CN104446412A - High-performance permanent-magnet ferrite pre-sintered material prepared based on NdFeB wastes and preparation method thereof - Google Patents
High-performance permanent-magnet ferrite pre-sintered material prepared based on NdFeB wastes and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-performance permanent-magnet ferrite pre-sintered material prepared based on NdFeB wastes and a preparation method thereof. The ferrite pre-sintered material has a hexagonal-crystal-system ferrite structure and is subjected to combined ion substitution through rare-earth elements and non-rare-earth elements, such as Co; in the pre-sintered material, a Fe element is totally originated from the NdFeB wastes; various metallic rare-earth elements for combined ion substitution are totally or partially originated from the NdFeB wastes. According to the high-performance permanent-magnet ferrite pre-sintered material prepared based on the NdFeB wastes and the preparation method thereof, in the production process, secondary process wastes, which are plentifully generated during the hydrometallurgical rare-earth element recovery of the NdFeB wastes and have no proper resource values, are fully utilized; in the implementation of the technical scheme, the technology adopted by the invention and the currently-industrialized NdFeB waste rare-earth resource recovery process flows are docked in a seamless manner, and organic and reasonable combination is realized in the aspects of the improvement of performance of magnets through carrying out resource utilization and ion substitution on the secondary wastes, the simplicity and convenience of process implementation and the like.
Description
Technical field
The invention belongs to the technical field of waste resource comprehensive utilization, be specifically related to a kind of high-performance permanent-magnet ferrite Preburning material based on neodymium iron boron waste material production and preparation method.
Background technology
Nd-Fe-Bo permanent magnet material 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.Along with the fast development of information industry, consumer electronics industry and novel energy power truck industry, the Application Areas of Nd-Fe-Bo permanent magnet material also constantly expands thereupon.The output of domestic neodymium iron boron magnetic materials is in recent years in rapid growth situation, and oneself reaches the scale of annual 100000 tons at present, and still in continuous growth.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%; Calculate accordingly, domestic neodymium iron boron waste material generation has reached annual more than 30,000 tons.
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%; In order to obtain different performance, in magnetic material, normal adding portion other rare earth elements such as Pr, Dy, Tb, Gd are with alternative Nd, and with metallic element Some substitute Fe such as Co, Zn, Al, Cu, Nb.We gather neodymium iron boron magnetic materials component situation on market, and the content situation of all kinds of Addition ofelements is as following table (mean value).
The production of Neodymium iron boron magnetic is all generally batching row manufacture more in advance, so the neodymium iron boron waste material produced in each process for processing link, 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, Dy, Pr, Gd 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, main processing method adopts hydrometallurgical processes, and its basic fundamental method adopts first to leach, and then to leach liquor in addition extracting and separating and obtain all kinds of rare-earth products.With regard to industry Situation, in the technique of various hydrometallurgical recovery rare earth, the common employing of domestic enterprise be " oxidizing roasting-hydrochloric acid excellent molten-extracting and separating " scheme.Based on above-mentioned hydrometallurgical processes, while realizing rare earth element extraction, the Fe element accounting for most component ratio in neodymium iron boron waste material system almost can enter among all kinds of technique waste residue completely.
Calculate according to current neodymium iron boron waste material generation, have the high-quality Fe element more than 20,000 tons to enter into all kinds of technique waste residue every year, all kinds of technique waste residue quantity formed are more than 40,000 tons/year.These " secondary processes wastes ", its component is formed based on trivalent Fe element, and comprises the non-thulium such as Co, Zn, Al, Cu, Nb of part in original neodymium iron boron waste material system, and carry a small amount of rare earth element secretly, component situation is comparatively complicated simultaneously; Owing to lacking effective comprehensive utilization technique and Industry support, for a long time by low value process or discard in vain, fail to embody due resource utilization far away and be worth.
Comprehensive utilization technique outside neodymium iron boron waste material recovering rare earth element, especially after neodymium iron boron waste material recovering rare earth, in " secondary processes waste " and neodymium iron boron waste material system, the technology report of the comprehensive utilization aspect of Fe element is less.Domestic published report mainly adopts coprecipitation method that Fe cycling of elements in waste material is prepared Mn-Zn ferrite.The people such as Zhong Xiaolin, Song Ning report the waste residue after adopting neodymium iron boron waste material Extraction of rare earth element, manganous carbonate, zinc sulfate are raw material, by leaching, purification, co-precipitation, calcining and obtain the higher Mn-Zn ferrite of quality; Purifying solution formula before co-precipitation is Fe
2o
3: MnO:ZnO=70.20:21.89:7.91(mass ratio).Be spinel soft magnetic ferrite structure by the Mn-Zn ferrite prepared by technique scheme, with regard to MFe
2o
4basic form, it needs add a large amount of Mn, Zn elements (mole partition reaches 50% of Fe element) and entirely soak together with Fe element, need to use a large amount of sulfuric acid, ammonium sulfide, Neutral ammonium fluoride, lime and precipitation agent bicarbonate of ammonia in leaching, purification, co-precipitation link, the consumption of resource and the energy is very large, and overall economic worth is not high.[reference: " preparing the research of Mn-Zn ferrite micropowder with neodymium iron boron waste material recycling waste residue ", magnetic material material and parts, 2007,38 (6), 57-60; " preparing the research of Mn-Zn ferrite micropowder with the waste residue after neodymium iron boron waste material Extraction of rare earth ", China rare earth journal, 2006,24,369-371; " Mn-Zn ferrite is prepared in the microwave heating of neodymium iron boron secondary residue ", rare metal, 2008,32 (4), 454-458]
Summary of the invention
Object of the present invention produces a kind of high performance permanent ferrite prefiring material based on the comprehensive utilization of neodymium iron boron waste material, and announces its preparation method.Mentality of designing of the present invention is based on the technology of domestic neodymium iron boron waste material resource reclaim and industry Situation, make full use of in neodymium iron boron waste material recovering rare earth process by the element components of secondary waste and partition basis, according to configuration characteristic and the molecular design theory of high-performance permanent-magnet ferrite, according to the easy process program of " many utilizations, few interpolation ", manufacture and design a kind of high performance permanent ferrite prefiring material.
In order to the technical scheme of the present invention of statement clearly, first set forth the extract technology of neodymium iron boron waste material recovering rare earth element, consequent secondary processes waste situation is illustrated.
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: simple substance element in alloying constituent (each rare earth element, Fe and Addition ofelements Co, Zn, Al etc.), through oxidizing roasting, is fully converted into oxide compound (rare earth oxide, Fe by neodymium iron boron waste material
2o
3, Co
2o
3, ZnO, Al
2o
3deng), adopt the excellent row that dissolves into of hydrochloric acid excellent molten, wherein highly active 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 this excellent molten waste residue, Fe element is all almost with Fe
2o
3form exists.Usually, still containing elements such as a small amount of Fe, Co in the leach liquor obtained under the excellent molten technique of hydrochloric acid, disadvantageous effect is existed to extraction and separation technology and rare-earth products quality, so first carried out extracting the process of deironing to leach liquor before extracting and separating, the iron produced in this link component of mixing is another class " secondary processes waste "; This iron component Fe element in strip liquor of mixing is with Fe
3+complexing salt form exists, and can be converted into Fe (OH) through alkaline chemical precipitation
3form.
In order to the technical scheme of the present invention of statement clearly, next need set forth the structure of permanent-magnet ferrite and the ultimate principle of ion replacement and promote effect.
In recent decades, people are found by a large amount of research work, there is the permanent-magnet ferrite mainly hexgonal screw of industrial value, be divided into six types from crystal configuration: M type, W type, X-type, Y type, Z-type and U-shaped, wherein simple and the most the most frequently used is M type ferrite.At present in actual industrial production, the mainly M type ferrite of the permanent-magnet ferrite material used, is wherein mainly represented as strontium ferrites and barium ferrite, and its chemical constitution molecular formula is MeFe
12o
19, also can be write as MeO6Fe
2o
3this expression-form, wherein Me=Ba, Sr, Pb plasma, its crystalline structure is hexaplanar magnetoplumbite type.M type hexgonal screw owing to having the chemical stability of superior cost performance, higher coercive force and saturation magnetization, high magnetocrystalline anisotropy, excellent mechanical endurance and excellence, always in occupation of very important status in permanent magnet material.Along with the performance requriements of high speed development to permanent-magnet ferrite material of modern science and technology improves constantly, the high-performance permanent-magnet ferrite of high remanent magnetism Br, high-coercive force Hcj, high energy product (BH) max is also the focus of permanent magnet material research always.
The magnetic wood property of permanent-magnet ferrite can depend primarily on its microstructure and preparation method.Many research work show, in order to obtain high performance permanent-magnet ferrite, just must carry out ion replacement to it, the principle of replacement is: (1) will keep the balance of number of ions, and before and after namely replacing, ion populations should remain unchanged; (2) electricity price to be kept to balance.Will consider that the radius replacing ion should be close with the radius of replaced ion, ion is replaced mainly to the Me in permanent-magnet ferrite simultaneously
2+and Fe
3+replace; One is to Me
2+replacement, more stable crystalline structure and larger magnetocrystalline anisotropy can be obtained; One is to Fe
3+replacement, to obtain larger Bohr magnetron number, thus increase saturation magnetization, can the most directly, farthest affect the magnetic structure of permanent-magnet ferrite, thus improve the magnetic property of magnet.
For many years, scientific worker has carried out a large amount of scientific efforts, finds appropriate substitution ion and alternative techniques, carries out ion replacement to hexagonal permanent magnetic ferrite, and has obtained some high performance permanent-magnet ferrites.To have the M type ferrite of most widespread use, the research work having obtained important application actual effect at present comprises: (1) rare earth element Re
3+replace Me
2+ion; (2) transition element Co
2+replace Fe
3+ion; (3) Al
3+replace Fe
3+ion; (4) Cu
2+replace Fe
3+ion; (5) La
3+-Zn
2+combine and replace Sr
2+-Fe
3+; (6) Zn
2+-Nb
4+combination replacement Fe
3+; (7) La-Co combines replacement Me
2+-Fe
3+etc..This wherein the revolutionary industry meaning of most be that La-Co combines replacement, La
3+replacement can stablize magnetoplumbite type, Co
2+at 4f
2the replacement of position can make 4f
2the reverse magnetic moment of brilliant position reduces, and cause the magnetocrystalline anisotropy of material to strengthen, magnet performance obviously promotes.Based on such technological principle, 1999 ~ 2000 years, Japanese TDK company developed lanthanum cobalt substituted type FB9 series high-performance permanent-magnet ferrite (main model is FB9B, FB9H, FB9N); 2007, Japanese TDK company researched and developed again and releases FB12 series product.Similar, the high-performance Y BM-9 series of Hitachi Metals company (Hitachi Matals) also utilizes La-Co to combine displaced type product just.Cochardt can make the maximum magnetic energy product of strontium ferrites obtain theoretical value at prophesy ionic replacement in 1963, and with regard to the FB12 series product performance of current Japanese TDK company, the prophesy of Cochardt is almost achieved.With regard to this point, also exactly demonstrate ionic association and replace the technical way realizing high performance ferrite material just.
According to the molecular design theory of high performance permanent magnetic materials, contrast the elementary composition situation in neodymium iron boron waste material and aforementioned secondary processes waste, elaboration is described as follows:
1, the secondary processes waste produced in the process of hydrometallurgical processes Extraction of rare earth, its main component is Fe element; In general, the Fe element more than 98% in neodymium iron boron waste material can enter into secondary waste thing, and with Fe
3+ionic forms exists, and wherein the overwhelming majority is with Fe
2o
3form exists, and Fe (OH)
3also being easy to receive thermal transition is Fe
2o
3.
As everyone knows, high-quality iron oxide red (Fe
2o
3) raw material produces the important foundation of high performance permanent magnetic materials, as a kind of industrial chemicals, it obtains difficulty and manufacturing cost much larger than iron sand and iron scale.Domestic permanent-magnet ferrite enterprise about 70% is with iron scale (Fe
3o
4) for raw material carries out the production of permanent-magnet ferrite, being difficult to produce high-grade permanent-magnet ferrite has been common recognition, and product majority is the low-and-medium-grade products being equivalent to the TDK company FB4 series trade mark.In this regard, produce high performance permanent magnetic materials from neodymium iron boron waste material and secondary processes waste thereof and possess important resource base.
2, for the performance and application requirement of Nd-Fe-Bo permanent magnet material, on the basis of NdFeB alloy, all kinds of rare earth element and non-metallic metal element are used as Addition ofelements wherein, comprise non-Nd rare earth element (in order to replace Nd) and non-thulium Co, Al, Zn, Cu, Nb(in order to alternative Fe).According to the extract technology of hydrometallurgical recovery rare earth, in secondary processes waste, the non-thulium such as Co, Zn, Al, Cu, Nb containing considerable part in above-mentioned neodymium iron boron waste material system, carries a small amount of rare earth element secretly simultaneously.From the practical operation situation of our company's neodymium iron boron waste material recovering rare earth element technique, secondary processes waste roughly contains Co element, the Al element of 5 ~ 20%, Zn element, the Cu element of 30 ~ 90%, the Nb element of 20 ~ 50% of 10 ~ 50% of in former neodymium iron boron waste material system 10 ~ 60%, and is entrained with the rare earth element accounting for waste gross weight 0.5 ~ 5%.
Large quantifier elimination illustrates: the above-mentioned rare earth element Re in secondary processes waste
3+replace Me in permanent-magnet ferrite crystal configuration just
2+a kind of ideal chose of ion, Co
2+, Zn
2+, Al
3+, Cu
2+, Nb
4+ion replaces Fe in crystal configuration just
3+a kind of ideal chose of ion, follows same principle, and in secondary processes waste, the doping system of Re-CoZnAlNb meets the molecular design theory that permanent-magnet ferrite carries out the element associating ion replacement of rare earth element-transition race.
The object of the present invention is achieved like this: a kind of high-performance permanent-magnet ferrite Preburning material produced based on neodymium iron boron waste material, is characterized in that:
(1) described neodymium iron boron waste material is that various Nd-Fe-Bo permanent magnet material process for processing link produces waste material or waste product;
(2) described high-performance permanent-magnet ferrite Preburning material is hexgonal screw structure, and has carried out the replacement of associating ion by rare earth element and the non-rare earth comprising Co to hexgonal screw;
(3) in described high-performance permanent-magnet ferrite Preburning material, Fe element all derives from neodymium iron boron waste material, and the rare earth element being used as the replacement of associating ion derives from neodymium iron boron waste material with the non-thulium comprising Co is all or part of.
As preferably:
Based on the high-performance permanent-magnet ferrite Preburning material that neodymium iron boron waste material is produced, it is characterized in that:
(1) mixture of one or more among the grinding powder produced in the ultrafine powder that the slag that 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;
(2) described high-performance permanent-magnet ferrite Preburning material is M type ferrite structure, and has carried out the replacement of associating ion by rare earth element and the non-rare earth comprising Co to M type ferrite;
(3) in described high-performance permanent-magnet ferrite Preburning material, Fe element all derives from neodymium iron boron waste material; As among the rare earth element that ion is replaced, contain the whole rare earth component of neodymium iron boron waste material in the secondary processes waste of hydrometallurgical recovery rare earth; As among the non-thulium comprising Co that ion is replaced, contain the whole non-rare earth metal component of neodymium iron boron waste material in the secondary processes waste of hydrometallurgical recovery rare earth except Fe element.
Prepare a method for above-mentioned high-performance permanent-magnet ferrite Preburning material, it is characterized in that the method comprises following several step:
(1) process of neodymium iron boron waste material:
Neodymium iron boron waste material is carried out oxidizing roasting; Material after oxidation calcination is added hydrochloric acid and carries out excellent molten leaching, solid-liquid separation is carried out to leaching product, after separation, obtains leach liquor and excellent molten waste residue; Carry out extraction deironing to leach liquor, carry out back extraction, alkaline chemical precipitation in strip liquor by water or dilute hydrochloric acid, sediment separate out to be mixed component as iron;
Leach liquor after extraction deironing is used for recovering rare earth element;
Excellent molten waste residue and iron mix component for the production of high performance ferrite Preburning material;
(2) elution:
Elution is carried out to the excellent molten waste residue obtained after neodymium iron boron waste material process and iron component of mixing;
(3) batching before pre-burning:
Main batching: based on the excellent molten waste residue after elution, or to mix component based on the iron after elution, or the mixture of component of mixing based on the excellent molten waste residue after elution and iron, adds containing Sr compound or contains Ba compound or contain Pb compound as main batching; Described is SrCO containing Sr compound
3, SrO, Sr (OH)
2in one or more mixtures, described containing Ba compound be BaCO
3, BaO, Ba (OH)
2in one or more mixtures, described containing Pb compound be PbCO
3, PbO, PbO
2, P
3o
4, Pb (OH)
2, Pb (OH)
4one or more mixtures;
Doping batching: add doping agent one, doping agent two as doping batching in the material after main batching, described doping agent one is rare-earth compound, and described doping agent two is except Fe and rare earth element, to comprise I B and II B race element in periodic table of elements transition metal element compound;
Additive formulations: add additive as additive formulations in the material after main batching and doping batching, described additive is one or more mixtures in calcium material, aluminium material, silicon material, boron material, and described calcium material is CaCO
3, CaO, Ca (OH)
2in one or more mixtures, described aluminium material is Al
2o
3, Al (OH)
3, H
3alO
3in one or more mixtures, described silicon material is SiO
2, H
2siO
3in one or both mixtures, described boron material is B
2o
3, H
3bO
3in one or both mixtures;
(4) material of having prepared burden is carried out pre-burning, obtain Preburning material.
As preferably:
In order to improve the changing effect of oxidizing roasting, 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.
The maturing temperature of oxidizing roasting described in step (1) is 600 DEG C ~ 1100 DEG C; Described extraction temperature is 70 DEG C ~ 100 DEG C, and the pH value leaching terminal controls 1.0 ~ 2.5; The extraction agent that described extraction deironing uses is N235 extraction agent.
Step (2) described elution adopts deionized water to carry out wash-out, or first carry out wash-out with deionized water again with dilute hydrochloric acid wash-out; The eluting water that elution produces directly mixes with leach liquor, or as processing wastewater after repeatedly recycling.
In order to lift technique effect, avoid interference the impact of ion, further, step (2) described elution refers to that in material, chloride ion content is less than 50ppm after elution.
Further, step (3) described batching is that each raw material is according to formula M e
1-xre
x(Fe
12-y1-y2-y3-y4-y5co
y1al
y2zn
y3cu
y4nb
y5)
zo
19prepare burden, in general formula, Me is Sr or Ba or Pd, in general formula, Re is rare earth element, and in general formula, the mol ratio of Me, Re, Fe, Co, Zn, Cu, Nb element is 1-x:x:(12-y1-y2-y3-y4-y4-y5) × z:y1 × z: y2 × z:y3 × z:y4 × z:y5 × z;
Wherein, x=0.01 ~ 0.80, y1=0.01 ~ 5.0, y2=0 ~ 2.0, y3=0 ~ 2.0, y4=0 ~ 2.0, y5=0 ~ 2.0, y1+y2+y3+y4+y5 ﹤ 12, z=0.7 ~ 1.2;
The batching of Me, Re, Co, Al, Zn, Cu, Nb element is with the Fe amount of element in material after elution for benchmark, calculates each feed proportioning amount according to the mol ratio of Me, Re, Co, Al, Zn, Cu, Nb element and Fe element; Wherein:
Me element all derives from main batching;
Re element is all or part of derives from neodymium iron boron waste material, is supplied time not enough by doping agent one;
Co, Zn, Cu, Nb element is all or part of derives from neodymium iron boron waste material, is supplied time not enough by doping agent two;
Al element derives from neodymium iron boron waste material wholly or in part, is supplied time not enough by additive-aluminium material;
The dosage of additive calcium material is by weight being 0 ~ 4.0% of batching total amount;
The dosage of additive silicon material is by weight being 0 ~ 4.0% of batching total amount;
The dosage of additive boron material is by weight being 0 ~ 4.0% of batching total amount.
Further, described in step (3), doping agent one is La
2o
3, La (OH)
3, La
2cO
3in one or more mixtures; Described doping agent two is CoO, Co
3o
4, Co
2o
3, Co (OH)
3, ZnO, Zn (OH)
2, CuO, Cu (OH)
2, Nb
2o
5, Nb
2o
3one or more mixtures.
In order to promote the effect of pre-burning, further, step (4) had also carried out mixing, pulverizing, pelletizing, drying and processing to material before material carries out pre-burning.
In order to promote pre-burning effect, further, the calcined temperature of pre-burning described in step (4) is between 800 DEG C ~ 1400 DEG C.
In order to ensure pre-burning effect, further, pre-burning operation described in step (4) also comprises allows material be down to the temperature-fall period of room temperature from calcined temperature, adopts the way cool to room temperature quenched by Preburning material, or adopts furnace cooling.
The conveniently application of Preburning material, further, Preburning material described in step (4) also adopts one or more coarse reduction equipment in jaw crusher, dry type vibrating ball mill, planetary ball mill to carry out coarse reduction, crushing material is become the Preburning material meal of 3 ~ 10 μm.
Compared with prior art, its advantage is in the present invention:
1, the present invention is based on neodymium iron boron waste material and produce high performance ferrite, take full advantage of in the process of neodymium iron boron waste material hydrometallurgical recovery rare earth element and produce in a large number and fail to embody " the secondary processes waste " that should have resource value always.From the realization of technical scheme, the technology of the present invention realizes " slitless connection " with the neodymium iron boron waste material resource utilization recovering rare earth technical process of industrialization at present, in technic index and technical object, there is clear and definite complementarity.
2, the present invention takes full advantage of the rejecting element in neodymium iron boron waste material hydrometallurgic recovery rare-earth process, comprise Fe, Co, Al, Zn, Cu, Nb element, one of main element that whole Fe element is prepared burden as ferrite, using the element such as Co, Al, Zn, Cu, Nb that adds as Fe element substitution in original neodymium iron boron waste material system as the appropriate doping agent of permanent-magnet ferrite, appropriate additive, thus reach optimize crystalline structure and promote magnetic wood property can object.Meanwhile, the present invention is using the appropriate doping agent of the rare earth element of entrained with in secondary processes waste as permanent-magnet ferrite.
In fact, with regard to the technique of current neodymium iron boron waste material hydrometallurgical recovery rare earth, in secondary processes waste except Fe element, be inevitable containing the various Addition ofelements (Co, Al, Zn etc.) in a certain amount of original waste material system and the rare earth element (mainly Nd) of carrying some amount secretly.If for the technical purpose of single utilization wherein Fe element, the removal of Co, Al, Zn and rare earth element will be very difficult, need complicated technique and a large amount of raw material consumption as cost.
Based on this, the present invention replaces at the utilization of resources of secondary waste thing, ion and organically, reasonably combines achieving in the simplicity that performance boost and the technique of magnet realize etc. three.
3, based on the technical scheme that the present invention improves, in the processing links of neodymium iron boron waste material according to the quite easy technique means of the control etc. of waste material apolegamy, element components collocation, leaching condition and elution requirement, the concrete partition requirement that high-performance permanent-magnet ferrite intermediate ion exchanges can well be met.Therefore, technical solution of the present invention has good controllability and Technological adaptability.
Accompanying drawing explanation
Accompanying drawing is process flow sheet of the present invention.
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 and a collection ofly derive from the mixture of grinding powder produced in the scrap stock and bruting process that Nd-Fe-Bo permanent magnet material machining link produces, wherein the weight ratio of scrap stock and grinding powder is 82:18.After testing, in above-mentioned every 100g neodymium iron boron waste material, metallic element comprises: rare earth element total amount 32.77g(is Nd 29.57g, Pr 2.13g, Dy 0.65g, Gd 0.42g wherein), Fe constituent content 60.35g, Co constituent content 2.11g, Al constituent content 0.42g, Zn constituent content 0.25g(Cu, Nb constituent content do not detect).
Get 2000Kg material in above-mentioned a collection of neodymium iron boron waste material, undertaken grinding below median size 100 order by ball mill, material after pulverizing is carried out oxidizing roasting (maturing temperature 900 DEG C in rotary kiln, roasting time 1 hour), with the hydrochloric acid of 3N concentration, (extraction temperature 85 DEG C is leached to the material after oxidizing roasting again, the pH value controlling to leach terminal is 1.9), the material after having leached obtains leach liquor and excellent molten waste residue after press filtration is separated.Carry out extraction deironing for leach liquor by N235-octanol-hydrochloric acid system, carry out back extraction with deionized water, in back extraction mutually, add NaOH solution precipitate, obtain iron after solid-liquid separation and to mix component.Leach liquor after extraction deironing is used for recovering rare earth element.
Collect above-mentioned excellent molten waste residue and iron component of mixing to be mixed, and with the dilute hydrochloric acid drip washing of 2% concentration once, then use deionized water washing by soaking twice; After press filtration, material solid content is 92%, detects Cl in material
-ion content is 30ppm, illustrates and reaches elution effect, above-mentioned wet feed 185.91Kg can conduct for subsequent use in ensuing burden process.
Material after above-mentioned elution is detected, wherein containing Fe element total amount 119.50Kg, Co element 1.65Kg, Al element 0.082Kg, Zn element 0.16Kg.Compare original each constituent content in neodymium iron boron waste material, the ratio entered in above-mentioned material of Fe, Co, Al, Zn element is respectively 99.01%, 39.10%, 9.76%, 32.00%.After testing, material rare earth elements total amount is 4.09Kg(wherein Nd content 2.01Kg), account for 2.2% of material gross weight.
Be listed as follows:
Get 20% of above-mentioned material total amount for carrying out the batching before pre-burning.
According to Sr
0.75re
0.25fe
11.75co
0.20al
0.03zn
0.02o
19prepare burden, in batching 100% the material of Fe element source after above-mentioned elution; With this Fe amount of element for benchmark, calculate each feed proportioning amount according to the mol ratio of Sr, Re, Co, Al, Zn element and Fe element.
Batching list is calculated as follows:
Based on above-mentioned batching list, separately add CaCO
3(98% purity) 0.25Kg, boric acid (98% purity) 0.084Kg are as additive, and the adding proportion of relative material total amount is respectively 0.6wt%, 0.2wt%.
By the material after above-mentioned batching and and water stir by 1:1 after add planetary ball mill ball milling 3h, rotating speed and ratio of grinding media to material are respectively 200r/min and 8:1, use three kinds of diameters be respectively 8,10 and 12mm hardened steel ball carry out ball milling.Material after ball milling carries out drying, sieve after cause some diameters to be the bead of 1cm.Material after pelletizing is carried out pre-burning in pre-burning stove, and calcined temperature is 1210 DEG C, and pre-burning soaking time is 2h, the material after insulation is cooled to room temperature with stove and obtains Preburning material.
By dry type ball milling, the crushing material after pre-burning is become the Preburning material meal of 4 ~ 8 μm.
The crystallinity analysis of Preburning material:
SEM scanning electron microscope analysis is carried out in sampling, analyzes the ferrite crystal grains of generation under different resolution, and analyze the crystallization of display Preburning material fine and closely woven, even, crystal particle scale is between 1 ~ 2 μm.
The magnetic property of Preburning material detects:
Get Preburning material meal sample, add the secondary additive of different content respectively, carry out wet-milling; After wet-milling, powder particle size is 0.8 μm, and filter cloth hangs dry, and in the magnetic field of 10KOe, orientation wet pressing becomes magnetic shoe.Sample sinters at roller kiln at 1240 DEG C of temperature in air, obtained series of samples after furnace cooling.
As can be seen from the above table:
(1) sample 1 ~ 4 has reached the magnetic property index of FB9 series product all; According to SJ/10410-2002 standard, reach the magnetic property index of the sintered permanent ferrite of YH40.
(2) because Preburning material adds CaCO in compounding links
3and boric acid, if add secondary additive again can there is disadvantageous effect among double sintering, Br value and (BH) max value decline all to some extent.
embodiment 2:
20% of material total amount batching before pre-burning is carried out after elution in another Example 1.Prepare burden according to the allocation sheet of embodiment 1, as different from Example 1, in batching, do not add CaCO
3, boric acid.
Preburning material meal is obtained according to the same method of embodiment 1.
The crystallinity analysis of Preburning material:
SEM scanning electron microscope analysis is carried out in sampling, analyzes the ferrite crystal grains of generation under different resolution, and analyze the crystallization of display Preburning material fine and closely woven, even, crystal particle scale is between 1 ~ 2 μm.
The magnetic property of Preburning material detects:
Get Preburning material meal sample, add the secondary additive of different content respectively, carry out wet-milling; After wet-milling, powder particle size is 0.8 μm, and filter cloth hangs dry, and in the magnetic field of 10KOe, orientation wet pressing becomes magnetic shoe.Sample sinters at roller kiln at 1240 DEG C of temperature in air, obtained series of samples after furnace cooling.
As can be seen from the above table:
(1) sample 6 ~ 9 has reached the magnetic property index of FB9 series product all; According to SJ/10410-2002 standard, reach the magnetic property index of the sintered permanent ferrite of YH40.
(2) Preburning material does not add CaCO in compounding links
3and boric acid, among double sintering, add the magnetic property of secondary additive meeting global optimization magnetic material, the amount of additive is with 0.6wt%CaCO
3+ 0.2wt%H
3bO
3for suitable, addition continuation rising will reach Br value and (BH) max value declines to some extent.
(3) comparative sample 1 and sample 8, additive before pre-burning add to Br value and (BH) max value favourable, but certain Hcb value and Hcj value can be sacrificed, Integrated comparative from magnetic material application characteristic, the front interpolation of pre-burning is understood relatively favourable.
embodiment 3:
20% of material total amount batching before pre-burning is carried out after elution in another Example 1.
According to Sr
0.72re
0.28fe
11.75co
0.25al
0.015zn
0.015o
19prepare burden, all the other are with embodiment 1.
In batching list basis, the another CaCO adding relative material total amount 0.4wt% ratio
3the boric acid (98% purity) of (98% purity), 0.1wt% ratio is as additive.
Obtain Preburning material meal according to the similar approach of embodiment 1, the calcined temperature not being both employing is 1250 DEG C.
The crystallinity analysis of Preburning material:
SEM scanning electron microscope analysis is carried out in sampling, analyzes the ferrite crystal grains of generation under different resolution, and analyze the crystallization of display dry method Preburning material fine and closely woven, even, crystal particle scale is between 1 ~ 2 μm.
The magnetic property of Preburning material detects:
Get Preburning material meal sample, add the secondary additive of different content respectively, carry out wet-milling; After wet-milling, powder particle size is 0.8 μm, and filter cloth hangs dry, and in the magnetic field of 10KOe, orientation wet pressing becomes magnetic shoe.Sample sinters at roller kiln at 1270 DEG C of temperature in air, obtained series of samples after furnace cooling.
As can be seen from the above table:
(1) sample 10-12 has reached the magnetic property index of FB9 series product all; According to SJ/10410-2002 standard, reach the magnetic property index of the sintered permanent ferrite of YH40.
(2) because Preburning material adds CaCO in compounding links
3and boric acid, if add secondary additive again can there is disadvantageous effect among double sintering, Br value and (BH) max value decline all to some extent.
(3) comparative sample 1 and sample 10, when doping ratio of preparing burden is larger, suitably reduces CaCO
3suitable with the addition of Boric Additive.
embodiment 4:
20% of material total amount batching before pre-burning is carried out after elution in another Example 1.Prepare burden according to the allocation sheet of embodiment 3, as different from Example 3, in batching, do not add CaCO
3, boric acid.
Preburning material meal is obtained according to the same method of embodiment 3.
The crystallinity analysis of Preburning material:
SEM scanning electron microscope analysis is carried out in sampling, analyzes the ferrite crystal grains of generation under different resolution, and analyze the crystallization of display Preburning material fine and closely woven, even, crystal particle scale is between 1 ~ 2 μm.
The magnetic property of Preburning material detects:
Get Preburning material meal sample, add the secondary additive of different content respectively, carry out wet-milling; After wet-milling, powder particle size is 0.8 μm, and filter cloth hangs dry, and in the magnetic field of 10KOe, orientation wet pressing becomes magnetic shoe.Sample sinters at roller kiln at 1270 DEG C of temperature in air, obtained series of samples after furnace cooling.
As can be seen from the above table:
(1) sample 13 ~ 16 has reached the magnetic property index of FB9 series product all; According to SJ/10410-2002 standard, reach the magnetic property index of the sintered permanent ferrite of YH40.
(2) Preburning material does not add CaCO in compounding links
3and boric acid, among double sintering, add the magnetic property of secondary additive meeting global optimization magnetic material, the amount of additive is with 0.4wt%CaCO
3+ 0.1wt%H
3bO
3for suitable, addition continuation rising will reach Br value and (BH) max value declines to some extent.
(3) comparative sample 10 and sample 15, additive before pre-burning add to Br value and (BH) max value favourable, but certain Hcb value and Hcj value can be sacrificed, Integrated comparative from magnetic material application characteristic, the front interpolation of pre-burning is understood relatively favourable.
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., based on the high-performance permanent-magnet ferrite Preburning material that neodymium iron boron waste material is produced, it is characterized in that:
(1) described neodymium iron boron waste material is that various Nd-Fe-Bo permanent magnet material process for processing link produces waste material or waste product;
(2) described high-performance permanent-magnet ferrite Preburning material is hexgonal screw structure, and has carried out the replacement of associating ion by rare earth element and the non-rare earth comprising Co to hexgonal screw;
(3) in described high-performance permanent-magnet ferrite Preburning material, Fe element all derives from neodymium iron boron waste material, and the rare earth element being used as the replacement of associating ion derives from neodymium iron boron waste material with the non-thulium comprising Co is all or part of.
2. according to claim 1 a kind of based on neodymium iron boron waste material produce high-performance permanent-magnet ferrite Preburning material, it is characterized in that:
(1) mixture of one or more among the grinding powder produced in the ultrafine powder that the slag that 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;
(2) described high-performance permanent-magnet ferrite Preburning material is M type ferrite structure, and has carried out the replacement of associating ion by rare earth element and the non-rare earth comprising Co to M type ferrite;
(3) in described high-performance permanent-magnet ferrite Preburning material, Fe element all derives from neodymium iron boron waste material; As among the rare earth element that ion is replaced, contain the whole rare earth component of neodymium iron boron waste material in the secondary processes waste of hydrometallurgical recovery rare earth; As among the non-thulium comprising Co that ion is replaced, contain the whole non-rare earth metal component of neodymium iron boron waste material in the secondary processes waste of hydrometallurgical recovery rare earth except Fe element.
3. prepare a method for high-performance permanent-magnet ferrite Preburning material according to claim 1 and 2, it is characterized in that the method comprises following several step:
(1) process of neodymium iron boron waste material:
Neodymium iron boron waste material is carried out oxidizing roasting; Material after oxidation calcination is added hydrochloric acid and carries out excellent molten leaching, solid-liquid separation is carried out to leaching product, after separation, obtains leach liquor and excellent molten waste residue; Carry out extraction deironing to leach liquor, carry out back extraction, alkaline chemical precipitation in strip liquor by water or dilute hydrochloric acid, sediment separate out to be mixed component as iron;
Leach liquor after extraction deironing is used for recovering rare earth element;
Excellent molten waste residue and iron mix component for the production of high performance ferrite Preburning material;
(2) elution:
Elution is carried out to the excellent molten waste residue obtained after neodymium iron boron waste material process and iron component of mixing;
(3) batching before pre-burning:
Main batching: based on the excellent molten waste residue after elution, or to mix component based on the iron after elution, or the mixture of component of mixing based on the excellent molten waste residue after elution and iron, adds containing Sr compound or contains Ba compound or contain Pb compound as main batching; Described is SrCO containing Sr compound
3, SrO, Sr (OH)
2in one or more mixtures, described containing Ba compound be BaCO
3, BaO, Ba (OH)
2in one or more mixtures, described containing Pb compound be PbCO
3, PbO, PbO
2, P
3o
4, Pb (OH)
2, Pb (OH)
4one or more mixtures;
Doping batching: add doping agent one, doping agent two as doping batching in the material after main batching, described doping agent one is rare-earth compound, and described doping agent two is except Fe and rare earth element, to comprise I B and II B race element in periodic table of elements transition metal element compound;
Additive formulations: add additive as additive formulations in the material after main batching and doping batching, described additive is one or more mixtures in calcium material, aluminium material, silicon material, boron material, and described calcium material is CaCO
3, CaO, Ca (OH)
2in one or more mixtures, described aluminium material is Al
2o
3, Al (OH)
3, H
3alO
3in one or more mixtures, described silicon material is SiO
2, H
2siO
3in one or both mixtures, described boron material is B
2o
3, H
3bO
3in one or both mixtures;
(4) material of having prepared burden is carried out pre-burning, obtain Preburning material.
4. the method preparing high-performance permanent-magnet ferrite Preburning material according to claim 3, is characterized in that: 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.
5. the method preparing high-performance permanent-magnet ferrite Preburning material according to claim 3, is characterized in that: the maturing temperature of oxidizing roasting described in step (1) is 600 DEG C ~ 1100 DEG C; Described extraction temperature is 70 DEG C ~ 100 DEG C, and the pH value leaching terminal controls 1.0 ~ 2.5; The extraction agent that described extraction deironing uses is N235 extraction agent.
6. the method preparing high-performance permanent-magnet ferrite Preburning material according to claim 3, is characterized in that: step (2) described elution adopts deionized water to carry out wash-out, or first carry out wash-out with deionized water again with dilute hydrochloric acid wash-out; The eluting water that elution produces directly mixes with leach liquor, or as processing wastewater after repeatedly recycling; Step (2) described elution refers to that in material, chloride ion content is less than 50ppm after elution.
7. the method preparing high-performance permanent-magnet ferrite Preburning material according to claim 3, is characterized in that: step (3) described batching is that each raw material is according to formula M e
1-xre
x(Fe
12-y1-y2-y3-y4-y5co
y1al
y2zn
y3cu
y4nb
y5)
zo
19prepare burden, in general formula, Me is Sr or Ba or Pd, in general formula, Re is rare earth element, and in general formula, the mol ratio of Me, Re, Fe, Co, Zn, Cu, Nb element is 1-x:x:(12-y1-y2-y3-y4-y4-y5) × z:y1 × z: y2 × z:y3 × z:y4 × z:y5 × z;
Wherein, x=0.01 ~ 0.80, y1=0.01 ~ 5.0, y2=0 ~ 2.0, y3=0 ~ 2.0, y4=0 ~ 2.0, y5=0 ~ 2.0, y1+y2+y3+y4+y5 ﹤ 12, z=0.7 ~ 1.2;
The batching of Me, Re, Co, Al, Zn, Cu, Nb element is with the Fe amount of element in material after elution for benchmark, calculates each feed proportioning amount according to the mol ratio of Me, Re, Co, Al, Zn, Cu, Nb element and Fe element; Wherein:
Me element all derives from main batching;
Re element is all or part of derives from neodymium iron boron waste material, is supplied time not enough by doping agent one;
Co, Zn, Cu, Nb element is all or part of derives from neodymium iron boron waste material, is supplied time not enough by doping agent two;
Al element derives from neodymium iron boron waste material wholly or in part, is supplied time not enough by additive-aluminium material;
The dosage of additive calcium material is by weight being 0 ~ 4.0% of batching total amount;
The dosage of additive silicon material is by weight being 0 ~ 4.0% of batching total amount;
The dosage of additive boron material is by weight being 0 ~ 4.0% of batching total amount.
8. the method preparing high-performance permanent-magnet ferrite Preburning material according to claim 3, is characterized in that: doping agent one described in step (3) is La
2o
3, La (OH)
3, La
2cO
3in one or more mixtures; Described doping agent two is CoO, Co
3o
4, Co
2o
3, Co (OH)
3, ZnO, Zn (OH)
2, CuO, Cu (OH)
2, Nb
2o
5, Nb
2o
3one or more mixtures.
9. the method preparing high-performance permanent-magnet ferrite Preburning material according to claim 3, is characterized in that: step (4) had also carried out mixing, pulverizing, pelletizing, drying and processing to material before material carries out pre-burning.
10. the method preparing high-performance permanent-magnet ferrite Preburning material according to claim 3, is characterized in that: the calcined temperature of pre-burning described in step (4) is between 800 DEG C ~ 1400 DEG C; Pre-burning operation described in step (4) also comprises allows material be down to the temperature-fall period of room temperature from calcined temperature, adopts the way cool to room temperature quenched by Preburning material, or adopts furnace cooling; Preburning material described in step (4) also adopts one or more coarse reduction equipment in jaw crusher, dry type vibrating ball mill, planetary ball mill to carry out coarse reduction, crushing material is become the Preburning material meal of 3 ~ 10 μm.
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