CN102212711B - Method for treating hydrogen storage alloy waste residues - Google Patents
Method for treating hydrogen storage alloy waste residues Download PDFInfo
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- CN102212711B CN102212711B CN2011101516589A CN201110151658A CN102212711B CN 102212711 B CN102212711 B CN 102212711B CN 2011101516589 A CN2011101516589 A CN 2011101516589A CN 201110151658 A CN201110151658 A CN 201110151658A CN 102212711 B CN102212711 B CN 102212711B
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Abstract
The invention relates to a method for treating hydrogen storage alloy waste residues, comprising the following steps of: (1) firstly putting 50-97% of hydrogen storage alloy smelted waste residues, 3-30% of fusion agent and 0-20% of coke as a reducing agent in a crucible of a vacuum induction smelting furnace, wherein the sum of the three components is 100%; (2) vacuumizing the vacuum induction smelting furnace, and introducing inert gas to the vacuum induction smelting furnace; (3) heating until all materials are smelted; (4) pouring the materials in a ladle pot; and (5) after cooling, taking out the ladle pot, and removing slag on the materials to obtain nickel base alloy. Compared with the prior art, the method disclosed by the invention has the benefits of simple equipment process, no smoke dust, high alloy extraction rate and the like; and experiences prove that the overall recovery rate of three elements of Ni, Co and Mn in the slag is up to above 98%.
Description
Technical field
The present invention relates to a kind of treatment process of hydrogen storage alloy waste residue.
Background technology
Along with the continuous progress of science and technology, human more and more to demands for energy, cause environmental pollution to be on the rise, primary energy source such as oil, coal are in short supply day by day.Existent environment of people caused seriously influence, the development and utilization of new forms of energy is the optimal paths that address the above problem.Ni-MH battery (nickel metal hydride battery) is a kind of novel energy of environmental protection; But has the loading capacity height, an advantage such as the heavy-current discharge that has extended cycle life; Be widely used at present the every field of industry and family; The use of power truck, hybrid-electric car, electric bicycle, power tool etc. has greatly promoted the application of Ni-MH battery, as the hydrogen storing alloy powder of Ni-MH cell negative electrode material, also is widely used thereupon.
Mostly adopt the crucible of materials such as corundum, Mg0 in the hydrogen storage alloy production process, under the situation of vacuum high-temperature melting, have hydrogen storage alloy in a small amount and the crucible material generation slag that reacts.The weight of slag accounts for about the 3-5% of charging capacity, wherein contains valuable metals such as a large amount of nickel, cobalt, rare earth.Most hydrogen storage alloy manufacturing enterprise because the restriction of aspects such as technical qualification, cost can't be recycled the metal in the slag of this part, causes the serious waste of ERM.Because these heavy metals in the slag can cause environmental pollution, state's laws do not allow to abandon, and can only give the enterprise with processing qualification and handle, and need pay the processing costs of great number, thereby greatly improve the operation cost of enterprise.
Summary of the invention
The treatment process that the purpose of this invention is to provide the hydrogen storage alloy waste residue of a kind of environmental protection, economy reduces noble metal and runs off, and reduces operation cost of enterprises.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of treatment process of hydrogen storage alloy waste residue, this method may further comprise the steps:
1) earlier hydrogen storage alloy smelting waste, flux, reductive agent coke are put into the vacuum induction melting furnace crucible, the weight percent of its each component is:
Hydrogen storage alloy smelting waste 50～97%, flux 3～30%, 0～20%, three kinds of component sums of coke are 100%;
The one-tenth of said hydrogen storage alloy smelting waste is grouped into by weight percentage: Ni 20～50%, and Co 0～15%, and Mn is 0～10%, and Al is 0～10%, and rare earth (La, Ce, Pr, Nd, Sm) summation is 10～50%, and oxygen O is 5～50%;
At least contain CaO, MgO, SiO in the said flux
2, Al
2O
3, B
2O
3, CaCO
3, NaCO
3In one or more;
2) vacuum induction melting furnace is vacuumized, vacuum tightness charges into rare gas element less than 0.5Pa in vacuum induction melting furnace, control inflation pressure to be-0.09MPa～-0.03MPa;
3) vacuum induction melting furnace is heated to 1800～2800 ℃, all melts until material;
The material that 4) will melt is fully poured in the casting ladle;
5) 0.5～5 hour to be cooled, temperature of charge took out casting ladle less than after 200 ℃, dials and removes top slag, can obtain nickel-base alloy.
Said crucible is a plumbago crucible.
Said rare gas element is one or more in nitrogen, argon gas, helium, the carbonic acid gas.
Compared with prior art; The invention has the beneficial effects as follows: this method has that apparatus and process is simple, no flue dust, nickel-base alloy extraction yield advantages of higher; Facts have proved; The recovery of Ni, Co, Mn reaches more than 98% in the slag, is particularly suitable for hydrogen storage alloy manufacturing enterprise the slag that produces in the fusion process is handled.
Embodiment
Following specific embodiments of the invention is described further:
Embodiment 1
Example is got 95% slag and 5% flux by weight percentage, carries out melting on the vacuum induction melting furnace of plumbago crucible being equipped with, and adopts rare gas element to protect in the fusion process, last output nickel-base alloy and secondary slag.
Embodiment 2
Example is got 90% slag+8% flux+2% coke by weight percentage, carries out melting on the vacuum induction melting furnace of plumbago crucible being equipped with, and adopts rare gas element to protect in the fusion process, last output nickel-base alloy and secondary slag.
Embodiment 3
Example is got 82% slag+12% flux+6% coke by weight percentage, carries out melting on the vacuum induction melting furnace of plumbago crucible being equipped with, and adopts rare gas element to protect in the fusion process, last output nickel-base alloy and secondary slag.
Embodiment 4
Example is got 72% slag+18% flux+10% coke by weight percentage, carries out melting on the vacuum induction melting furnace of plumbago crucible being equipped with, and adopts rare gas element to protect in the fusion process, last output nickel-base alloy and secondary slag.
Embodiment 5
Example is got 60% slag+25% flux+15% coke by weight percentage, carries out melting on the vacuum induction melting furnace of plumbago crucible being equipped with, and adopts rare gas element to protect in the fusion process, last output nickel-base alloy and secondary slag.
Embodiment 6
Example is got 50% slag+30% flux+20% coke by weight percentage, carries out melting on the vacuum induction melting furnace of plumbago crucible being equipped with, and adopts rare gas element to protect in the fusion process, last output nickel-base alloy and secondary slag.
In the foregoing description, the one-tenth of hydrogen storage alloy smelting waste is grouped into by weight percentage and is: Ni 20～50%, and Co 0～15%, and Mn is 0～10%, and Al is 0～10%, and rare earth (La, Ce, Pr, Nd, Sm) summation is 10～50%, and oxygen O is 5～50%; Flux is CaO, MgO, SiO
2, Al
2O
3, B
2O
3, CaCO
3, NaCO
3In one or more, CaO>=50%, MgO≤20%, SiO2≤20%, Al
2O
3≤10%, B
2O
3≤10%.Vacuum induction melting furnace vacuum tightness after material adds vacuum induction melting furnace, charges into rare gas element less than 0.5Pa in stove, control inflation pressure to be-0.09MPa～-0.03MPa; Be heated to 1800～2800 ℃, all melt until material; With the material that melts fully, pour in the casting ladle; 0.5～5 hour to be cooled, temperature of charge took out casting ladle less than after 200 ℃, dials the secondary slag that removes the surface, can obtain nickel-base alloy.
Nickel-base alloy output capacity situation such as table 1 are calculated as follows:
The weight * 100% of the weight of nickel-base alloy output capacity=output nickel-base alloy/input slag.
Nickel-base alloy and the test of secondary slag composition are carried out on inductively coupled plasma atomic emission (ICP) appearance that Tianjin, island company produces, and the composition test result sees table 2, table 3.
Table 1 nickel-base alloy output capacity
| Instance | The nickel-base alloy output capacity |
| Embodiment 1 | 58.6％ |
| Embodiment 2 | 57.2％ |
| Embodiment 3 | 57.5％ |
| Embodiment 4 | 58.2％ |
| Embodiment 5 | 58.3％ |
| Embodiment 6 | 57.9％ |
Table 2 nickel-base alloy composition test
| Instance | La | Ce | Pr | Nd | Ni | Co | Mn | Al | Fe | Cu |
| Embodiment 1 | 2.93 | 3.54 | 0.76 | 1.40 | 75.07 | 8.48 | 6.78 | 2.03 | 0.092 | 0.007 |
| Embodiment 2 | 1.88 | 2.63 | 0.60 | 1.05 | 76.93 | 8.70 | 6.82 | 1.39 | 0.091 | 0.007 |
| Embodiment 3 | 1.95 | 2.53 | 0.65 | 1.23 | 76.42 | 8.62 | 6.69 | 1.47 | 0.090 | 0.007 |
| Embodiment 4 | 1.83 | 2.49 | 0.68 | 1.13 | 76.34 | 8.27 | 6.59 | 1.51 | 0.091 | 0.007 |
| Embodiment 5 | 1.85 | 2.46 | 0.59 | 1.31 | 75.96 | 8.31 | 6.63 | 1.43 | 0.091 | 0.007 |
| Embodiment 6 | 1.92 | 2.53 | 0.63 | 1.25 | 76.14 | 8.56 | 6.72 | 1.53 | 0.090 | 0.007 |
The test of table 3 secondary slag composition
| Instance | La | Ce | Pr | Nd | Ni | Co | Mn | Al | Fe | Cu |
| Embodiment 1 | 50.98 | 14.57 | 1.89 | 6.56 | 0.74 | 0.31 | 0.77 | 2.42 | 0.086 | 0.007 |
| Embodiment 2 | 45.36 | 12.96 | 1.68 | 5.83 | 0.66 | 0.27 | 0.69 | 2.15 | 0.089 | 0.007 |
| Embodiment 3 | 37.63 | 10.75 | 1.40 | 4.84 | 0.55 | 0.23 | 0.57 | 1.78 | 0.087 | 0.007 |
| Embodiment 4 | 29.59 | 8.45 | 1.10 | 3.80 | 0.43 | 0.18 | 0.45 | 1.40 | 0.083 | 0.007 |
| Embodiment 5 | 21.81 | 6.23 | 0.81 | 2.80 | 0.32 | 0.13 | 0.33 | 1.03 | 0.082 | 0.007 |
| Embodiment 6 | 16.62 | 4.75 | 0.62 | 2.14 | 0.24 | 0.10 | 0.25 | 0.79 | 0.087 | 0.007 |
Can know that by table in the hydrogen storage alloy waste residue treatment process in embodiment 1 to embodiment 6, the weight percentage of nickel, cobalt and manganese has reached more than 90% in the nickel-base alloy that melting obtains; The weight percentage of secondary slag middle-weight rare earths element has reached that (La, Ce, Pr, Nd weight percent sum are greater than 20% more than 20%; Especially when the slag proportion scale reached 95%, the weight percent sum of secondary slag middle-weight rare earths element surpassed 70%); The weight percentage of nickel, cobalt, manganese is below 1% in the secondary slag; The recovery extraction yield that shows nickel in the secondary slag, cobalt, three kinds of elements of manganese has surpassed 98% (calculate according to Ni, Co, Mn sum 2% in the weight percentage 90% of nickel, cobalt and manganese in nickel-base alloy output capacity 55%, the nickel-base alloy, the secondary slag, can calculate nickel, cobalt, the total output capacity of manganese by formula 0.55*0.9/ (0.55*0.9+0.02*0.45)).
Claims (3)
1. the treatment process of a hydrogen storage alloy waste residue is characterized in that, this method may further comprise the steps:
1) earlier hydrogen storage alloy smelting waste, flux, reductive agent coke are put into the vacuum induction melting furnace crucible, the weight percent of its each component is:
Hydrogen storage alloy smelting waste 50～97%, flux 3～30%, 0～20%, three kinds of component sums of coke are 100%;
The one-tenth of said hydrogen storage alloy smelting waste is grouped into by weight percentage: Ni 20～50%, and Co 0～15%, and Mn is 0～10%, and Al is 0～10%, rare earth La, Ce, Pr, Nd, and the Sm summation be 10～50%, oxygen O is 5～50%;
At least contain CaO, MgO, SiO in the said flux
2, Al
2O
3, B
2O
3, CaCO
3, NaCO
3In one or more;
2) vacuum induction melting furnace is vacuumized, vacuum tightness charges into rare gas element less than 0.5Pa in vacuum induction melting furnace, control inflation pressure to be-0.09MPa～-0.03MPa;
3) vacuum induction melting furnace is heated to 1800～2800 ℃, all melts until material;
The material that 4) will melt is fully poured in the casting ladle;
5) 0.5～5 hour to be cooled, temperature of charge took out casting ladle less than after 200 ℃, dials and removes top slag, can obtain nickel-base alloy.
2. the treatment process of a kind of hydrogen storage alloy waste residue according to claim 1 is characterized in that, said crucible is a plumbago crucible.
3. the treatment process of a kind of hydrogen storage alloy waste residue according to claim 1 is characterized in that, said rare gas element is one or more in nitrogen, argon gas, helium, the carbonic acid gas.
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|---|---|---|---|
| CN2011101516589A CN102212711B (en) | 2011-06-08 | 2011-06-08 | Method for treating hydrogen storage alloy waste residues |
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| CN102212711B true CN102212711B (en) | 2012-07-18 |
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| CN110714139A (en) * | 2018-07-13 | 2020-01-21 | 有研工程技术研究院有限公司 | Rare earth-nickel-based hydrogen storage alloy material and preparation method thereof |
| CN109704793A (en) * | 2019-02-25 | 2019-05-03 | 包头稀土研究院 | The application method of vacuum induction melting production hydrogen bearing alloy coating |
| CN109776100A (en) * | 2019-02-25 | 2019-05-21 | 包头稀土研究院 | Vacuum induction melting coating |
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| JPS61235519A (en) * | 1985-04-09 | 1986-10-20 | Nippon Jiryoku Senko Kk | Production of sintered raw material from ferro nickel slag |
| CN1257295C (en) * | 2004-11-15 | 2006-05-24 | 四川川投峨眉铁合金（集团）有限责任公司 | Production method for extracting nickel by pyrogenic process |
| CN101445878B (en) * | 2008-12-30 | 2010-07-14 | 鞍山鑫普新材料有限公司 | Preparation method of AB5 type hydrogen-storage alloy used on MH-Ni battery |
| CN101748279B (en) * | 2010-01-22 | 2011-12-14 | 内蒙古科技大学 | Method for recycling smelting slag of AB5 type rare earth-based hydrogen storage alloy |
| CN101831555B (en) * | 2010-05-20 | 2012-05-02 | 牛庆君 | Method for producing artificial rich iron ore from nickel smelting waste slag by utilizing new sintering process |
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