KR101697996B1 - Recovery Method of Metal of Photovoltaic Ribbon using Mixed Acid - Google Patents

Recovery Method of Metal of Photovoltaic Ribbon using Mixed Acid Download PDF

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KR101697996B1
KR101697996B1 KR1020150103555A KR20150103555A KR101697996B1 KR 101697996 B1 KR101697996 B1 KR 101697996B1 KR 1020150103555 A KR1020150103555 A KR 1020150103555A KR 20150103555 A KR20150103555 A KR 20150103555A KR 101697996 B1 KR101697996 B1 KR 101697996B1
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ribbon
acid
copper
recovering
recovered
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KR1020150103555A
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Korean (ko)
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이진석
안영수
강기환
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한국에너지기술연구원
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00—Obtaining lead
    • C22B13/04—Obtaining lead by wet processes
    • C22B13/045—Recovery from waste materials
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0063—Hydrometallurgy
    • C22B15/0065—Leaching or slurrying
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B25/00—Obtaining tin
    • C22B25/04—Obtaining tin by wet processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching

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  • Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
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  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
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  • Processing Of Solid Wastes (AREA)

Abstract

The present invention relates to a method for recovering metal from a sunlight ribbon using a mixed acid. More specifically, the present invention relates to a method for recovering metal from a sunray ribbon by immersing the solar light ribbon in a mixed acid containing nitric acid and hydrofluoric acid or hydrochloric acid and sulfuric acid in a weight ratio of 99: 1 to 51:49 (Step 1); And recovering copper from the photovoltaic ribbon immersed in step 1 (step 2). In the method for recovering the metal of the solar ribbon using the mixed acid of the present invention, when the copper of the photovoltaic ribbon is recovered using the mixed acid of the present invention, the mixed acid selectively reacts with lead and tin on the surface of the ribbon, Copper that is both a material and a high price can be recovered. In addition, lead and tin can be further recovered after copper is recovered from the ribbon. Therefore, by reusing copper, which is a central material of the solar light ribbon, economical gain can be obtained and environmental pollution can be prevented.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for recovering metal from a photovoltaic ribbon,

The present invention relates to a metal recovery method of a solar ribbon using a mixed acid. In particular, the present invention relates to a method for recovering copper, lead and tin using the reaction of a mixed acid with a solar ribbon containing copper, lead and tin.

The need for solar power, a sustainable energy, is higher than ever, due to concern about depletion of fossil fuels, warming due to its abuse, climate change, and safety concerns in nuclear energy. Of course, not all of the energy from the sun can be exploited, but because of its relatively less localized characteristics and inherent eco-friendliness, photovoltaics has always been regarded as one of the most attractive renewable energy sources.

On the other hand, since the electromotive force generated in a unit cell is very small in practical use, a solar cell module having a proper electromotive force is constructed by connecting a plurality of solar cell devices. Therefore, in order to use the solar cell for a predetermined purpose, the capacity of the solar cell module is adjusted according to the application. In order to increase the generated voltage per unit area of the solar cell module, the solar cell elements are connected to each other in series by the conductor ribbon It is common. These conductor ribbons are coated with lead and tin on the surface of copper.

These solar cells must be removed over time as their use reduces the power conversion efficiency. At this time, the expensive material contained in the solar cell must be recovered together with the removal of the solar cell. This recovery can conserve expensive resources, recycle them, and preserve the environment.

In order to recover the expensive copper contained in the solar cell ribbon, the coated lead and tin must be removed. As a method for removing lead and tin, a simple acid such as hydrochloric acid, hydrofluoric acid, phosphoric acid, nitric acid, and sulfuric acid was reacted with the ribbon, but it was difficult to selectively remove lead and tin.

Accordingly, in the present invention, a copper mixed in a solar cell ribbon was recovered and a mixed acid of nitric acid and hydrofluoric acid and a mixed acid of hydrochloric acid and sulfuric acid having a certain range of ratio capable of selectively removing lead and tin on the surface thereof were developed . We have also developed a method for recovering metals from solar cells using mixed acid, which can recover not only copper contained in the ribbon but also lead and tin.

Patent Document 10-2015-0039006

'Recovery of Copper from Spent Photovoltaic Ribbon in Solar Module', J. of Korean Inst. of Resources Recycling Vol. 22, No. 5, 2013, 50-55

It is an object of the present invention to provide a metal recovery method of a solar ribbon using a mixed acid.

In order to achieve the above object,

Immersing the solar ribbon in a mixed acid comprising nitric acid and hydrofluoric acid in a weight ratio of 99: 1 to 51:49 (step 1); And

And recovering the copper from the photovoltaic ribbon immersed in step 1 (step 2).

In addition,

Immersing the solar ribbon in a mixed acid comprising nitric acid and hydrofluoric acid in a weight ratio of 99: 1 to 51:49 (step 1);

Recovering copper from the photovoltaic ribbon immersed in step 1 (step 2);

Recovering lead (Pb) in the leachate 1 after recovering copper in the step 2 (step 3); And

And recovering tin (Sn) from the leachate 2 after the lead is recovered in the step 3 (step 4).

Further,

Immersing the solar ribbon in a mixed acid comprising hydrochloric acid and sulfuric acid in a weight ratio of 99: 1 to 51:49 (step 1); And

And recovering the copper from the photovoltaic ribbon immersed in step 1 (step 2).

Further,

Immersing the solar ribbon in a mixed acid comprising hydrochloric acid and sulfuric acid in a weight ratio of 99: 1 to 51:49 (step 1);

Recovering copper from the photovoltaic ribbon immersed in step 1 (step 2);

Recovering tin (Sn) in the leachate 1 after recovering copper in step 2 (step 3); And

And recovering lead (Pb) from the leachate 2 after recovering the tin in the step 3 (step 4).

In the method for recovering the metal of the solar ribbon using the mixed acid of the present invention, when the copper of the photovoltaic ribbon is recovered using the mixed acid of the present invention, the mixed acid selectively reacts with lead and tin on the surface of the ribbon, Copper that is both a material and a high price can be recovered. In addition, lead and tin can be further recovered after copper is recovered from the ribbon. Therefore, by reusing copper, which is a central material of the solar light ribbon, economical gain can be obtained and environmental pollution can be prevented.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flowchart showing a metal recovery method for a photovoltaic ribbon and a method for recovering lead and tin from a leach solution for a mixed acid of nitric acid and hydrofluoric acid;
FIG. 2 is a flowchart showing a metal recovery method for a solar ribbon and a method for recovering tin and lead from a leach solution for a mixed acid of hydrochloric acid and sulfuric acid;
Figure 3 is a graph showing the reactivity of copper, lead and tin to nitric acid;
4 is a photograph showing the reaction process of copper nitrate and hydrofluoric acid to the ribbon;
Figure 5 is a graph showing the reactivity of copper, lead and tin to hydrochloric acid and sulfuric acid;
Figure 6 shows the reaction process of hydrochloric acid and sulfuric acid to the copper ribbon;
7 is a photograph showing the reaction process of mixed acid and copper ribbon according to the ratio of nitric acid and hydrofluoric acid;
8 is a photograph showing reaction results of mixed acid and copper ribbon according to the ratio of nitric acid and hydrofluoric acid;
9 is a photograph of the precipitate (PbF 2 ) observed by a scanning electron microscope;
FIG. 10 is a graph of the precipitate (PbF 2 ) analyzed by X-ray diffraction analysis;
11 is a photograph showing the reaction process of mixed acid and copper ribbon according to the ratio of hydrochloric acid and sulfuric acid;
12 is a photograph showing reaction results of mixed acid and copper ribbon according to the ratio of hydrochloric acid and sulfuric acid;
13 is a photograph of a precipitate (PbSO 4 , PbCl 2 ) observed with a scanning electron microscope;
FIG. 14 is a graph of the precipitate (PbSO 4 , PbCl 2 ) analyzed by X-ray diffraction analysis.

According to the present invention,

Immersing the solar ribbon in a mixed acid comprising nitric acid and hydrofluoric acid in a weight ratio of 99: 1 to 51:49 (step 1); And

And recovering the copper from the photovoltaic ribbon immersed in step 1 (step 2).

Hereinafter, the copper recovery method of the solar ribbon according to the present invention will be described in detail for each step.

In the copper recovery method of the photovoltaic ribbon according to the present invention, step 1 is a step of immersing the photovoltaic ribbon in a mixed acid containing nitric acid and hydrofluoric acid in a weight ratio of 99: 1 to 51:49.

The photovoltaic ribbon of step 1 is a material for connecting solar cell elements constituting the solar cell module of solar photovoltaic power generation, which is sustainable energy, to each other in series. When the solar cell is later removed due to a decrease in power conversion efficiency, A problem of wasting expensive resources may arise. Thus, a simple wet process would be required to recover the copper of the ribbon, but if, for example, a copper ribbon is treated with a simple acid, there is little reaction between the single acid and the solar ribbon, or the copper reacts with the copper to be recovered, There is a problem in that it is not suitable for recovering the copper of the photovoltaic ribbon.

Accordingly, the copper recovery method of the present invention is a method for recovering copper by using a mixed acid capable of selectively removing and reacting metals other than copper of the solar ribbon, for example, lead, tin, Copper is recovered.

(Cu) -containing mixed acid containing nitric acid and hydrofluoric acid in a weight ratio of 99: 1 to 51:49 may be used, and the concentration may be 5 to 50% by weight each of nitric acid and hydrofluoric acid, It is not.

At this time, the mixing ratio of nitric acid to hydrofluoric acid contained in the mixed acid for effectively removing lead and tin on the surface of the ribbon is preferably in a weight ratio of 99: 1 to 51:49. If the hydrofluoric acid is mixed at the same or higher ratio than nitric acid, there may be a problem that the precipitate fluorophosphate (PbF 2 ) is generated. That is, if the mixing ratio of nitric acid and hydrofluoric acid is mixed in a weight ratio of 50:50 to 1:99, a precipitate (PbF 2 ) may be generated and become inadequate for effectively recovering copper.

In addition, the higher the ratio of nitric acid in the mixed acid, the higher the rate at which the ribbon reacts with the mixed acid. If nitric acid alone reacts with the ribbon, it is difficult to recover the copper since it is highly reactive with the copper to be recovered than the lead and tin to be removed. However, by mixing with hydrofluoric acid, the reaction rate is controlled and lead and tin react first, It is possible to recover.

In the method for recovering copper of the solar ribbon according to the present invention, step 2 is a step of recovering copper from the solar ribbon immersed in step 1 above.

After the lead and tin on the surface of the solar ribbon have reacted with the mixed acid, the copper remaining in the center of the ribbon can be recovered.

In addition,

Immersing the solar ribbon in a mixed acid comprising nitric acid and hydrofluoric acid in a weight ratio of 99: 1 to 51:49 (step 1);

Recovering copper from the photovoltaic ribbon immersed in step 1 (step 2);

Recovering lead (Pb) in the leachate 1 after recovering copper in the step 2 (step 3); And

And recovering tin (Sn) from the leachate 2 after the lead is recovered in the step 3 (step 4). A flowchart of a method of recovering a metal of the solar ribbon according to the present invention is shown in FIG.

In the metal recovery method of the solar ribbon according to the present invention, steps 1 and 2 are described in the copper recovery method of the above-described solar ribbon, and steps 3 and 4 will be described in detail.

In the metal recovery method of the solar ribbon according to the present invention, the step of removing fluorine from the leach solution 1 after recovering copper in the step 2 may further include the step of step 3.

(Ca (OH) 2 ), magnesium oxide (MgO), and magnesium hydroxide (Mg (OH) 2 ) as a step for controlling fluorine using magnesium (Mg) and calcium 2 ) may be added to remove fluorine in the form of calcium fluoride (CaF 2 ) or magnesium fluoride (MgF 2 ).

In the metal recovery method of the solar ribbon according to the present invention, step 3 is a step of recovering lead (Pb) from the leach solution 1 after recovering copper in step 2 above.

The leach liquor 1 after recovering copper in the step 2 contains tin and lead dissolved in a mixed acid of nitric acid and hydrofluoric acid and mixed acid. From the leach liquor 1, lead sulfate (PbSO 4 ) is formed by the sulfuric acid method using sulfuric acid (H 2 SO 4 ) in particular, whereby lead can be recovered.

In the metal recovery method of the solar ribbon according to the present invention, step 4 is a step of recovering tin (Sn) in the leach solution 2 after recovery of lead in step 3 above.

(NH 4 OH), potassium hydroxide (KOH), and sodium hydroxide (NaOH), for example, by recovering tin from the leachate 2 after recovery of lead in step 3 by neutralization using an alkali solution Tin hydroxide (Sn (OH) 2 ) is formed by a neutralization method using at least one of them, and tin can be recovered through it.

In the method for recovering the metal of the solar ribbon according to the present invention, after the step 4 is performed, the residual leach solution may contain very small amounts of tin and lead, which can be disposed of and treated.

Further,

Immersing the solar ribbon in a mixed acid comprising hydrochloric acid and sulfuric acid in a weight ratio of 99: 1 to 51:49 (step 1); And

And recovering the copper from the photovoltaic ribbon immersed in step 1 (step 2).

Hereinafter, the copper recovery method of the solar ribbon according to the present invention will be described in detail for each step.

In the copper recovery method of the photovoltaic ribbon according to the present invention, Step 1 is a step of immersing the photovoltaic ribbon in a mixed acid containing hydrochloric acid and sulfuric acid in a weight ratio of 99: 1 to 51:49.

In step 1, a mixed acid comprising hydrochloric acid (HCl) and sulfuric acid (H 2 SO 4 ) is used for the copper recovery method of the solar ribbon. Hydrochloric acid reacts with lead and tin on the surface of the ribbon, and since it is reactive with copper, copper may be lost, while sulfuric acid is less reactive with lead, tin and copper on the ribbon surface. Thus, mixed acid with sulfuric acid in hydrochloric acid can reduce the loss of copper by forming a passivation on the copper surface.

Mixed acids containing hydrochloric acid and sulfuric acid in a weight ratio of 99: 1 to 51:49 may be used, and the concentrations of hydrochloric acid and sulfuric acid may each be 10 to 35% by weight, But are not limited thereto.

At this time, the mixing ratio of hydrochloric acid and sulfuric acid contained in the mixed acid for effectively removing lead and tin on the surface of the ribbon is preferably in the weight ratio of 99: 1 to 51:49. If sulfuric acid is mixed at the same or higher ratio than hydrochloric acid, there may be a problem that lead precipitate (PbSO 4 ) and lead chloride (PbCl 2 ) are generated. That is, if the mixing ratio of hydrochloric acid and sulfuric acid is mixed in a weight ratio of 50:50 to 1:99, precipitates (PbSO 4 , PbCl 2 ) may be generated, which may be inadequate for effectively recovering copper.

In addition, the higher the ratio of hydrochloric acid in the mixed acid, the higher the rate at which the ribbon reacts with the mixed acid. If hydrochloric acid alone is reacted with the ribbon, it reacts with the copper to be recovered, which makes it difficult to recover the copper. However, by mixing with sulfuric acid, the reaction rate can be controlled and effective copper recovery is possible.

In the method for recovering copper of the solar ribbon according to the present invention, step 2 is a step of recovering copper from the solar ribbon immersed in step 1 above.

After the lead and tin on the surface of the solar ribbon have reacted with the mixed acid, the copper remaining in the center of the ribbon can be recovered.

Further,

Immersing the solar ribbon in a mixed acid comprising hydrochloric acid and sulfuric acid in a weight ratio of 99: 1 to 51:49 (step 1);

Recovering copper from the photovoltaic ribbon immersed in step 1 (step 2);

Recovering tin (Sn) in the leachate 1 after recovering copper in step 2 (step 3); And

And recovering lead (Pb) from the leachate 2 after recovering the tin in the step 3 (step 4). 2 is a flowchart illustrating a method of recovering a metal ribbon according to an embodiment of the present invention.

In the metal recovery method of the solar ribbon according to the present invention, steps 1 and 2 are described in the copper recovery method of the above-described solar ribbon, and steps 3 and 4 will be described in detail.

In the metal recovery method of the solar ribbon according to the present invention, step 3 is a step of recovering tin (Sn) in the leached solution 1 after recovering copper in step 2 above.

The leachate 1 after recovering copper in the step 2 contains tin and lead dissolved in mixed acid of hydrochloric acid and sulfuric acid and mixed acid. At least one of ammonium hydroxide (NH 4 OH), potassium hydroxide (KOH) and sodium hydroxide (NaOH) is used, for example, by recovering tin from the leach liquor 1 by neutralization using an alkali solution Tin hydroxide (Sn (OH) 2 ) is formed by a neutralization method, and tin can be recovered through this.

In the metal recovery method of the solar ribbon according to the present invention, step 4 is a step of recovering lead (Pb) from the leach solution 2 after recovering tin in step 3 above.

The lead is recovered from the leachate 2 after the tin is recovered in the step 3 by the sulfiding method or the sulfation method and the sulfiding method using, for example, sodium sulfide (Na 2 S) or hydrogen sulfide (H 2 S) Lead can be recovered by forming lead sulfide (PbS) or by forming sulfuric acid lead (PbSO 4 ) by sulfation method using sulfuric acid (H 2 SO 4 ).

In the method for recovering the metal of the solar ribbon according to the present invention, after the step 4 is performed, the residual leach solution may contain very small amounts of tin and lead, which can be disposed of and treated.

Hereinafter, the present invention will be described in more detail with reference to examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Example 1 Recovery of Copper by Reaction of Solar Ribbon with Mixed Acid 1

Step 1: 2 g of the photovoltaic ribbon disassembled from the photovoltaic module was immersed in a 20 wt% mixed acid containing nitric acid and hydrofluoric acid in a weight ratio of 9: 1 for 10 minutes. The compositional analysis of the above-described solar ribbon is shown in Table 1 below.

sample Element and content (wt%) Cu Pb Sn Ag Cu-ribbon
(electrode) 85.309 9.033 5.652 0.002

As shown in Table 1, the photovoltaic ribbon contained 1.7 g of copper in an amount of 85.309% by weight, 0.18 g of lead in 9.033% by weight, 0.113 g of tin in an amount of 5.652% by weight, 0.002% And 0.00004 g, respectively.

Step 2: 1.70 g of copper was recovered from the photovoltaic ribbon immersed in step 1 above. As a result, most of the copper contained in the photovoltaic ribbon was recovered.

≪ Example 2 > Copper recovery according to the reaction between a photovoltaic ribbon and a mixed acid 2

Step 1: 2 g of photovoltaic ribbon disassembled from the photovoltaic module was immersed in a mixed acid of 20% by weight concentration containing nitric acid and hydrofluoric acid in a weight ratio of 3: 1 for 10 minutes.

Step 2: 1.69 g of copper was recovered from the photovoltaic ribbon immersed in step 1 above. As a result, most of the copper contained in the photovoltaic ribbon was recovered.

≪ Example 3 > Copper recovery according to the reaction between a photovoltaic ribbon and a mixed acid 3

Step 1: 2 g of the photovoltaic ribbon disassembled from the photovoltaic module was immersed for 40 minutes in a 35 wt% mixed acid containing hydrochloric acid and sulfuric acid in a weight ratio of 9: 1.

Step 2: 1.7 g of copper was recovered from the photovoltaic ribbon immersed in step 1 above. As a result, most of the copper contained in the photovoltaic ribbon was recovered.

Example 4 Copper Recovery by Reaction of Solar Ribbon with Mixed Acid 4

Step 1: 2 g of the photovoltaic ribbon disassembled from the photovoltaic module was immersed in a 35 wt% mixed acid containing hydrochloric acid and sulfuric acid in a weight ratio of 3: 1 for 1 hour.

Step 2: 1.69 g of copper was recovered from the photovoltaic ribbon immersed in step 1 above. As a result, most of the copper contained in the photovoltaic ribbon was recovered.

Example 5 Recovery of Copper by Reaction of Solar Ribbon with Mixed Acid 5

Step 1: 2 g of photovoltaic ribbon disassembled from the photovoltaic module was immersed in a mixed acid containing 99: 1 by weight of nitric acid and hydrofluoric acid.

Step 2: Copper was recovered from the photovoltaic ribbon immersed in step 1 above.

Example 6 Recovery of Copper by Reaction of Solar Ribbon with Mixed Acid 6

Step 1: 2 g of the solar ribbon disassembled from the photovoltaic module was immersed in a mixed acid containing nitric acid and hydrofluoric acid in a weight ratio of 4: 1.

Step 2: Copper was recovered from the photovoltaic ribbon immersed in step 1 above.

Example 7 Recovery of Copper by Reaction of Solar Ribbon with Mixed Acid 7

Step 1: 2 g of the solar ribbon disassembled from the photovoltaic module was immersed in a mixed acid containing nitric acid and hydrofluoric acid in a weight ratio of 3: 2.

Step 2: Copper was recovered from the photovoltaic ribbon immersed in step 1 above.

Example 8 Recovery of Copper by Reaction of Solar Ribbon with Mixed Acid 8

Step 1: 2 g of the solar ribbon disassembled from the photovoltaic module was immersed in a mixed acid containing nitric acid and hydrofluoric acid in a weight ratio of 51:49.

Step 2: Copper was recovered from the photovoltaic ribbon immersed in step 1 above.

Example 9 Copper Recovery by Reaction of Solar Ribbon with Mixed Acid 9

Step 1: 2 g of photovoltaic ribbon disassembled from the photovoltaic module was immersed in a mixed acid containing hydrochloric acid and sulfuric acid in a weight ratio of 99: 1.

Step 2: Copper was recovered from the photovoltaic ribbon immersed in step 1 above.

Example 10 Copper Recovery by Reaction of Solar Ribbon with Mixed Acid 10

Step 1: 2 g of the solar ribbon disassembled from the photovoltaic module was immersed in a mixed acid containing hydrochloric acid and sulfuric acid in a weight ratio of 4: 1.

Step 2: Copper was recovered from the photovoltaic ribbon immersed in step 1 above.

Example 11 Copper Recovery by Reaction of Solar Ribbons with Mixed Acids 11

Step 1: 2 g of the solar ribbon disassembled from the photovoltaic module was immersed in a mixed acid containing hydrochloric acid and sulfuric acid in a weight ratio of 3: 2.

Step 2: Copper was recovered from the photovoltaic ribbon immersed in step 1 above.

Example 12 Copper Recovery by Reaction of Solar Ribbons with Mixed Acids 12

Step 1: 2 g of the solar ribbon disassembled from the photovoltaic module was immersed in a mixed acid containing hydrochloric acid and sulfuric acid in a weight ratio of 51:49.

Step 2: Copper was recovered from the photovoltaic ribbon immersed in step 1 above.

≪ Comparative Example 1 &

Step 1: 2 g of photovoltaic ribbon disassembled from the photovoltaic module was immersed in a mixed acid of 20 wt% concentration containing nitric acid and hydrofluoric acid in a weight ratio of 1: 1 for 13 minutes.

Step 2: 1.71 g of copper was recovered from the photovoltaic ribbon immersed in step 1, but it was confirmed that the precipitate (PbF 2 ) was generated.

≪ Comparative Example 2 &

Step 1: 2 g of the photovoltaic ribbon disassembled from the photovoltaic module was immersed in a 20 wt% mixed acid containing nitric acid and hydrofluoric acid in a weight ratio of 1: 3 for 17 minutes.

Step 2: 1.68 g of copper was recovered from the photovoltaic ribbon immersed in step 1, but it was confirmed that a precipitate (PbF 2 ) was generated.

≪ Comparative Example 3 &

Step 1: 2 g of photovoltaic ribbon disassembled from the photovoltaic module was immersed in a mixed acid of 20 wt% concentration containing nitric acid and hydrofluoric acid in a weight ratio of 1: 9 for 25 minutes.

Step 2: 1.70 g of copper was recovered from the photovoltaic ribbon immersed in step 1, but it was confirmed that the precipitate (PbF 2 ) was generated.

≪ Comparative Example 4 &

Step 1: 2 g of the photovoltaic ribbon disassembled from the photovoltaic module was immersed in a 35 wt% mixed acid containing hydrochloric acid and sulfuric acid in a weight ratio of 1: 1 for 90 minutes.

Step 2: 1.70 g of copper was recovered from the photovoltaic ribbon immersed in step 1, but it was confirmed that precipitates (PbSO 4 , PbCl 2 ) were generated.

≪ Comparative Example 5 &

Step 1: 2 g of the photovoltaic ribbon disassembled from the photovoltaic module was immersed in a 35 wt% mixed acid containing hydrochloric acid and sulfuric acid in a weight ratio of 1: 3 for 6 hours.

Step 2: 1.66 g of copper was recovered from the photovoltaic ribbon immersed in step 1, but it was confirmed that precipitates (PbSO 4 , PbCl 2 ) were generated.

≪ Comparative Example 6 >

Step 1: 2 g of the photovoltaic ribbon disassembled from the photovoltaic module was immersed in a 35 wt% mixed acid containing hydrochloric acid and sulfuric acid in a weight ratio of 1: 9 for 24 hours.

Step 2: 1.58 g of copper was recovered from the photovoltaic ribbon immersed in step 1, but it was confirmed that precipitates (PbSO 4 , PbCl 2 ) were generated.

analysis

Analysis of reaction of monoacidic acid

In order to analyze the degree of reaction between the solar ribbon and monoacid, 2 g of the solar ribbon was immersed in nitric acid, hydrofluoric acid, hydrochloric acid and sulfuric acid to compare the degree of reaction. The results are shown in FIGS. 3, 4, 5 and 6 .

As shown in FIG. 3, it is confirmed that there is little reactivity with silver nitrate, lead and tin, but high reactivity with copper.

As shown in Fig. 4, the copper ribbon reacted with nitric acid showed a reaction of nitric acid with the ribbon at a reduced value of 1.49 g, and the copper ribbon reacted with hydrofluoric acid showed almost the same reaction as the initial copper ribbon of 1.99 g .

As shown in FIG. 5, hydrochloric acid reacts with lead and tin on the surface of the ribbon, and because of its reactivity with copper, copper may be lost, while sulfuric acid reacts with lead, tin, Is almost impossible. Therefore, it can be seen that mixed acid in which sulfuric acid is added to hydrochloric acid can reduce the loss of copper by forming a passivation on the copper surface.

As shown in FIG. 6, hydrochloric acid reacts with copper ribbon at room temperature but has a reduced rate of 1.70 g due to the slower reaction rate, whereas at 50 ° C, the reaction rate is faster, resulting in a loss of 0.37 g Can be confirmed. In addition, the copper ribbon reacted with sulfuric acid has a value of 1.84 g, indicating that it hardly reacts.

EXPERIMENTAL EXAMPLE 1 Reactivity and Sediment Analysis of Mixed Acid to Copper Ribbon 1

The process of reacting the copper ribbon with the mixed acid for 24 hours according to the ratio of nitric acid and hydrofluoric acid in the mixed acid of Examples 1 and 2 and Comparative Examples 1, 2 and 3 is shown in FIG. 7, The results after time are shown in Fig.

As shown in FIG. 7, the higher the ratio of nitric acid, the faster the reaction speed, and the copper ribbon is completely melted.

As shown in FIG. 8, in the case of Examples 1 and 2, the recovery rate is 97.1% and 96.6%, respectively, and the reaction rate is fast. Thus, it can be confirmed that the mixing ratio is suitable for copper recovery in the solar ribbon. On the other hand, in Comparative Examples 1, 2 and 3, the recovery rates were 97.7%, 96.0%, and 97.1%, respectively. However, the proportion of hydrofluoric acid was equal to or higher than that of nitric acid to cause precipitation (PbF 2 ) .

The precipitate was observed through a scanning electron microscope (SEM-4700) and an X-ray diffraction analysis (DMAX-2500), and the results are shown in FIGS.

As shown in Figs. 9 and 10, it can be confirmed that the precipitate is fluoropropane (PbF 2 ) from the size of the component and the sharp PEAK point.

<Experimental Example 2> Reactivity and sediment analysis of mixed acid to copper ribbon 2

11 shows the reaction of the copper ribbon with the mixed acid for 24 hours according to the ratio of hydrochloric acid and sulfuric acid in the mixed acid of Examples 3 and 4 and Comparative Examples 4, 5 and 6. The reaction The results after the time are shown in Fig.

As shown in FIG. 11, the higher the ratio of hydrochloric acid is, the faster the reaction speed is, and a large number of copper ribbons are melted.

As shown in FIG. 12, in the case of Examples 3 and 4, the recovery rate is 97.1% and 96.6%, respectively, and the reaction rate is fast. Thus, it can be confirmed that the mixing ratio for the copper recovery in the photovoltaic ribbon is proper. On the other hand, the recovery rates of Comparative Examples 4, 5 and 6 were 97.1%, 94.9%, and 90.3%, respectively. However, the ratio of sulfuric acid was higher than that of hydrochloric acid to produce precipitates (PbSO 4 and PbCl 2 ) You can confirm the growth.

The precipitate was observed through a scanning electron microscope (SEM-4700) and an X-ray diffraction analysis (DMAX-2500), and the results are shown in FIGS.

As shown in FIGS. 13 and 14, it can be confirmed that the precipitate is lead sulfate (PbSO 4 ) and lead chloride (PbCl 2 ) from the size of the component and clear PEAK point.

Claims (14)

Immersing the solar ribbon in a mixed acid comprising nitric acid and hydrofluoric acid in a weight ratio of 99: 1 to 51:49 (step 1); And
And recovering the copper from the photovoltaic ribbon immersed in step 1 (step 2).
Immersing the solar ribbon in a mixed acid comprising nitric acid and hydrofluoric acid in a weight ratio of 99: 1 to 51:49 (step 1);
Recovering copper from the photovoltaic ribbon immersed in step 1 (step 2);
Recovering lead (Pb) in the leachate 1 after recovering copper in the step 2 (step 3); And
And recovering tin (Sn) from the leachate 2 after the lead is recovered in the step 3 (step 4).
Immersing the solar ribbon in a mixed acid comprising hydrochloric acid and sulfuric acid in a weight ratio of 99: 1 to 51:49 (step 1); And
And recovering the copper from the photovoltaic ribbon immersed in step 1 (step 2).
Immersing the solar ribbon in a mixed acid comprising hydrochloric acid and sulfuric acid in a weight ratio of 99: 1 to 51:49 (step 1);
Recovering copper from the photovoltaic ribbon immersed in step 1 (step 2);
Recovering tin (Sn) in the leachate 1 after recovering copper in step 2 (step 3); And
And recovering lead (Pb) from the leachate 2 after recovering the tin in the step 3 (step 4).
The method of claim 1, wherein the concentrations of nitric acid and hydrofluoric acid are 5 to 50 wt%, respectively.
The method of claim 2, wherein the concentrations of nitric acid and hydrofluoric acid are 5 to 50 wt%, respectively.
The method of claim 3, wherein the concentrations of hydrochloric acid and sulfuric acid are 10 to 35 wt%, respectively, and step 1 is performed at a temperature of 30 ° C or more.
The method of claim 4, wherein the concentrations of hydrochloric acid and sulfuric acid are 10 to 35 wt%, respectively, and the step 1 is performed at a temperature of 30 ° C or more.
The method of claim 2, further comprising the step of removing fluorine from the leachate (1) after copper is recovered in step (2).
The method of claim 2, wherein the lead in step 3 is recovered by sulfation using sulfuric acid (H 2 SO 4 ).
The method according to claim 2, wherein the tin in step 4 is recovered by a neutralization method using at least one of ammonium hydroxide (NH 4 OH), potassium hydroxide (KOH) and sodium hydroxide (NaOH) A method of recovering metal from a light ribbon.
The method according to claim 4, wherein the tin in step 3 is recovered by neutralization using at least one of ammonium hydroxide (NH 4 OH), potassium hydroxide (KOH) and sodium hydroxide (NaOH) A method of recovering metal from a light ribbon.
5. The method according to claim 4, wherein the lead in step 4 is a sulfiding method using at least one of sodium sulfide (Na 2 S) or hydrogen sulfide (H 2 S), or a sulfation method using sulfuric acid (H 2 SO 4 ) Wherein the metal ribbon is recovered by the method.
Of claim 9 wherein the removal method, the fluoride is calcium (CaO), calcium hydroxide (Ca (OH) 2), of magnesium oxide (MgO) and magnesium hydroxide (Mg (OH) 2) at least by the addition of any one oxide Characterized in that the metal recovery method of the solar ribbon.
KR1020150103555A 2015-07-22 2015-07-22 Recovery Method of Metal of Photovoltaic Ribbon using Mixed Acid KR101697996B1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005264252A (en) * 2004-03-19 2005-09-29 Dowa Mining Co Ltd TREATMENT METHOD FOR SUBSTANCE CONTAINING Sn, Pb AND Cu
KR20100106551A (en) * 2008-01-10 2010-10-01 각코호진 시바우라고교다이가쿠 Method of recycling useful metal
KR20150039006A (en) 2013-10-01 2015-04-09 한국에너지기술연구원 Apparatus and Method for Recovery of Metal of Photovoltaic Module

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005264252A (en) * 2004-03-19 2005-09-29 Dowa Mining Co Ltd TREATMENT METHOD FOR SUBSTANCE CONTAINING Sn, Pb AND Cu
KR20100106551A (en) * 2008-01-10 2010-10-01 각코호진 시바우라고교다이가쿠 Method of recycling useful metal
KR20150039006A (en) 2013-10-01 2015-04-09 한국에너지기술연구원 Apparatus and Method for Recovery of Metal of Photovoltaic Module

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