CN1220630C - Method for separating boron from mud containing boron alloy - Google Patents
Method for separating boron from mud containing boron alloy Download PDFInfo
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- CN1220630C CN1220630C CNB021073694A CN02107369A CN1220630C CN 1220630 C CN1220630 C CN 1220630C CN B021073694 A CNB021073694 A CN B021073694A CN 02107369 A CN02107369 A CN 02107369A CN 1220630 C CN1220630 C CN 1220630C
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- boron
- body refuse
- alloy body
- dissolving
- separating
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention provides a method for separating boron from boron containing alloy sludge such as rare earth magnet alloy sludge by which boron can selectively and easily be separated from the alloy sludge with high efficiency without dissolving the whole of the sludge, and without dissolving a part of the alloy.In the method for separating boron from the boron-containing alloy sludge, the boron-containing alloy sludge and an alkali aqueous solution are reacted, and boron is selectively eluted, and is thereafter separated.
Description
Technical field
The present invention relates to separate from the boron-containing alloy body refuse method of boron, this method can selectivity also be separated boron efficiently from boron-containing alloy body refuses such as rare earth class magneticalloy body refuse.
Background technology
R (rare earth class)-Fe-B magnetic body refuse etc. contains the alloy body refuse of boron owing to oil, the organism of having sneaked into from the body refuse production process, and the body refuse former state can't be utilized as the magnetic raw material again.Therefore, these materials are recovered as the magnetic body refuse.
The recycling of magnetic body refuse is usually adopted it is dissolved in the acid etc., separates each component with step-by-step precipitation method then, the method that reclaims.
But, resemble the old method body refuse all with sour dissolved method since all elements that constitutes alloy all ionization exist in solution, thereby reclaim each element with step-by-step precipitation method and need a plurality of steps.When having the boron ion, be very difficult with metal with purified isolated in form particularly with step-by-step precipitation method.When the form with fluorochemical reclaims in the solution existing rare-earth metal ion respectively, must handle and reclaim the fluorion that is contained in the waste liquid behind the rare earth class, and when having fluorion and boron ion in the solution, the two powerful combination, handle fluorion and will become difficult, and produce the problem of the cost increase of liquid waste disposal.Therefore, wish to develop easy, need not to dissolve the cost effective method that body refuse promptly optionally separates boron.
Summary of the invention
The object of the present invention is to provide the method for from the boron-containing alloy body refuse, separating boron, this method need not boron-containing alloy body refuses such as rare earth class magneticalloy body refuse are all dissolved, perhaps need not alloy is partly dissolved, can selectivity, efficiently and easily from this alloy body refuse, separate boron.
Present inventors found that by making the reaction of boron-containing alloy body refuse and alkali aqueous solution through further investigation, need not the alloy body refuse all dissolved or need not alloy is partly dissolved, and can only boron selective ground be dissolved and separate out, thereby finish the present invention.And find when making the boron-containing alloy body refuse with specific alkali aqueous solution reaction, by adopting kind, concentration or the consumption of selection alkali aqueous solution, to control the method for the particle diameter of alloy body refuse, can further improve the separation efficiency of boron, thereby finish the present invention.
That is to say, the invention provides from the boron-containing alloy body refuse method of separating boron, this method comprises makes boron-containing alloy body refuse and alkali aqueous solution reaction, optionally boron is dissolved the isolating separating step of boron that the dissolving of separating out is separated out step and dissolving is separated out.
Embodiment
In the method for the invention, at first make the reaction of boron-containing alloy body refuse and alkali aqueous solution, optionally step is separated out in the dissolving that the boron dissolving is separated out.
As long as above-mentioned boron-containing alloy body refuse contains boron and is the body refuse of alloy, then it is not particularly limited.The alloy body refuse that preferably contain the alloy body refuse of rare earth metal and transition metal and boron, in fact constitutes by rare earth metal and transition metal and boron.Especially preferably contain iron in the method for the invention as transition metal, for example R-Fe-B is the magnetic body refuse.
The dissolving of boron is just separated out and is needed the time if the particle diameter of boron-containing alloy body refuse is big, therefore preferred its median size is equal to or less than 100 μ m, in addition, and in order to improve the dissolving eduction rate of boron more, preferable particle size is equal to or less than 50 μ m, more preferably is equal to or less than 10 μ m.The following 0.1 μ m that is limited to of preferable particle size.
As long as alkali aqueous solution used in the step is separated out in above-mentioned dissolving, optionally dissolve the material of separating out boron and get final product, for example the aqueous solution of an alkali metal salt, ammonia soln or ammonium salt aqueous solution.
The example of above-mentioned an alkali metal salt has alkali-metal oxyhydroxide or carbonate such as sodium, potassium, lithium, particularly from the angle of reactive and efficient, and oxyhydroxide such as preferred lithium hydroxide, potassium hydroxide, sodium hydroxide.The example of above-mentioned ammonium salt aqueous solution has ammonium carbonate solution.
The aqueous solution, ammonia soln or ammonium salt aqueous solution as an alkali metal salt of above-mentioned alkali aqueous solution can be used separately in use, if do not follow the dissolving of metal to separate out during reaction, also can 2 kinds or multiple mixing use.The example that the above-mentioned dissolving of following metal is separated out has: mixture rare earth metal, alkali metal hydrocarbonate and alkaline carbonate is separated out in dissolving under oxidizing condition.
Separate out in the step in above-mentioned dissolving, the concentration of alkali aqueous solution preferably is equal to or greater than 0.1mol/L when making the reaction of boron-containing alloy body refuse and alkali aqueous solution, because it is high more to have concentration, the tendency that the dissolving precipitation ability of boron is also high more is so especially preferably be equal to or greater than 1mol/L.In addition, even because concentration is higher than 5mol/L, the dissolving precipitation ability does not change yet, thereby preferred 0.1-5mol/L, more preferably 1-3mol/L.
Separate out in the step in above-mentioned dissolving, owing to exist the consumption of alkali aqueous solution when making boron-containing alloy body refuse and alkali aqueous solution reaction high more with respect to the mole number of institute's boracic in the boron-containing alloy body refuse, the high more tendency of dissolving eduction rate of boron, thereby being decided to be more than 1 times or 1 times of mole number with respect to described boron by amount with alkali, the dissolving eduction rate of boron will improve.Therefore, preferred alkali number is more than 1 times or 1 times of mole number of boron, and is preferred especially more than 4 times or 4 times.In addition, even because addition surpasses 20 times, effect also can not get improving, thus be limited on it 20 times more suitable, be limited to 15 times on more preferably.
Exist with molten antalkaline amount as long as constitute the water of above-mentioned alkali aqueous solution,, then also can contain water material in addition so long as in fact do not dissolve the liquid of the material beyond the boron in the alloy body refuse.
The reaction of above-mentioned boron-containing alloy body refuse and alkali aqueous solution can be carried out in the temperature that is equal to or higher than room temperature.Because under the low situation of temperature of reaction, the dissolving of boron is separated out and needed the time,, need to increase concentration, the usage quantity of alkali aqueous solution in order to obtain identical dissolving precipitation ability.Therefore, temperature of reaction preferably is equal to or higher than 40 ℃, especially preferably is equal to or higher than 60 ℃, when having considered other condition, then is not limited thereto.As long as the upper limit of temperature of reaction is lower than the boiling point of solution, then it is not particularly limited.Reaction times can be 6 hours, but preferred 24 hours or above, 7 days or below.Above-mentioned reaction can be carried out under ultrasonic irradiation, carries out under the condition of also can use autoclave in addition, pressurizeing actually.
In the method for the invention, after above-mentioned reaction, carry out the separating step of the boron that separate dissolved optionally separates out.The separation of described boron can be separated into solid matter (alloy body refuse) and boracic ion solution and carry out by above-mentioned dissolving being separated out for example process filtration of reactant that step obtains.The gained solid matter through super-dry etc., for example can use utilizing in the step again of magneticalloy again.On the other hand, when the boracic ion solution that is reclaimed is alkaline solution, it can be used repeatedly as above-mentioned alkali aqueous solution, until boron concentration reach higher till, re-use while also can add new alkali aqueous solution.
The boracic ion solution that is reclaimed can be by the form recovery boron of methods such as for example known evaporate to dryness with boron compound, and the boron compound of recovery can utilize again.
In the method for the invention, owing to boron-containing alloy body refuse and alkali aqueous solution are reacted optionally dissolve and separate out boron, therefore need not the whole dissolvings of boron-containing alloy body refuse are maybe separated out a part of dissolving metal in this body refuse, promptly optionally and easily from this alloy body refuse, separate boron.And in the particle diameter of the consumption of the concentration of the kind by when reaction control alkali aqueous solution, alkali aqueous solution, alkali aqueous solution, alloy body refuse each, perhaps with more than two or two in conjunction with control, can further improve the separation efficiency of boron.
Embodiment
The present invention will be described in more detail below by embodiment, but the present invention is not limited to this.
Embodiment 1
It is that the Nd-Fe-B of 10 μ m is that the alloy body refuse is dispersed in the 70ml pure water that 30g is contained 0.8% weight boron, median size, alloyage body refuse solution.Next, Yi Bian stir this alloy body refuse solution, Yi Bian the mole number that adds with respect to institute's boracic is the NaOH of 4 times of moles, be warming up to 60 ℃, stir then and made it reaction in 24 hours, boron is separated out in dissolving.After the reaction,, be separated into solid matter (body refuse) and solution with reacting liquid filtering.100 ℃ of dryings, the ICP emmission spectrometric analysis device made from セ イ コ one イ Application ス Star Le メ Application ト company (SPS-1100H) is analyzed the boron in the solid matter afterwards with the gained solid matter, obtains the dissolving eduction rate of boron.The result is as shown in table 1.
In addition, measure size-grade distribution as solvent and trade(brand)name " SVR " as sample with laser diffraction formula particle size distribution device (trade(brand)name " マ イ Network ロ ト ラ Star Network 7997-10 type "), water that マ イ Network ロ ト ラ Star Network company makes, calculate the median size of alloy body refuse again by this size-grade distribution.
Embodiment 2-23
Concentration, temperature of reaction, the reaction times of alkali aqueous solution and the Nd-Fe-B that contains 0.8% weight boron are the median size of alloy body refuse during except that the kind of alkali aqueous solution shown in the employing table 1, with respect to the usage quantity of the alkali aqueous solution of the mole number of institute's boracic, reaction, equally with embodiment 1 react and filter, measure the dissolving eduction rate of boron from the gained solid matter.In addition, embodiment 23 usefulness autoclaves at high temperature react.The result is as shown in table 1.
Table 1
| The kind of alkali | Alkali/boron amount | The concentration of alkali aqueous solution (mol/l) | Temperature of reaction (℃) | Reaction times (hour) | Alloy particle diameter (μ m) | Dissolving eduction rate (%) | |
| Embodiment 1 | NaOH | 4 times of moles | 1 | 60 | 24 | 10 | 90 |
| Embodiment 2 | NaOH | 8 times of moles | 2 | 60 | 24 | 10 | 92 |
| Embodiment 3 | NaOH | 12 times of moles | 3.5 | 60 | 24 | 10 | 95.3 |
| Embodiment 4 | NaOH | 16 times of moles | 4 | 60 | 24 | 10 | 97 |
| Embodiment 5 | NaOH | 20 times of moles | 4 | 60 | 24 | 10 | 97 |
| Embodiment 6 | NaOH | 16 times of moles | 1.5 | 20 | 24 | 10 | 91 |
| Embodiment 7 | NaOH | 8 times of moles | 1.5 | 40 | 24 | 10 | 90 |
| Embodiment 8 | NaOH | 8 times of moles | 1.5 | 80 | 24 | 10 | 96 |
| Embodiment 9 | NaOH | 8 times of moles | 1.5 | 60 | 24 | 78 | 94 |
| Embodiment 10 | NaOH | 4 times of moles | 1 | 60 | 12 | 33 | 85 |
| Embodiment 11 | NaOH | 4 times of moles | 1 | 60 | 24 | 33 | 90 |
| Embodiment 12 | NaOH | 4 times of moles | 1 | 60 | 36 | 33 | 92 |
| Embodiment 13 | NaOH | 4 times of moles | 1 | 60 | 48 | 33 | 94 |
| Embodiment 14 | KOH | 12 times of moles | 3 | 60 | 24 | 6 | 91 |
| Embodiment 15 | NaOH | 2 times of moles | 0.5 | 60 | 24 | 10 | 44 |
| Embodiment 16 | NaOH | 4 times of moles | 0.3 | 60 | 24 | 10 | 55 |
| Embodiment 17 | NH 4HCO 3 | 32 times of moles | 1.5 | 30 | 24 | 10 | 76.5 |
| Embodiment 18 | NH 4HCO 3 | 32 times of moles | 1.5 | 30 | 48 | 10 | 70.6 |
| Embodiment 19 | Na 2CO 3 | 14 times of moles | 1 | 25 | 24 | 10 | 67.9 |
| Embodiment 20 | Na 2CO 3 | 14 times of moles | 1 | 25 | 48 | 10 | 79.8 |
| Embodiment 21 | Na 2CO 3 | 14 times of moles | 1 | 60 | 24 | 10 | 86.9 |
| Embodiment 22 | Na 2CO 3 | 14 times of moles | 1 | 60 | 48 | 10 | 86.9 |
| Embodiment 23 | NaOH | 1.5 doubly the mole | 0.1 | 120 | 24 | 10 | 94.0 |
Claims (4)
1. the method for separating boron from the alloy body refuse that contains rare earth metal and transition metal and boron, this method comprise makes the alloy body refuse that contains rare earth metal and transition metal and boron and NaOH, KOH, NH
4HCO
3, Na
2CO
3Or the reactant aqueous solution of their mixtures more than 2 kinds, the optionally dissolving that boron dissolving the is separated out isolating separating step of boron of separating out step and dissolving being separated out.
2. the method for separating boron from the alloy body refuse that contains rare earth metal and transition metal and boron of claim 1, wherein said dissolving separate out that the concentration of the above-mentioned aqueous solution is equal to or greater than 0.1mol/L in the step.
3. the method for from the alloy body refuse that contains rare earth metal and transition metal and boron, separating boron of claim 1, wherein separate out in the step mole number of institute's boracic in the aforementioned alloy body refuse that contains rare earth metal and transition metal and boron, NaOH, KOH, NH with respect to described dissolving
4HCO
3, Na
2CO
3Or the consumption of their mixtures more than 2 kinds is equal to or greater than 1 times of amount.
4. the method for separating boron from the alloy body refuse that contains rare earth metal and transition metal and boron of claim 1, the wherein said median size that contains the alloy body refuse of rare earth metal and transition metal and boron is equal to or less than 100 μ m.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP71635/01 | 2001-03-14 | ||
| JP2001071635A JP4699622B2 (en) | 2001-03-14 | 2001-03-14 | Method for separating boron-containing solution from R (rare earth) -Fe-B magnet alloy sludge |
| JP71635/2001 | 2001-03-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1375454A CN1375454A (en) | 2002-10-23 |
| CN1220630C true CN1220630C (en) | 2005-09-28 |
Family
ID=18929329
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021073694A Expired - Fee Related CN1220630C (en) | 2001-03-14 | 2002-03-14 | Method for separating boron from mud containing boron alloy |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4699622B2 (en) |
| CN (1) | CN1220630C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102139899B (en) * | 2010-11-25 | 2012-09-26 | 汪晋强 | Method for preparing magnesium sulfate monohydrate and co-producing manganese sulfate and calcium sulfate by using boric sludge |
| CN102139900B (en) * | 2010-11-25 | 2012-05-23 | 汪晋强 | Method for preparing magnesium sulfate heptahydrate co-produced with manganese sulfate and calcium sulfate from boric sludge |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000030919A (en) * | 1998-07-09 | 2000-01-28 | Sumitomo Metal Mining Co Ltd | MANUFACTURE OF MATERIAL POWDER FOR R-Fe-B MAGNET |
-
2001
- 2001-03-14 JP JP2001071635A patent/JP4699622B2/en not_active Expired - Fee Related
-
2002
- 2002-03-14 CN CNB021073694A patent/CN1220630C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1375454A (en) | 2002-10-23 |
| JP2002275548A (en) | 2002-09-25 |
| JP4699622B2 (en) | 2011-06-15 |
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Granted publication date: 20050928 Termination date: 20210314 |