Process and system for recovering valent metals from refuse secondary batteries

Abstract

A process comprises a separating process to mechanically separate refuse secondary batteries and to separate them into a separated cathode material and a separated anode material, and a process to recover valent metals from the separated anode and the separated cathode material separated in the separating process is disclosed.

What is claimed is:  
     
         1 . A process for recovering valent metals from refuse secondary batteries, characterized in that the process is constituted by a separating process to mechanically separate the refuse secondary batteries and to separate them into a separated cathode material and a separated anode material, and a process to recover valent metals from the separated cathode material and the separated anode material obtained in the separating process.  
     
     
         2 . A system for recovering valent metals from refuse secondary batteries, characterized in that system comprises a separating means to mechanically separate the refuse secondary batteries and to separate them into a separated cathode material and a separated anode material, and a means to recover valent metals from the separated cathode material and the separated anode material obtained by the separating means.  
     
     
         3 . The recovering process for valent metals from refuse secondary batteries according to  claim 1 , characterized that the process comprises a cooling means to refrigerate the refuse secondary batteries with liquid nitrogen and a first crushing process to crush the refrigerated refuse secondary batteries to thereby recover the valent metals from the crushed batteries.  
     
     
         4 . The recovering process for valent metals from refuse secondary batteries according to  claim 1 , characterized in that the process comprises a water rinsing process to rinse the crushed material obtained in the crushing process and the first sieving process to carry out the first sieving.  
     
     
         5 . The recovering process for valent metals from refuse secondary batteries according to  claim 4 , characterized in that the process comprises a second sieving process to sieve the material remained over a sieve in the first sieving process, a second crushing process to crush the material remained over a sieve in the first sieving process and a third sieving process to sieve the crushed material obtained in the second crushing process.  
     
     
         6 . The recovering process for valent metals from refuse secondary batteries according to  claim 5 , characterized in that the material sieved down in the second sieving process is mainly consisted of the separated cathode material.  
     
     
         7 . The recovering process for valent metals from refuse secondary batteries according to  claim 6 , characterized in that the separated cathode material is mainly consisted of hydrogen-occluded alloy.  
     
     
         8 . The recovering process for valent metals from refuse secondary batteries according to  claim 5 , characterized in that the process comprises a rubbing process to rub a mixture of a component remained over a sieve in the second sieving process and a component sieved down in the third sieving process, and a wet magnetic separation process to magnetically separate the crushed-material under wet condition following to subjecting it to the rubbing process.  
     
     
         9 . The recovering process for valent metals from refuse secondary batteries according to  claim 8 , characterized in that the component remained over a sieve in the third sieving process is mainly consisted of iron scrap, the magnetic component obtained in the wet magnetic separation process is mainly consisted of spumous nickel, and the non-magnetic component is mainly consisted of nickel hydroxide.  
     
     
         10 . The recovering system for valent metals from refuse secondary batteries according to  claim 2 , characterized in that the separating means comprises a cooling means to refrigerate the refuse secondary batteries with liquid nitrogen and a crushing means to crush the refrigerated refuse secondary batteries to thereby recover the valent metals from the crushed material.  
     
     
         11 . The recovering process for valent metals from refuse secondary batteries according to  claim 1 , characterized in that the process further contains a fusing process to fuse the separated cathode material separated in the separating process following to addition of calcium to the separated cathode material.  
     
     
         12 . The recovering process for valent metals from refuse secondary batteries according to  claim 11 , characterized in that the additional amount of calcium is in a range of from 1 to 50 parts by weight based on 100 parts by wieght of the cathode material.  
     
     
         13 . The recovering process for valent metals from refuse secondary batteries according to  claim 11 , characterized in that the addition of calcium is carried out following to the fusing of the separated cathode material.  
     
     
         14 . The recovering process for valent metals from refuse secondary batteries according to  claim 11 , characterized in that nickel is added into the separated cathode material as a starting metal in the fusing process.  
     
     
         15 . The recovering process for valent metals from refuse secondary batteries according to  claim 11 , characterized in that the fusing process is taken place under an atmosphere of an inactive gas.  
     
     
         16 . The recovering process for valent metals from refuse secondary batteries according to  claim 11 , characterized in that the separated cathode material is crushed and separated after subjecting the refuse secondary batteries to refrigeration with liquid nitrogen during the mechanical separation process.  
     
     
         17 . The recovering system for valent metals from a refuse secondary batteries according to  claim 2 , characterized in that the system comprises a fusing means to add calcium into the separated cathode material separated by the separating means and then to fuse it to recover the valent metals.  
     
     
         18 . The recovering process for valent metals from refuse secondary batteries according to  claim 1 , characterized in that the process comprises an oxidizing process to oxidize the separated cathode material separated in the separating process at a low temperature.  
     
     
         19 . The recovering process for valent metals from refuse secondary batteries according to  claim 18 , characterized in that the oxidizing process is taken place at a temperature lower than 300° C. and the oxygen concentration is adjusted to a range of from 5 to 25%.  
     
     
         20 . The recovering process for valent metals from refuse secondary batteries according to  claim 18 , characterized in that nickel hydroxide as an anode material is added for the adjustment of the oxygen concentration.  
     
     
         21 . The recovering process for valent metals from refuse secondary batteries according to  claim 18 , characterized in that the separated cathode material is one being crushed and separated by means of refrigerating the refuse secondary batteries with liquid nitrogen during the mechanical separation process.  
     
     
         22 . The recovering system for valent metals from refuse secondary batteries according to  claim 2 , characterized in that the system comprises an oxidizing means to oxidize the cathode material separated by the separating means at a low temperature for recovering the valent metals.  
     
     
         23 . The recovering process for valent metals from refuse secondary batteries according to  claim 1 , characterized in that the process comprises a rare earth elements removing process to add an acid in an amount of 0.1-2.5 times equivalent based on the weight of the separated cathode material, which is required for dissolving the rare earth elements, in the separating process, a drying process to dry the cathode material from which the rare earth elements have been removed, and a fusing process to fuse the dried cathode material and then to recover the valent metals.  
     
     
         24 . The recovering process for valent metals from refuse secondary batteries according to  claim 23 , characterized in that the oxidizing process to gradually oxidize the cathode material while bubbling air into the aqueous solution is constituted in a place prior to the drying process.  
     
     
         25 . The recovering process for valent metals from refuse secondary batteries according to  claim 23 , characterized in that the fusing process is constituted with the addition of nickel as a starting metal into the material to be subjected to the fusing process.  
     
     
         26 . The recovering process for valent metals from refuse secondary batteries according to  claim 23 , characterized in that the separated cathode material is one being crushed and separated by refrigerating the refuse secondary batteries with liquid nitrogen during the mechanical separation process.  
     
     
         27 . The recovering system for valent metals from refuse secondary batteries according to  claim 2 , characterized in that the system comprises a rare earth elements removing means to remove rare earth elements after adding an acid in an amount of 0.1-2.5 times equivalent based on the weight of the separated cathode material separated by the separating means, which is required for dissolving the rare earth elements, a drying means to dry the separated cathode material from which the rare earth elements have been removed, and a fusing means to fuse the dried cathode material to recover the valent metals.  
     
     
         28 . The recovering process for valent metals from refuse secondary batteries according to  claim 1 , characterized in that the process comprises a reduction fusing process to reduce and fuse the separated cathode material separated in the separating process after adding either carbon or plastic into the cathode material and a decarbonizing process to heat the separated cathode material under an oxidized atmosphere to oxidize and remove carbon contained in the valent metals either prior or following to the reduction fusing process, thereby recovering the valent metals.  
     
     
         29 . The recovering process for valent metals from refuse secondary batteries according to  claim 28 , characterized in that the separated cathode material comprises a refuse anode material and refuse sintered nickel.  
     
     
         30 . The recovering process for valent metals from refuse secondary batteries according to  claim 28 , characterized in that the process has a step of adding CaF2 in the decarbonizing process.  
     
     
         31 . The recovering process for valent metals from refuse secondary batteries according to  claim 28 , characterized in that the oxidizing agent is either of oxygen or nickel oxide.  
     
     
         32 . The recovering process for valent metals from refuse secondary batteries according to  claim 28 , characterized in that the separated cathode material is prepared by crushing and separation of the refuse secondary batteries following to the refrigeration of the refuse secondary batteries with liquid nitrogen during the mechanical separation process.  
     
     
         33 . The recovering system for valent metals from refuse secondary batteries according to  claim 2 , characterized in that the system comprises a reduction fusing means to reduce and fuse the separated cathode material separated by the separating means after adding either carbon or plastic into the cathode material and a decarbonizing means to heat the separated cathode material under an oxidized atmosphere and to oxidize and remove carbon contained in the valent metals either prior or following to the reduction fusing process, thereby recovering the valent metals.  
     
     
         34 . The recovering process for valent metals from refuse secondary batteries according to  claim 1 , characterized in that the refuse secondary battery is any of nickel-hydrogen secondary battery, refuse nickel-hydrogen secondary battery and nickel-cadmium secondary battery.  
     
     
         35 . The recovering process for valent metals from refuse secondary batteries according to  claim 1 , characterized in that the valent metal is mainly consisted of hydrogen-occluded alloy, spumous nickel, nickel hydroxide and iron scrap.  
     
     
         36 . The recovering process for valent metals from refuse secondary batteries according to  claim 1 , characterized in that the recovering process to recover valent metals is taken place under an atmosphere of an inactive gas.