Patent ID: 12227819

DETAILED DESCRIPTION

The terminology used herein is for the purpose of describing uniticular embodiments only and is not intended to be limiting of the present disclosure. As used herein, the singular forms “a” and “an” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms “comprises”, “comprising”, “includes”, and “including” when used in this specification, specify the presence of the stated features, integers, operations, elements, and/or components, but do not preclude the presence or addition of one or greater other features, integers, operations, elements, components, and/or portions thereof.

Unless otherwise defined, all terms including technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this inventive concept belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

A method of recovering copper, bronze and lead from a mixture of copper oxide, tin oxide and lead oxide according to the present disclosure may include a step S100of placing a mixture of copper oxide, tin oxide and lead oxide into a reactor; a step S200of raising a temperature inside the reactor; and a step S300of introducing reductive gas into the reactor and heat-treating the mixture.

First, the step S100of placing the mixture of copper oxide, tin oxide and lead oxide into the reactor is performed. In this connection, the mixture of copper oxide, tin oxide and lead oxide may be obtained by burning a waste solar power module. The disclosure is not limited thereto.

Specifically, the reactor includes a mesh structure therein. The mixture of copper oxide, tin oxide and lead oxide is placed on a top face of the mesh structure. Further, a recovering unit for recovering molten material is disposed below the mesh structure.

The molten material is produced in the heat-treatment step as described later, and includes copper-tin alloy.

Next, the step S200of raising the temperature inside the reactor is performed.

Specifically, it is preferable to raise the temperature inside the reactor until the temperature reaches 700° C. to 900° C. as a temperature condition under which all of copper oxide, tin oxide and lead oxide may be reduced. In the step S200of increasing the temperature, nitrogen or argon gas may be introduced into the reactor in a rate of 300 cc/min to maintain an inert atmosphere.

As described above, introducing the nitrogen or argon gas as an inert gas in the step S200of increasing the temperature may allow oxygen in the reactor may be removed therefrom when raising the temperature.

Further, the nitrogen or argon gas as an inert gas may be introduced even when lowering the temperature inside the reactor.

Subsequently, the step S300of introducing the reductive gas into the reactor and heat-treating the mixture is performed. In this connection, it is most preferable that the reductive gas be methane gas, which allows the copper oxide, tin oxide, and lead oxide to be reduced. In particular, the methane gas reacts with residual oxygen in the reactor to continuously remove oxygen such that an oxidation reaction of the lead does not occur.

Further, the heat-treatment step S300is preferably performed at 700° C. to 900° C., whereby the copper of the mixture is reduced and remains on a top face of the mesh structure, and portions of the copper oxide and tin oxide are converted to the copper-tin alloy which is melt, flows through the mesh structure to a bottom of the reactor, and is recovered in the recovering unit, so that copper and bronze may be separated from each other.

That is, the mixture of copper oxide, tin oxide, and lead oxide may be placed on the top face of the mesh structure, and then heat-treating the inside of the reactor at a temperature of 700° C. to 900° C. may be performed under a methane gas atmosphere. Thus, at the temperature, the solid copper, and molten copper-tin alloy (bronze) may be separated from each other.

Therefore, it is preferable that a melting point of the mesh structure is higher than a temperature at which the copper-tin alloy is melted.

In one example, the step S300of the heat-treatment may include applying at least one of inertial force, impact force and rotational force to the mixture or the reactor, such that a larger amount of the molten copper-tin alloy of the mixture may be separated from the solid copper.

Specifically, the inertial force and impact force may be applied to the mixture or the reactor (that is, the mesh structure) 10 times for 1 minute to 3 minutes using a pressure device such as a hydraulic cylinder.

In another example, a rotation device such as a rotational motor may be used for the reactor to apply the rotational force thereto 10 times for 1 to 3 minutes.

Accordingly, the larger amount of the copper-tin alloy may flow to the bottom using the inertial force, the impact force and the rotational force, so that copper and bronze may be more effectively separated from each other.

In one example, after placing the mixture of copper oxide, tin oxide and lead oxide on the top face of the mesh structure, heat-treating the inside of the reactor at a temperature of 700° C. to 900° C. under the methane gas atmosphere may be performed, such that the lead oxide is reduced to the lead which in turn is vaporized.

Specifically, in the heat-treatment step S300, the lead oxide has a significantly higher vapor pressure than that of each of the copper oxide and tin oxide in an entire temperature region of 700° C. to 900° C., so that the lead is vaporized in the temperature range. Having the higher vapor pressure means that it is easy to break an attraction force between molecules under a certain condition, and thus a boiling point of the lead is lowered and the leads evaporates easily.

Therefore, it is preferable that the recovering line for recovering the vaporized lead is connected to a top of the reactor.

In this connection, the step of recovering the lead through the recovering line may include cooling and depositing the vaporized lead; dust-collecting lead not deposited in the deposition step; and recovering the lead not dust-collected in the dust-collecting step.

First, the vaporized lead moves to the upper end or the top of the reactor, and then is discharged to an outside of the reactor through the recovery line connected to the upper end of the reactor. Thereafter, a step of moving the vaporized lead to a device such as a condenser having a cooling plate to cool and deposit the vaporized lead is performed.

In this connection, the step of depositing may be performed one or more times, such that the vaporized lead may be efficiently recovered.

Thereafter, the step of dust-collecting the lead not deposited in the deposition step is performed. The undeposited lead may be recovered by dust-collecting one more time using a dust-collector connected in series to the condenser.

Finally, the method may proceed with the step of recovering the lead that has not been dust-collected in the step of the dust-collecting. This step may be performed using a scrubber connected in series to the dust-collector. Finally, the lead may be recovered, thereby preventing a trace amount of lead from being discharged to the atmosphere.

In one example, referring toFIG.2, an apparatus for recovering copper, bronze and lead from a mixture of copper oxide, tin oxide and lead oxide according to another embodiment of the present disclosure may include a reactor100, a mesh structure200, a recovering unit300, a heater400and a recovering line500.

The reductive gas is introduced into the reactor100, and the mesh structure is received therein, so that a mixture of copper oxide, tin oxide and lead oxide may be disposed on the top face of the mesh structure.

Further, the heater400for heating the inside of the reactor100is received inside the reactor100. The recovering line500is connected to an upper end thereof, so that lead vaporized by heating inside the reactor100may be discharged to the outside.

In this connection, it is most preferable that the methane gas as the reductive gas flows into the reactor100. The methane gas allows the copper oxide, tin oxide and lead oxide to be reduced. In particular, the methane gas may react with the residual oxygen in the reactor100to continuously removes oxygen so that the oxidation reaction of the lead does not occur.

Further, while the temperature of the reactor100is increased using the heater400, nitrogen or argon gas as an inert gas may be introduced into the reactor100at an amount of 300 cc/min to remove the oxygen inside the reactor100when the temperature is increased.

Further, the nitrogen or argon gas as an inert gas may be introduced even when the temperature of the inside of the reactor100is lowered.

The mesh structure200is disposed inside the reactor100, and a mixture of copper oxide, tin oxide, and lead oxide is placed on a top face of the structure200. Further, the recovering unit300capable of recovering molten material due to the heat of the heater400is disposed below the structure200.

The mixture of the copper oxide, tin oxide and lead oxide is heat-treated in the presence of the methane gas inside the reactor100to produce a molten copper-tin alloy. Therefore, copper of the mixture of the copper oxide, tin oxide and lead oxide is reduced and remains on the top face of the mesh structure200, and portions of the copper oxide and tin oxide constitute the copper-tin alloy which is melt and flows through the mesh structure200to the bottom and gathers in the recovering unit. That is, copper and bronze may be separated from each other using the mesh structure200.

The recovering unit300is disposed below the mesh structure200, and serves to recover the molten copper-tin alloy.

The heater400heats the inside of the reactor100, and may be disposed in the inside of the reactor100and may be embodied in a form of a heating coil. In this connection, the heater200preferably heats the inside of the reactor100to 700° C. or higher and 900° C. or lower.

When the temperature of the inside of the reactor100is lower than 700° C., a recovery rate of the molten material is low. When it exceeds 900° C., the copper reduced from the copper oxide may melt. Therefore, it is most preferable that the heater400heats the inside of the reactor100to 700° C. or higher and 900° C. or lower.

The recovering line500is connected to the upper end of the reactor100, and may recover the lead vaporized inside the reactor100and at the same time discharge the lead vaporized inside the reactor100to the outside.

Specifically, the recovering line500may include one or more condensers510, a dust-collector520and a scrubber530.

The condenser510is configured for depositing the vaporized lead discharged from the reactor100. One or more condensers may be connected in series to each other. At least one cooling plate511is provided inside the condenser510, so that the vaporized lead may be liquefied and deposited and recovered.

The dust-collector520is connected in series to the condenser510, and dust-collects the lead that has not been deposited on the condenser510to further recover the lead.

The scrubber530is connected in series to the dust-collector520, and finally recovers the lead that is not dust-collected in the dust-collector520, and thus prevents a trace amount of lead from being released into the atmosphere.

Therefore, the apparatus according to the present disclosure may recover the vaporized lead, as well as may prevent the lead from scattering into the atmosphere, thereby achieving an environmentally friendly effect.

In one example, the apparatus for recovering the copper, bronze and lead according to the present disclosure may further include a pressing device600and a rotating device.

The pressing device600is configured for applying an impact force or inertial force to the mixture or the reactor100, and may include, for example, a pressure device such as a hydraulic cylinder.

Specifically, the pressing device600may apply an impact force or inertial force 10 times for 1 minute to 3 minutes to the mixture or the mesh structure200inside the reactor100. Thus, the larger amount of the molten material, that is, the copper-tin alloy flows to the bottom of the reactor due to the inertial force and impact force, so that the copper and bronze may be separated from each other more effectively.

In particular, it is most preferable to apply the impact force or inertial force at a temperature of 900° C. 10 times for 2 minutes. This is because a larger amount of bronze is melted at a temperature of 900° C., and further, when the impact or inertia force is applied thereto 10 times for 2 minutes, the copper and bronze may not be compressed, and thus the copper and bronze may be effectively separated from each other.

Although not shown inFIG.2, the rotating device is configured for rotating the reactor100and thus applying the rotational force to a waste ribbon electrode. For example, a rotating motor may be used as the rotating device.

The rotating device also applies the rotational force to the reactor10010 times for 1 to 3 minutes, so that the larger amount of the molten material, that is, the molten copper-tin alloy flows to the bottom of the reactor due to the rotational force, so that the copper and bronze may be separated from each other more effectively.

In particular, it is most preferable to rotate the reactor10010 times for 2 minutes under the temperature condition of 900° C. This is because a large amount of the copper-tin alloy is melted at a temperature of 900° C., and, further, when the rotational force is applied thereto 10 times for 2 minutes, sufficient rotational force is applied to the mixture, such that the copper and bronze may be effectively separated from each other.

Hereinafter, the method and the apparatus for recovering copper, bronze and lead according to the present disclosure will be described in more detail based on specific examples.

Experimental Example 1

A waste ribbon battery having a copper base material and coated with lead-tin alloy was placed on a top face of the mesh structure according to the present disclosure. Then, while nitrogen gas was introduced into the reactor at an amount of 300 cc/min, the temperature inside the reactor was increased. Thereafter, methane gas was introduced into the reactor, and the heat-treatment was performed for 1 hour under temperature conditions at 700° C., 800° C. and 900° C., respectively.

Further, during the heat-treatment, the inertial force and the impact force were applied to the mixture at a rate of 10 times for 1 minute, 10 times for 2 minutes, and 10 times for 3 minutes, respectively. At the same time, the reactor was rotated at the same speed to apply a rotational force thereto. The photograph of the resulting copper ribbon and the copper purity measurement result of the copper ribbon are shown inFIGS.3to5.

Examples according to specific experimental conditions are shown in Table 1 below.

TABLE 1Temperature condition1 hr application700° C.800° C.900° C.Inertia force,10 times/PresentPresentPresentimpact force,1 minexample 1-1example 2-1example 3-1and rotational10 times/PresentPresentPresentforce2 minsexample 1-2example 2-2example 3-210 times/PresentPresentPresent3 minsexample 1-3example 2-3example 3-3

Referring toFIG.3, in the present example 1-1, the copper purity of the copper ribbon was 88.36 wt. %. The copper purity of the copper ribbon was 88.96 wt. % in the present example 1-2. The copper purity of the copper ribbon was 87.93% in the present example 1-3. It could be identified that the effect due to the vibration and rotation was not relatively considerable because the tin oxide of the waste ribbon battery was hardly melted under the temperature condition of 700° C.

In one example, referring toFIG.4, in the present example 2-1, the copper purity of the copper ribbon was 89.15 wt. %. In the present example 2-1, the copper purity of the copper ribbon was 90.75 wt. %. In the present example 2-3, the copper purity of the copper ribbon was 88.84%. This indicates that the present examples 2-1 to 203 exhibited relatively high copper purity, compared to the present examples 1-1 to 1-3. Further, it was identified that when the inertial force, impact force, and rotational force of 10 times per 2 minutes (present example 2-2) were applied to the waste ribbon battery under the temperature condition of 800° C., the copper purity was the highest, and thus the effect due to the vibration and rotation was the highest.

Referring toFIG.5, in the present example 3-1 to present example 3-3 having a temperature condition of 900° C., the copper purity of the copper ribbon was 90 wt. % or greater. Thus, the largest amount of the tin oxide of the waste ribbon battery was melted.

Further, it was identified that the highest copper purity was obtained and thus the effect due to the vibration and rotation was the highest when the rotational force and inertia force were applied to the waste ribbon battery 10 times/2 mins under the condition of 900° C. temperature (present example 3-2).

Therefore, the larger amount of the tin oxide melts as the temperature increases. It may be identified that when the inertial force, impact force, and rotational force were applied 10 times per 2 minutes under the same temperature condition, the effect due to the vibration and rotation is the highest.

Experimental Example 2

The experiment was performed in the same manner as in Experimental Example 1, except that the temperature condition was fixed to 900° C. and a reaction time was changed to 1 hour, 2 hours and 3 hours. As a result, the photograph of the obtained copper ribbon and the copper purity measurement result of the copper ribbon are shown inFIG.5toFIG.7.

Examples according to specific experimental conditions are shown in Table 2 below.

TABLE 2Reaction time condition900° C.1 hr2 hr3 hrInertia force,10 times/PresentPresentPresentimpact force,1 minsexample 3-1example 4-1example 5-1and rotational10 times/PresentPresentPresentforce2 minsexample 3-2example 4-2example 5-210 times/PresentPresentPresent3 minsexample 3-3example 4-3example 5-3

In the present example 3-1 to present example 3-3, the results are shown inFIG.5. In the present example 3-1 to present example 3-3, the same results as those of Experimental Example 1 are achieved. Thus, the description thereof is omitted.

Referring toFIG.6, in the present example 4-1, the copper purity of the copper ribbon was 91.76 wt. %. The copper purity of the copper ribbon was 95.96 wt. % in the present example 4-2. The copper purity of the copper ribbon was 93.73% in the present example 4-3. Thus, the present examples 4-1 to 4-3 exhibited higher copper purity under the same inertial force, impact force and rotational force conditions than those in the present example 3-1 to present example 3-3.

In particular, it was identified that the highest copper purity was achieved in the present example 4-2, and thus the effect due to the vibration and rotation was the highest when the inertial and rotational forces were applied thereto 10 times per 2 minutes.

On the contrary, it was identified that in the present example 4-1, the copper base material and the tin-lead coating layer were compressed according to the vibration and rotation 10 times per minute, resulting in deterioration of purity.

Further, it could be identified that in the example 4-3, the larger amount of the molten tin oxide did not flow down along the mesh structure due to insufficient amount of the vibration and rotation.

In one example, as shown inFIG.7, in the present example 5-2 in which the vibrations and rotations were applied thereto 10 times per 2 minutes, an appearance of the copper base material was completely exposed, and most of the tin oxide was melted. Thus, it was identified that a content of each of tin and lead was smaller than 1 wt. % when analyzing the copper ribbon.

On the contrary, in the present example 5-1, the purity of the copper ribbon was lowered due to compression resulting from excessive vibration and rotation, compared to the present example 5-2. In the present example 5-3, the molten tin oxide remained in the copper base material due to an insufficient amount of the vibration and rotation as in the present example 4-3.

Therefore, it could be identified that the larger amount of the tin oxide was melted as the temperature increased and the reaction time increased. When the inertial force and rotational force are applied thereto 10 times per 2 minutes under the same temperature condition, the effect due to the vibration and rotation is the highest.

In one example,FIG.8shows a photograph of a copper-tin alloy obtained according to each of present example 5-1 to present example 5-3 of Experimental Example 2, and the copper and tin measurement result of the copper-tin alloy.

As shown inFIG.8, it may be identified that the recovery of the copper-tin alloy having a relatively uniform composition is realized regardless of the vibration and rotation conditions of the copper-tin alloy.

Experimental Example 3

The vaporized lead according to the present example 5-2 of Experimental Example 2 was recovered using the recovering line according to the present disclosure, and the finally obtained lead was analyzed using ICP. Further, the photograph of the finally obtained lead and the lead purity result are shown inFIG.9.

Specifically, the vaporized lead was deposited and recovered using primary and secondary condensers. The undeposited lead was finally recovered using the dust-collector. Then, the lead that was not dust-collected using the dust-collector was recovered using the scrubber. Thus, the lead may not be discharged into the atmosphere.

As shown inFIG.9, based on a result of ICP analysis, it was identified that the purity of the vaporized lead was 99.9 wt. % and was classified as 3N grade.

The disclosure has been made with reference to the preferred embodiment of the present disclosure. Those skilled in the art will understand that various modifications and changes may be made to the present disclosure without departing from the spirit and scope of the present disclosure set forth in the following claims.