydrolyze gained oxidation precipitation slag A for one-pot oxidation, after addition sulphuric acid carries out heating for dissolving, uses yellow ferrum
Vitriol method removes ferrum, after filtering scum, add in filtrate the one in oxalic acid, oxalates, carbonate, bicarbonate, inorganic base or
Several mixture carry out precipitation and obtain CoC2O4、CoCO3、Co(OH)2In one or more mixture, more fired obtain cobalt
Oxide；
Method two: for two-step method oxydrolysis gained oxidation precipitation slag C, carries out pickling, washing, obtains Co (OH) after drying3；
In oxidation precipitation slag C, add hydrochloric acid or sulphuric acid carry out heating for dissolving, add oxalic acid, oxalates, carbonate, bicarbonate,
One or more mixture in inorganic base carry out precipitation and obtain CoC2O4、CoCO3、Co(OH)2In one or more mixing
Thing, the more fired oxide obtaining cobalt.
The simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material the most according to claim 1, its feature
It is: leftover pieces, vacuum melting that step (1) described neodymium iron boron waste material produces by Nd-Fe-B permanent magnet material machining link are produced
Among the grinding powder produced in the micropowder of the slag of life, pulverizing process generation, bruting process, defective permanent magnet waste product one
Kind or several mixture；Step (1) had also carried out physics to neodymium iron boron waste material before neodymium iron boron waste material carries out oxidizing roasting
Pulverize or chemically fragmenting processes；Material oxidation uses roasting oxidation, and sintering temperature is 600 DEG C～1100 DEG C.
The simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material the most according to claim 1, its feature
It is: the step (2) material after oxidation calcination adds also to enter the material after oxidation calcination before hydrochloric acid carries out excellent molten leaching
Row is pulverized；While addition hydrochloric acid carries out excellent molten leaching, in material system, also with the addition of the one in sulphuric acid, nitric acid or two
Kind of mixture, sulphuric acid, nitric acid addition by H ionic equivalent than based on less than the 10% of hydrochloric acid total amount；Step (2) described hydrochloric acid
Molar concentration between 2.0N～5.0N；Described excellent molten extraction temperature is more than 70 DEG C.
The simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material the most according to claim 1, its feature
It is: step (3) described oxidant A is the one in hypochlorite, ferrate, ozone, chlorine；According to by excellent molten leachate
Middle bivalence Fe, Co element are all oxidized to trivalent Fe, the theoretical equivalence of Co element requisite oxygen agent, and oxidant A addition is reason
The 105～120% of opinion equivalent value.
The simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material the most according to claim 1, its feature
It is: step (3) described oxidant B is the one in chlorate, hydrogen peroxide；According to by complete for bivalence Fe element in excellent molten leachate
Portion is oxidized to the theoretical equivalence of trivalent Fe element requisite oxygen agent, and oxidant B addition is the 105～120% of theoretical equivalence value.
The simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material the most according to claim 1, its feature
It is: step (3) described oxidant C is the one in hypochlorite, ferrate, ozone, chlorine；According to by leachate B
Bivalence Co element is all oxidized to the theoretical equivalence of trivalent Co element requisite oxygen agent, and oxidant C addition is theoretical equivalence value
105～120%.
The simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material the most according to claim 1, its feature
It is: step (4) described ihleite method is after solution is heated to more than 90 DEG C except ferrum, adds NaCO in the solution3、NaOH
In one, by the Fe in solution3+It is converted into NaFe3(SO4)2(OH)6The sodium ihleite precipitate of structure and reach except ferrum mesh
's.
The simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material the most according to claim 1, its feature
It is: step (4) described pickling is to use mass fraction dilute hydrochloric acid below 5% or dilute sulfuric acid to wash material.
The simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material the most according to claim 1, its feature
It is: it is dense that the terminal point determining of step (3) described one-pot oxidation hydrolysis is based on Co element residual in the liquid-phase system of leachate
Degree controls below 0.4mg/L；In described two-step method, the terminal point determining of once oxidation hydrolysis is based in the liquid-phase system of leachate
Fe element residual concentration controls at below 0.2mg/L；In described two-step method, the terminal point determining of secondary oxidation hydrolysis is based on leaching
In the liquid-phase system of liquid, Co element residual concentration controls at below 0.4mg/L.
The simplified industrial method reclaiming Co element from neodymium iron boron magnetic materials waste material the most according to claim 1, its feature
It is: the described excellent molten waste residue of step (2) is mainly composed of Fe2O3, step (3) described oxidation precipitation slag B is mainly composed of Fe
(OH)3Or FeOOH, is used to produce iron oxide red and ferrite magnetic material；Step (3) described leachate A and the master of leachate C
Wanting composition is rare earth chloride, for by extract and separate recovering rare earth element.
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| CN105734296B (en) * | 2016-04-20 | 2017-10-31 | 南阳东方应用化工研究所 | A kind of method of comprehensive utilization of neodymium iron boron waste material acid leaching residue |
| 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 |
| 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 |
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