CN103343234B - Method for preparing neodymium and iron oxides by using neodymium iron boron oil sludge through regeneration and co-precipitation - Google Patents
Method for preparing neodymium and iron oxides by using neodymium iron boron oil sludge through regeneration and co-precipitation Download PDFInfo
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Abstract
The invention relates to a method for preparing neodymium and iron oxides by using neodymium iron boron oil sludge through regeneration and co-precipitation, belonging to the field of recycling of neodymium iron boron oil sludge. The method comprises the following steps of: adding hydrogen peroxide to oxidize a pickling liquid of the neodymium iron boron oil sludge, adjusting the PH value, adding a proper amount of sodium hydroxide, ammonium hydroxide or sodium oxalate precipitating agent at one step, preserving the heat of 60-100 DEG C for a period of time, centrifuging a sediment, drying, and roasting at high temperature to obtain a mixture of the neodymium and iron oxides. The method is short in operation process, simple in operation and capable of avoiding using a great deal of reagents.
Description
Technical field
The present invention relates to a kind of neodymium iron boron greasy filth and prepare regeneration neodymium iron boron one step co-precipitation neodymium-iron alloy and the method preparing neodymium ferriferous oxide, belong to the recycling of neodymium iron boron greasy filth.
Background technology
Nowadays, just have in every 6 new technologies one relevant with rare earth, this absolutely proves the role and importance of rare earth in new technology.Rare earth is 21 century important strategic resource, is modern industry " monosodium glutamate ".Why rare earth element is called as " 21 century strategy element ", is because it has other elements and does not possess specific physical character and chemical property.Based on many rare earth new materials that these characteristics are made, excellent performance, of many uses, by a large amount of for fields such as electronic information, mechanics of communication, automobile making, the energy and aerospace.Rare earth was described as once " material VITAMIN " and " 21 century high-tech and the treasure-house of functional materials " etc.
Rare earth element is as the rare and grand strategy resource of costliness, and the valuable element in synthetical recovery waste material is very valuable work; Reasonable recovering rare earth element, can not only save and protect national resource, reduce costs and increase economic efficiency, and is conducive to domestic each field and develops steadily in the long term, also helps the cycling and reutilization of rare earth element and the Sustainable development of country.
And as being rich in the neodymium iron boron of rare earth element didymium, neodymium iron boron reclaiming work is seemed very important naturally.Iron boron magnet magnetic energy product is 240 ~ 440kJ/m
3, being referred to as the present age " king of permanent magnetism ", is the permanent magnet material that over-all properties known is at present the highest.Compared with traditional magnet, the magnetic energy product of rare earth permanent-magnetic material will exceed 4 ~ 10 times, and other magnetic properties also far exceed conventional magnet; And the magnetic energy product of Nd-Fe-Bo permanent magnet material more will exceed 8 ~ 10 times of traditional magnetic material.
The technical process of NdFeB waste recovery has multiple, as acid-soluble depositing technology, double salt conversion process, the excellent molten technique of hydrochloric acid etc.List the recovery method that some are traditional as follows:
Comprehensive above current Rare earth recovery method, although these techniques can regain rare earth, but also there are problems: first finally, the endless chain of above technique formation useless circulation truly, the product that these technique obtains is only rare earth oxide, and does not make the mechanicals that can directly use.And rare-earth oxidation material desire purify for industrial can direct applied high-purity single rare earth, also need to carry out tens grades of extraction process, its extraction agent is very expensive especially, and social benefit obviously reduces.Secondly from economic benefit, except above-mentioned when purification high-purity single rare earth, extraction process by consume a large amount of acid solution, time and costliness extraction agent beyond, the common acid-soluble precipitator method will carry out secondary sedimentation to rare earth when recovering rare earth, not only flow process is longer for it, invest higher, and the rate of recovery is lower, economic benefit is obviously very low; And in the technique of full extraction process Extraction of rare earth, although the purity of this technique rare earth when recovering rare earth is higher, and the cobalt element of higher degree can be obtained, but its numerous and diverse chemical technology and high cost make this method at the very start cannot accept by industrial production.Again, from the angle of energy-conserving and environment-protective, no matter be the excellent molten method of hydrochloric acid, full extraction process or the sulfuric acid double salt precipitator method, they all can form a large amount of acid-base waste fluids and toxic and harmful in rare earth reclaims.Only in extraction process, because need higher liquid liquor ratio and better back extraction effect, the consumption of its acid is all more than 10 times of normal chemical metering, and the acid-base waste fluid that these processes are formed all is difficult to process at technique end; Moreover, the sulfuric acid double salt precipitator method will produce the SO very large to human injury in the process reclaiming iron
2and H
2s gas.
Summary of the invention
The present invention is directed to these problems above-mentioned, the method adopting the coprecipitation of single stage method neodymium iron to replace only selective precipitation neodymium reclaims the valuable element in acid-soluble rear solution.Neodymium iron reclaims by the method simultaneously, and technical process is short, not wasting of valuable element, and follow-up can be used to synthesizes NdFeB magnetic powder, realizes real recycle, the therefore economic and practical that had of the method.
The method of neodymium ferriferous oxide is prepared in a kind of neodymium iron boron greasy filth regeneration co-precipitation, it is characterized in that comprising the following steps: after hydrogen peroxide oxidation is added in the pickling liquor of neodymium iron boron greasy filth, after regulating pH value, once add appropriate sodium hydroxide, ammoniacal liquor or sodium oxalate precipitation agent, be incubated for some time at 60 ~ 100 DEG C of temperature after, pelleting centrifugation is dried, and at high temperature roasting, obtain the mixture of neodymium ferriferous oxide.
The technical scheme that the present invention formulates preferably includes following steps further:
(1) when being the precipitation agent of a step co-precipitation with sodium hydroxide, the top condition of its co-precipitation is: after acid-soluble for neodymium iron boron greasy filth filtration, and filtrate is added excessive mass concentration 30% hydrogen peroxide oxidation and do not stopped to stir; Generate for preventing ferric hydroxide colloid, select first to regulate pH value to be incubated again, therefore, first regulate preferred PH=7 ~ 9 of PH=4 ~ 9(), then controlling temperature of reaction is 60 ~ 100 DEG C, and the sodium hydroxide solution adding 1mol/L reacts 60mins under agitation, finally, being dried by pelleting centrifugation is placed in box-type furnace, roasting 90mins at T=400 ~ 600 DEG C; The consumption of preferred sodium hydroxide solution is the corresponding 30ml sodium hydroxide solution of every 5g neodymium iron boron greasy filth.
(2) when being the precipitation agent of a step co-precipitation with ammoniacal liquor, the top condition of its co-precipitation is: after acid-soluble for neodymium iron boron greasy filth filtration, filtrate is added extra mass concentration 30% hydrogen peroxide oxidation and is not stopped to stir, add 30% ammoniacal liquor until regulate rear preferred PH=5.5 ~ 7.5 of solution PH=8 ~ 10(of precipitation), then controlling temperature of reaction is 60 ~ 100 DEG C, standing and reacting 60mins, finally, pelleting centrifugation is dried and is placed in box-type furnace, roasting 90mins at T=400 ~ 600 DEG C.
(3) when being the precipitation agent of a step co-precipitation with sodium oxalate, the top condition of its co-precipitation is: after acid-soluble for neodymium iron boron greasy filth filtration, filtrate is added excessive mass concentration 30% hydrogen peroxide oxidation and is not stopped to stir, and for preventing ferric hydroxide colloid from generating, selects first to regulate pH value to be incubated again.Therefore, first regulate PH=1 ~ 3, then to control temperature of reaction be 60 ~ 100 DEG C, and add 0.1mol/L sodium oxalate solution that temperature is the heat of 35-50 DEG C and react 60mins under being allowed to condition at stirring.Finally, pelleting centrifugation is dried and is placed in box-type furnace, roasting 90mins at T=600 ~ 800 DEG C, preferably the corresponding 300ml sodium oxalate solution of every 5g neodymium iron boron greasy filth.
In the process that neodymium iron boron greasy filth described above is acid-soluble, solid-to-liquid ratio is (1g): (10-15ml).
In products therefrom of the present invention, the mass content of iron neodymium is respectively: 47.89% ~ 63.44%, 18.10% ~ 34.51%, basic consistent with the mass ratio of iron neodymium in starting material.
The invention has the beneficial effects as follows:
(1) can a step by the co-precipitation of neodymium iron, operating process is short, simple to operate, avoids the use of extensive reagent;
(2) inquired into sodium hydroxide, ammoniacal liquor, sodium oxalate three kinds of precipitation agents in the effect of single stage method co-precipitation iron neodymium, wherein the co-precipitation effect of sodium oxalate is better, and at the bottom of foreign matter content, powder particle is even;
(3) for follow-up preparation neodymium iron boron regeneration magnetic powder provides favourable condition, business cycle chain is realized, for " mine, city " lays a good foundation.
Accompanying drawing explanation
The XRD figure spectrum of the neodymium ferriferous oxide that Fig. 1 is embodiment 1 to be obtained when taking NaOH as precipitation agent at various ph values;
The XRD figure spectrum of the neodymium ferriferous oxide that Fig. 2 is embodiment 2 to be obtained when taking ammoniacal liquor as precipitation agent at various ph values;
The XRD figure spectrum of Fig. 3 to be embodiment 3 with sodium oxalate be neodymium ferriferous oxide that precipitation agent obtains.
Embodiment
Below in conjunction with example, the present invention is further described, but the present invention is not limited to following examples.Following hydrogen peroxide is mass concentration 30% hydrogen peroxide.
Embodiment 1:
First, get 5g neodymium iron boron greasy filth, in waste material, add 4mol/L hydrochloric acid 60ml, fully dissolve in backward filtrate and add excessive hydrogen peroxide stirring 10min.Then, be that the ammoniacal liquor of 1:1 regulates pH value to be respectively 4,7,9 by adding volume ratio, and filtrate is placed in heat collecting type heating stirrer, controlling temperature of reaction is 70 DEG C, slowly adds the sodium hydroxide 30ml of 1mol/L and is allowed to condition in agitator and reacts 60mins.Finally, dried by pelleting centrifugation and be placed in box-type furnace, roasting 90mins at T=400 DEG C, obtains neodymium Iron mixed oxide.By means of testing such as XRD, XRF, we obtain following result:
Thing phase, the constituent content of the neodymium Iron mixed oxide that roasting obtains after relatively adding sodium hydroxide when pH value is 4,7,9, and analyze discussion:
The XRF result (%) of the oxide compound that the roasting that table 1-1 obtains when taking NaOH as precipitation agent at various ph values obtains
By above Comparative result, think when PH7 ~ 9, be the pH value selection range of more satisfactory step precipitator method, its foreign matter content and kind are all lower, and by the conversion of yield, its rate of recovery is also higher.
Embodiment 2
First, get 5g neodymium iron boron greasy filth, in waste material, add 4mol/L hydrochloric acid 60ml, fully dissolve in backward filtrate and add excessive hydrogen peroxide stirring 10min.Then, and filtrate is placed in heat collecting type heating stirrer, controlling temperature of reaction is 70 DEG C, and the pH value that the ammoniacal liquor slowly adding 30% regulates is 5.5,7.5, and is allowed to condition in agitator and reacts 60mins.Finally, dried by pelleting centrifugation and be placed in box-type furnace, roasting 90mins at T=400 DEG C, obtains neodymium Iron mixed oxide.By means of testing such as XRD, XRF, obtain following result:
After relatively adding ammonia precipitation process when pH value is 5.5,7.5, roasting obtains thing phase, the constituent content of product, and analyzes discussion:
When table 1-2 take ammoniacal liquor as precipitation agent, roasting obtains the XRF result (%) of product at various ph values
As seen from Figure 2, when with ammoniacal liquor as precipitation agent time, only have ferric oxide phase and there is no Neodymium trioxide phase in XRD figure spectrum; And the peak of ferric oxide is strong very low.But XRF result display (table 1-2), have neodymium element to precipitate, and proportion is not low in precipitation, reaches 20.13% and 18.10% respectively when pH=5.5 and pH=7.5 in precipitation.The content of the impurity elements such as Al, Si, Zn, Ca and P is also very low.By the method for ammoniacal liquor one step precipitated iron ion and neodymium ion, the elemental composition obtained is better.
Embodiment 3
First, get 5g neodymium iron boron greasy filth, in waste material, add 4mol/L hydrochloric acid 60ml, fully dissolve in backward filtrate and add excessive hydrogen peroxide stirring 10min.Then, regulate pH value to be respectively 2 by the ammoniacal liquor adding 1:1, and filtrate is placed in heat collecting type heating stirrer, controlling temperature of reaction is 70 DEG C, slowly adds hot 0.1mol/L sodium oxalate solution 300ml and is allowed to condition in agitator and react 60mins.Finally, dried by pelleting centrifugation and be placed in box-type furnace, roasting 90mins at T=800 DEG C, obtains neodymium Iron mixed oxide.By means of testing such as XRD, XRF, we obtain following result:
Table 1-3 take sodium oxalate as the XRF result (%) of the neodymium Iron mixed oxide that precipitation agent roasting obtains
As seen from Figure 3, the spike halfwidth of the throw out thing phase spectral line obtained 800 DEG C of calcinations is minimum, and intensity is the highest, and the impact of impurity back end is minimum, and thus we can find out that precipitated crystal degree is at this moment best.The XRF result display of table 1-3, the yield of rare earth element is also very high, and neodymium element reaches 34.51%, and praseodymium element reaches 10.87%.
By adding a step precipitation of sodium oxalate, uniform particles can be obtained, the precipitation of better crystallinity degree.And foreign matter content is less; Sodium ion and chlorion can cleanings by experiment in process and removing.Can primary sedimentation Nd preferably using sodium oxalate as coprecipitator
3+and Fe
3+, and proportioning is more close to the material ratio of neodymium iron boron; Convenience can be provided for subsequent ball milling.
Claims (3)
1. the method for neodymium ferriferous oxide is prepared in neodymium iron boron greasy filth regeneration co-precipitation, it is characterized in that, comprise the following steps: after hydrogen peroxide oxidation is added in the pickling liquor of neodymium iron boron greasy filth, adjust ph, once add sodium hydroxide, ammoniacal liquor or sodium oxalate precipitation agent, be incubated for some time at 60 ~ 100 DEG C of temperature after, pelleting centrifugation is dried, and at high temperature roasting, obtain neodymium ferriferous oxide;
When being the precipitation agent of a step co-precipitation with sodium hydroxide, the condition of its co-precipitation is: after acid-soluble for neodymium iron boron greasy filth filtration, and filtrate is added excessive mass concentration 30% hydrogen peroxide oxidation and do not stopped to stir; First adjust ph is incubated again, first regulates pH=4 ~ 9, and then controlling temperature of reaction is 60 ~ 100 DEG C, and the sodium hydroxide solution adding 1mol/L reacts 60mins under agitation, finally, pelleting centrifugation is dried and is placed in box-type furnace, roasting 90mins at T=400 ~ 600 DEG C;
When being the precipitation agent of a step co-precipitation with ammoniacal liquor, the condition of its co-precipitation is: after acid-soluble for neodymium iron boron greasy filth filtration, filtrate is added extra mass concentration 30% hydrogen peroxide oxidation and is not stopped to stir, add 30% ammoniacal liquor until regulate rear pH value of solution=5.5 ~ 7.5 of precipitation, then controlling temperature of reaction is 60 ~ 100 DEG C, standing and reacting 60mins, finally, pelleting centrifugation is dried and is placed in box-type furnace, roasting 90mins at T=400 ~ 600 DEG C;
When being the precipitation agent of a step co-precipitation with sodium oxalate, the condition of its co-precipitation is: after acid-soluble for neodymium iron boron greasy filth filtration, filtrate is added excessive mass concentration 30% hydrogen peroxide oxidation and is not stopped to stir, generate for preventing ferric hydroxide colloid, select first adjust ph to be incubated again, therefore, first regulate pH=1 ~ 3, controlling temperature of reaction is again 60 ~ 100 DEG C, and adds 0.1mol/L sodium oxalate solution that temperature is the heat of 35-50 DEG C and react 60mins under being allowed to condition at stirring; Finally, pelleting centrifugation is dried and is placed in box-type furnace, roasting 90mins at T=600 ~ 800 DEG C.
2. according to the method for claim 1, it is characterized in that, when being the precipitation agent of a step co-precipitation with sodium hydroxide, regulate pH=7 ~ 9.
3. according to the method for claim 1, it is characterized in that, in the process that neodymium iron boron greasy filth is acid-soluble, solid-to-liquid ratio is (1g): (10-15ml).
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