JP2001172728A - Recycling method for scrapped air-conditioner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recycling method in which the separation between a copper material, particularly, coated with a resin and the resin is improved and is made efficient, and the treating efficiency of the whole of a scrapped air-conditioner is high. SOLUTION: Foreign matters to be used as raw materials for melting are previously removed from a scrapped air-conditioner, thereafter, a heat exchanger in the waste air-conditioner is charged into a crusing machine in a state in which a copper material and an Al material are joined, crushing is made till the Al fine pieces and the copper fine pieces are made into mixed crushed pieces in which they are respectively separated, and the Al fine pieces and the copper fine pieces are respectively separated and sorted from the mixed crushed pieces, on the other hand, a refrigerant piping member including a piping member in the waste air-conditioner is charged into a crushing machine in a state in which a copper material and a resin material are joined and is crushed while being heated to the softening temperature of the resin pieces, by which crushing is made till the copper fine pieces and the resin pieces are made into mixed crushed pieces in which they are respectively separated, the copper fine pieces are separated and sorted from the mixed crushed pieces, and the Al fine pieces and the copper fine pieces obtained by each sorting are respectively used as the raw materials for the melting of Al and copper.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for recycling a waste air conditioner.

[0002]

2. Description of the Related Art As is well known, air conditioners (air conditioners and coolers) for home use or business use include copper or copper alloy materials.
(Hereinafter, these are collectively referred to as a copper material) and aluminum or an aluminum alloy material (hereinafter, these are collectively referred to as an aluminum material, and aluminum is simply described as Al) are used in large quantities.

[0003] More specifically, a copper pipe through which a refrigerant or a heat medium passes is provided in an indoor unit or an outdoor unit of an air conditioner, and the copper pipe is joined to the copper pipe to increase the contact area with air to improve heat exchange efficiency. A heat exchanger combined with Al fins to increase the temperature is installed. In addition to the heat exchanger, the air conditioner has an in-machine piping member and a kit material member (hereinafter, these are collectively referred to as refrigerant piping members), and these include an accumulator and a main piping. A copper tube, a copper wire, a copper plate, and the like, which are thermally insulated and vibration-proof by a resin such as rubber, urethane foam, or styrene foam, are also used.

In recent years, these used air conditioners (waste air conditioners) have been used as part of the recycling of automobiles and home electric appliances.
Recycling is also a social issue. In waste air conditioners, Al materials such as the Al fins account for about 10%, and copper materials such as the copper pipes account for about 20% .If these Al materials and copper materials can be recycled, It has a great social significance as resource saving. Further, by enabling the separation of the Al material and the copper material in the waste air conditioner, it becomes possible to separate other iron materials and the like, which has the significance of being recyclable.

However, in the case of recycling automobiles and home electric appliances, since these are composed of many different materials, it is difficult to treat them integrally or collectively as they are. In general, after sorting, each material is crushed and reused as a raw material for dissolving each material. Therefore, for example, when recycling only the heat exchanger in the waste air conditioner,
Since different metal materials of copper tube and Al fin are mixed, the copper tube and Al fin constituting the waste heat exchanger are first separated manually, separated and crushed, and then crushed. It is generally used as a raw material for dissolving each material.

However, the method of manually separating copper and Al from the waste heat exchanger is inefficient and cannot be a practical method corresponding to an increase in the amount of waste heat exchanger recycled.
On the other hand, if the waste heat exchanger can be crushed by a crusher or the like as it is, the processing efficiency can be increased in response to an increase in the amount of waste heat exchanger recycled.

However, conventionally, it has been recognized that it is difficult to separate the strongly joined copper tube and the Al fin by mechanically and thermally conductively by the expansion process, and the waste heat exchanger is crushed as it is. However, it has been common general technical knowledge so far that copper tubes and Al fins cannot be separated well.

[0008] For this reason, various proposals have been made to crush the copper tube and the Al fin beforehand, instead of crushing the waste heat exchanger as it is, in a state where the copper tube and the Al fin are easily separated.

For example, Japanese Patent Application Laid-Open No. 7-171723 discloses that high pressure water containing abrasive grains is injected into a waste heat exchanger to bring Al fin to an end of a copper pipe, and then the Al fin is cut. A method of separating by plastic deformation is disclosed. Further, Japanese Patent Application Laid-Open No. 7-265986 discloses that a copper tube is stretched in the longitudinal direction to reduce the diameter (outer diameter) of the copper tube, to break the strong joint with Al fin, and then to separate the two. Is disclosed. Therefore, these publications disclose separation methods having a lower treatment efficiency than the crushing method, and common technical knowledge that even if the waste heat exchanger is crushed as it is, separation of the copper tube and the Al fin cannot be achieved properly. Based on

Further, Japanese Patent Application Laid-Open Nos. 9-57144 and 9-57
No. 145, Japanese Patent Application Laid-Open No. 9-155213, and the like disclose that the outer periphery of a copper tube is expanded in a predetermined direction to break Al fins and then the waste heat exchanger is crushed. Japanese Patent Application Laid-Open No. 8-11022 discloses that the waste heat exchanger is rolled in advance and crushed, and then the waste heat exchanger is crushed. These are all based on the common technical knowledge that the copper tube and the Al fin cannot be separated properly unless the joint between the copper tube and the Al fin is destroyed beforehand.

However, these conventional methods for separating a copper tube and an Al fin in advance all require complicated processes.
The fact is that it has not been put to practical use yet.

[0012] On the other hand, a copper tube formed by these conventional separation methods is used.
Considering the difficulty of separation from Al fin, heat exchanger itself
A method of replacing the aluminum pipe and the aluminum fin with all-aluminum is also being considered. In this method, the heat exchanger itself is configured so that different metal materials of the copper tube and the Al fin are not mixed. Therefore, if it is this type of heat exchanger, there is no need to separate different metal materials of copper and aluminum, so use it as a waste heat exchanger or crush it appropriately and use it as a raw material for dissolving Al. Becomes possible.

However, it cannot be denied that the efficiency of the all-aluminum heat exchanger itself is significantly lower than that of the copper tube heat exchanger. In addition, this method does not solve the problem of recycling the heat exchanger including the copper tubes and the Al fins, which is actually used in large quantities at the present time.

[0014] For this reason, the present inventors have previously described Japanese Patent Application No.
-351101, in order to provide a recycling method for waste heat exchangers in which copper pipes and aluminum fins in waste air conditioners are joined, metals that become impurities when waste heat exchangers are used as melting materials After removal, the waste heat exchanger is crushed in a state where the copper tube and the Al fin are still joined, and crushed until Al flakes and copper flakes are separated and mixed to become mixed crushed pieces. It was proposed to separate and sort Al flakes and copper flakes from the mixed crushed pieces, and then to use these flakes as raw materials for dissolving Al and copper, respectively. According to this method, it is possible to provide a recycling method with high processing efficiency of the waste heat exchanger.

[0015]

[Problems to be Solved by the Invention]
The invention of No. 51101 is intended only for the heat exchangers in which copper pipes and Al fins are joined among the waste air conditioners, and the aluminum and copper materials used in the entire waste air conditioners are subject to recycling. Not in.

That is, as described above, the waste air conditioner is not limited to the heat exchanger of the above-mentioned Japanese Patent Application No. 10-351101, and may be made of rubber or urethane foam as a refrigerant piping member including an in-machine piping member. Copper materials, such as copper tubes insulated with resin, copper wires, and copper plates, are also often used. And, like the other iron, brass, brazing materials, etc., the resin coated on the copper material becomes foreign matter when the copper material used as the refrigerant piping member is used as a melting raw material, and is removed in advance. I need to do it.

However, the separation and removal of the resin coated on the copper material is a difficult technical problem as in the separation of the copper tube and the Al fin in the heat exchanger. For example, a resin-coated copper material is crushed into pieces by a crusher as it is.
(Subdivision), the resin is not well separated from the copper material,
Most of the copper flakes are still covered with the resin, and the copper flakes and the resin flakes are not separated mixed crushed pieces. For this reason, unlike the mixed crushed pieces, even if a known sorting method such as particle size sorting, wind sorting, or specific gravity sorting is adopted thereafter, the resin and the copper material cannot be separated well.

Therefore, the resin-coated copper material used as the refrigerant pipe member in the waste air conditioner has been manually crushed to separate the resin and then to crush the resin. Is the actual situation. For this reason, in order to recycle the entire waste air conditioner, the main members that constitute the waste air conditioner
In the rough decomposition process of iron and copper materials, oil and copper materials, brazing material and copper materials, etc. This is a major factor that hinders the efficiency and economics of recycling methods.

The present invention has been made in view of such circumstances, and has as its object to improve the efficiency by improving the separation between the resin-coated copper material and the resin, and to improve the efficiency of the entire waste air conditioner. It is intended to provide a recycling method with high processing efficiency.

[0020]

SUMMARY OF THE INVENTION In order to achieve this object, the gist of the method for recycling a waste air conditioner according to the present invention is a recycling method of separating aluminum and copper from the waste air conditioner and using them as respective melting raw materials. After removing foreign matter when used as a raw material for melting from the waste air conditioner, the heat exchanger in the waste air conditioner is passed through a crusher with the copper and aluminum materials still joined, Pieces and copper pieces are crushed until they become mixed crushed pieces which are separated and mixed, and aluminum and copper pieces are separated and separated from the mixed crushed pieces, respectively. The refrigerant pipe member including the pipe member is subjected to a crusher with the copper material and the resin material being bonded together, and crushed while being heated to the softening temperature of the resin piece, so that the copper fine piece and the resin piece are separated. Mixed breaks separated from each other Crushed into pieces, and separated and sorted copper flakes from the mixed crushed pieces, by using the aluminum flakes and copper flakes obtained by each of these sorts as raw materials for dissolving aluminum and copper. is there.

According to the present invention, a heat exchanger in which a copper tube and an Al fin of a waste air conditioner, which is the gist of the Japanese Patent Application No. 10-351101, is separated into an Al strip and a copper strip. In addition to crushing until mixed crushed pieces are obtained, the refrigerant pipe member in the waste air conditioner is subjected to a crusher with the copper material and the resin material still being joined and used for crushing. By crushing while raising the temperature to the softening temperature of the resin piece by energy or heating from the outside or inside of the crusher, the copper flakes and the resin pieces are crushed separately to form mixed crushed pieces separated and mixed.

This makes up the majority of the heat exchanger
Al material and copper material, and copper material and resin material occupying most of refrigerant piping members can be efficiently separated, and separated Al
Material and copper material for the original product (especially Al for heat exchanger fins)
It can be used as a raw material for dissolving an alloy material (for a phosphor deoxidized copper material for a copper tube of a heat exchanger) (corresponding to claim 8). As a result, a highly efficient recycling method for the entire waste air conditioner can be provided.

When the present inventors crush a refrigerant pipe member in a waste air conditioner by a conventional crusher or a mill while the copper material and the resin material are still joined to each other,
By crushing while raising the temperature to the softening temperature of the resin piece, the resin coated on the copper material is softened and easily peeled off, the copper material and the resin material are separated from each other as fine pieces, and the copper fine pieces are separated. And the resin pieces were separated into mixed crushed pieces.

After the mixed crushed pieces are separated and mixed with each other, the mixed crushed pieces are separated by known sorting means such as wind force and specific gravity into copper flakes. The fine pieces and other crushed pieces (impurities) such as resin can be easily separated, and the separated and sorted copper fine pieces can be used as a raw material for melting copper.

Also, when the heat exchanger in the waste air conditioner is crushed by a crusher in a state where the copper tube and the Al fin are still joined by a normal crusher or a mill, if they are sufficiently finely crushed, Contrary to the common technical knowledge, Al which was fin and copper which was a copper tube were separated from each other as strips,
A mixed crushed piece in which fine pieces and copper fine pieces are separated and mixed is obtained. In other words, if crushed sufficiently finely, the Al and copper flakes remain separated from each other without being joined to each other, as in the state of the original waste heat exchanger, and then mixed. Separation and sorting of Al flakes and copper flakes from crushed pieces can be performed easily and easily.

After the Al strips and the copper strips are separated and sorted in this way, each of the Al strips is separated from the original Al fin, such as a pure aluminum series such as 1100 or an Al alloy series such as 3000 series. Copper material such as phosphorus deoxidized copper for copper pipes used as a raw material for dissolving Al material (Al wrought material)
Can be used as raw materials for dissolution (corresponding to claim 9).

[0027]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The significance of each requirement in the present invention will be described below.

(Foreign matter removal process) From each part of the waste air conditioner,
When obtaining raw materials for dissolution of Al and copper materials, iron (including steel), brass, brazing material, and waste air conditioners (copper (In the jurisdiction)
If the oil and refrigerant gas contained in the aluminum are mixed into the Al material and the copper material after the separation and separation, they become foreign materials as a raw material for melting, lowering the quality of the molten metal, and casting the Al material and the copper material (cast material). And subsequent wrought materials) lose quality and commercial value. In addition, there is also a problem that the process of melting the Al material and the copper material itself becomes difficult, such as smoke and generated gas.

Therefore, except for the exceptional case where these foreign matters contain only a trace amount of the Al material and the copper material after the separation and separation that do not cause the above-mentioned problem even if mixed in the raw material for melting,
Alternatively, depending on the amount of these foreign substances contained in the Al material and the copper material after the separation, the main members constituting the waste air conditioner (iron material and copper material, oil and copper material, brazing material and copper material, etc.) In the coarse decomposition process, these foreign substances are included, including when all are removed.
It is necessary to remove selectively (corresponding to claim 3)
.

More specifically, the iron (Fe) component coming from the iron material used as the panel material, the support plate, and the fastening material of the waste air conditioner is an impurity in the AA or JIS alloy standard of the Al material or the copper material. If it is contained too much, it deviates from the alloy standard of molten aluminum or molten copper, and impairs the basic characteristics of cast aluminum and copper. In addition, in the Al melting and refining process, it is basically difficult to remove the iron that has been mixed in a large amount from the molten Al because there is no effective removing means (melt refining means) as described later. It is necessary only to dilute with an inexpensive Al ingot, and there is a possibility that the significance of the recycling itself, which is the object of the present invention, may be lost. However, as mentioned above, up to the upper limit of the alloy specification of the target recycled Al material or copper material is allowed, so whether or not to remove the contamination source according to the standard and the degree of removal (amount)
Select

Further, since brass (brass) coming from brass screws used also in waste air conditioners has zinc (Zn) of 30 to 40 since it has higher strength than copper screws and has good workability such as cutting.
%, And if the content is increased, it deviates from the AA or JIS alloy standards of molten aluminum and molten copper, and impairs the basic characteristics of cast aluminum and copper. However, as mentioned above, up to the upper limit value of the alloy standard of the target recycled Al material or copper material is allowed, so depending on the standard, whether or not to remove the mixing source such as brass screw, and the degree of removal (amount) Select

Further, when the amount of lead (Pb), tin (Sn) or phosphorus (P) coming from the solder used as the brazing filler metal is increased, the AA or JIS alloy of molten aluminum or molten copper may be used. As well as deviating from the standard, it hinders the basic properties of cast Al and copper materials. Moreover, in the Al melting and refining process, the removal of lead, tin, and phosphorus, which have been mixed in a large amount, from the molten Al is basically performed because there is no effective removing means (melt refining means) as described later. difficult. However, as described above, up to the upper limit value of the alloy specification of the target recycled Al material or copper material is allowed, so according to the standard, remove the brazing material or the U-bend portion of the copper pipe with a large amount of the brazing material adhesion. Whether or not
Select the degree (amount) to be removed. The U-bend portion of this copper tube is separated from the copper tube, etc., so that it can be used as a brass brazing filler metal when it contains a lot of phosphorus, and a brass brazing filler metal when it contains a lot of lead and tin. There is also an advantage that the brazing material can be separately recycled.

In addition, if the amount of oil such as refrigerant oil or gas such as chlorofluorocarbon in the copper pipe becomes large, it contaminates the molten aluminum or the molten copper, and the basic characteristics of the cast Al and copper materials. Also inhibit.
In addition, there is a problem that the process of dissolving the Al material and the copper material itself becomes difficult, such as generation of smoke and combustion gas. Further, the oil component may include a metal component as an impurity, and easily contaminates the molten aluminum or the molten copper. However, since there is an allowable range of the mixing amount, the U bend portion or the like of the copper pipe is removed or cut in accordance with the extent that the above problem does not occur, and whether or not to remove these is determined. select.

When the waste heat exchanger or the like does not substantially contain the above-mentioned steel members and oil components other than the main components of the copper tube and aluminum fin, the waste heat exchanger is crushed by a crusher as it is. Can be.

(Crushing step) For crushing, a normal crusher or crusher can be used as appropriate, but there are also features of each member.
As described below, in consideration of obtaining each separation strip, the heat exchanger in the waste air conditioner is a crusher by cutting or shearing such as a cutter mill, and a refrigerant piping member including an in-machine piping member is: The crushing is preferably performed by an impact crusher such as a ring hammer crusher.

What is important in this crushing process is that, in the refrigerant pipe member, heat is applied when the aluminum fins are joined to the copper tube until the copper flakes and the resin flakes are separated and mixed into mixed crushed flakes. In the exchanger, it is to crush finely until the crushed Al flakes and copper flakes are separated and mixed. That is, in the copper strip of the refrigerant piping member, the copper material and the resin strip, and in the Al strip of the heat exchanger, Al and copper are partially bonded or adhered to each other, and crushed strips (state) are partially formed. If these are also left, the subsequent separation and separation of copper flakes and Al flakes from the mixed crushed pieces will be difficult or very inefficient.

As described above, when the refrigerant pipe member in the waste air conditioner is crushed by a crusher in a state where the copper material and the resin material are joined, the temperature rises to the softening temperature of the resin pieces. It is important to crush while heating. The resin piece referred to here is a resin material such as rubber, urethane foam, styrene foam, or the like that is bonded to a copper pipe of a refrigerant pipe member for heat insulation and vibration proof, or by bonding these resin materials to a copper pipe or the like. Adhesive such as resin or rubber glue. Resins such as urethane foam and styrofoam usually used in waste air conditioners soften at a temperature of about 60 to 80 ° C, so select a temperature of about 100 ° C due to frictional heat during crushing. If it is heated, the resin coated on the copper material softens and becomes easy to peel off, the copper material and the resin material are separated from each other as strips, and the copper strip and the resin strip are separated from each other. It becomes mixed crushed fragments. Further, although rubber and the like also have a higher softening temperature than ordinary resins, when they are crushed at the softening temperature of the resin, they are easily peeled from a copper tube or the like. However, the heating temperature
If the temperature exceeds 200 to 300 ° C., the resin may ignite. Therefore, it is preferable that the temperature for raising the temperature during crushing is suppressed to the ignition temperature or less. For this reason, the crushing energy (optimum crushing condition) for raising the temperature is selected depending on the model and type of the crusher, and if the crushing energy is insufficient for raising the temperature, the crushed And means for cooling by a coolant such as water that suppresses temperature rise.

Furthermore, when the heat exchanger is crushed using an impact crusher or a twin-shaft crusher, the crushing force is large, but at the time of crushing, the Al fins rub the copper tube surface, and Al fin residues may adhere and remain. This adhering Al residue can be mixed into the raw material for dissolving copper material, increasing the amount of Al as an impurity in the molten copper, deviating from the alloy specifications of the copper material, and obstructing the basic characteristics of the cast copper material There is. For this reason, when crushing a heat exchanger in which an Al fin is joined to a copper tube, it is preferable to use a shear-type vertical crusher or a cutter-type cutter mill so that the Al fin does not rub the copper tube surface.

In the case of a copper strip, the above-mentioned Al
When the adhesion of foreign substances such as is inevitable, the surface of the copper strip after crushing or during or after sorting to be described later is washed with a washing liquid using an acid, an alkali, a commercially available detergent or the like alone or in combination. Preferably, it is removed (corresponding to claim 4). At this time, in order to simultaneously remove dirt such as oil in addition to Al, it is particularly preferable to use a high-temperature (50 to 100 ° C.) cleaning solution and also to perform the cleaning solution with an alkaline aqueous solution such as NaOH. .

(Sorting Step) After the copper flakes and the resin flakes or the Al flakes and the copper flakes are separated and mixed into mixed crushed pieces, the mixed crushed pieces are It is possible to easily sort by known sorting means such as wind force, specific gravity, magnetic force, etc., and each separated and sorted Al strip or copper strip is used as a raw material for dissolving the original Al fin or copper tube. be able to. Among these, wind separation and / or magnetic separation are preferable in terms of simplicity and separation efficiency (corresponding to claim 2).

(Solution Step) The Al strip and the copper strip thus separated and separated from the Al strip are made of pure aluminum such as 11001200 or 1M30, or 3000 series, respectively.
Original aluminum material for Al fins, such as Al materials for Al fins and other Al alloy wrought materials, and phosphorus stripped copper for copper tubing and other copper alloys for copper strips As a raw material for dissolving copper, such as for a system-extended material, each recycled strip is used as a part or all of the raw material for melting and refining of Al and copper, and a refining process and a casting process are used to perform rolling and extrusion. Recycled as standard copper and Al for drawing. In addition, using each recycled strip as a part of the melting raw material means that it can be used together with copper or Al ingots or other copper or Al scrap materials as long as it does not violate the significance of recycling. Meaning. In addition, when Al flakes and copper flakes are directly introduced into the melting furnace for the melting raw material, depending on the furnace conditions,
Due to the small pieces, they are easily oxidized and disappear, and the yield may be reduced. In such a case, the Al strip or the copper strip,
For example, it is preferable to use a lump having an appropriate density by using a press or the like to increase the size and then use the lump as a material for melting.

The Al flakes and copper flakes for the melting raw material are removed into the iron, brass, brazing material and waste air conditioner, which can become foreign materials as a raw material for melting by the above-described foreign matter removal process of the waste air conditioner. The contained oil and refrigerant gas are selectively removed. However, actually, even if these foreign substances are removed,
It is impossible to completely remove them, and these foreign substances inevitably enter. In addition, some of the copper and Al materials to be melt-recycled according to the present invention include high-grade materials that require relatively low impurity purity, such as applications in the electronic field. Even if there are few, it is necessary to further reduce these foreign substances (impurities).

For this reason, when the foreign material is contained or remains in the molten raw material so as to substantially contaminate the molten metal of Al and copper, in the case of copper, the refining of the molten metal and / or recycling of the ingot is carried out for the purpose of recycling. These foreign substances are removed or the concentration is reduced by adding and diluting them to the extent that they do not conflict, or, in the case of Al, by adding and diluting a base metal.

The refining of molten copper in the case of copper will be described below. First, impurities such as iron, tin, zinc, Al, and phosphorus (P) contained in the molten copper have a greater tendency to oxidize than copper. It can be removed by removing the slag in the form of an object (slag, slag) (corresponding to claim 6). The method of oxidizing molten copper is
Dissolve the raw copper material in the air atmosphere, or add or blow an oxidizing agent such as silicic acid, borax, or boric acid into the molten copper, or blow or blow oxygen or air into the melting furnace. When transferring water from a holding furnace, a holding furnace to a mold, etc.
Means such as adding a head to entangle the atmosphere and blowing a flame to the molten metal by a burner or the like are appropriately selected. Among them, the method of dissolving the copper material in the air atmosphere is the simplest and most efficient method (corresponding to claim 7).

However, when performing this oxidation treatment, in order to remove the impurities by converting them into oxides,
The oxygen concentration in the molten copper needs to be as high as 300 to 30000 ppm, for example. On the other hand, in terms of quality,
It is necessary to reduce the oxygen concentration to 100 ppm or less, and thus a reduction treatment of the molten copper is required following the oxidation treatment. This reduction treatment makes the melting atmosphere in the melting furnace reducible, throws a (solid carbon source) reducing agent such as CO gas or raw pine into the molten copper or the surface of the molten copper in the melting furnace,
When the molten copper is transferred from the melting furnace to the holding furnace or from the holding furnace to a mold or the like, a means such as using the reducing agent in a hot water trough is appropriately selected. After the refining process, copper casting is performed in the mold.

[0046]

Next, an embodiment of the method of the present invention will be described. A plastic or steel frame was removed from a plurality of waste air conditioners of the same type, and a heat exchanger and a refrigerant piping member including an in-machine piping member and a kit member were separated. Furthermore, as shown in Table 1, the heat exchanger block and the refrigerant pipe member group from A to F, which were removed under different conditions, from the heat exchanger and the refrigerant pipe member when using as a raw material for dissolution, as shown in Table 1. Each was prepared separately. The removal of foreign matter was carried out by removing iron frame materials, support plates, fasteners, etc. for iron materials, brass screws etc. for brass materials, and U-bend portions of copper pipes for brazing material, oil and refrigerant gas. Was. Those marked with a cross in the foreign matter removal shown in Table 1 are those in which foreign matters were selectively removed by intentionally leaving some of these components.

The heat exchanger is crushed into small pieces having an average length of 5 cm or less by a cutter mill (Kinki Kogyo Co., Ltd., type V-1500), and the refrigerant piping member is a vertical ring hammer crusher. (Fujisha Co., Ltd., type FMS-1200) each crushed and crushed into strips with an average length of 10 cm or less, the heat exchanger is a separation of copper pipe and Al fin, the refrigerant pipe member is copper material And resin were separated. At this time, when crushing the refrigerant pipe member, as shown in the crushing conditions in Table 1, the temperature raising conditions during crushing were changed, and the temperature was raised to about 100 ° C in the case where the temperature was raised, and water-cooled in the case where the temperature was not raised. While crushing.

Table 1 also shows the separated state of copper and Al of the mixed crushed pieces of the heat exchanger and the separated state of copper material and resin of the mixed crushed pieces of the refrigerant pipe member. Among the mixed crushed pieces of the heat exchanger shown in Table 1, those having a good separation state indicate a state in which the mixed pieces are separated and mixed with Al flakes and copper flakes. Further, the partial bonding indicates a state in which crushed pieces in a state where Al and copper are still bonded are partially mixed in the mixed crushed pieces. Furthermore, in the mixed crushed pieces of the refrigerant pipe member in Table 1,
In the case of good separation, resin strips and copper strips are separated and mixed (resin strips are separated and mixed as resin blocks)
This shows a state of being mixed crushed pieces. In addition, the partial adhesion indicates a state in which crushed pieces in a state where the resin remains attached to the copper are partially mixed in the mixed crushed pieces.

Thereafter, the mixed and crushed pieces of the heat exchanger and the mixed and crushed pieces of the refrigerant pipe member were respectively subjected to a wind separator and a magnetic separator to separate Al and copper pieces from each of the mixed and crushed pieces. Sorted out.

The separated separated Al flakes were subjected to smelting test in a batch furnace by atmospheric melting in a batch furnace, using only these flakes as raw materials for melting, and using a 1100 Al alloy as a material for Al fin of a heat exchanger. . Table 2 shows the analysis results of the chemical components of the smelted Al alloy.

Further, the mixed crushed pieces of the heat exchanger and the mixed crushed pieces of the refrigerant pipe member are combined, and only these pieces are used as a raw material for dissolution, and the phosphorus deoxidation for the copper pipe of the heat exchanger is performed. Copper was melt tested in a batch furnace. Table 3 shows the copper dissolution conditions.
As shown in the figure, pretreatment of alkaline washing of strips (10% NaOH,
(80 ° C. aqueous solution × 5 minutes), and various conditions of the oxidation treatment and the reduction treatment at the time of dissolution were changed. When the oxidation treatment is performed in the atmosphere, the oxygen concentration in the molten metal is adjusted to 10,000 ppm, and iron, tin, lead, zinc, Al, and the like in the molten metal are oxidized.
A treatment for removing the slag of the generated oxide was performed. Also,
In the reduction treatment, CO gas was blown into the molten metal in a melting furnace or a hot water gutter, and a reducing agent for raw pine was injected into the surface of the molten metal. The analysis results of the chemical components of this melted phosphorus deoxidized copper are shown.
Figure 4 shows.

First, as shown in Tables 1 and 2, foreign matters (iron, brass, brazing material) were removed from the heat exchanger (Nos. A and B in Table 1). Mixed crushed pieces are mixed crushed pieces in which Al flakes and copper flakes are separately separated and mixed, and invention examples 1 and 2 in which the separation state is good are 11
Satisfies the component specification as a 00Al alloy. Therefore, this Inventive Example 1 requires 3003,
It also shows that it can be used (recycled) as various Al alloys by adding alloy elements, such as being able to be used as an Al alloy for Al fins of heat exchangers such as 3004. However, Invention Example 2 in which the foreign matter oil was not removed
The S content from the residual oil content is higher than that of Invention Example 1,
Smoke was generated at the time of melting, and the melting operation was difficult.

On the other hand, whether any of the foreign substances (iron, brass, brazing material) should be removed from the heat exchanger (see the numbers in Table 1)
C to E), even if foreign matter is removed, the mixed crushed pieces of the heat exchanger
The flakes and the copper flakes are not mixed crushed pieces separated from each other (No.F in Table 1) .Comparative Examples 3 to 6 show Fe, Cu, Zn, etc. derived from each foreign substance or copper tube. Is higher, 1100
It is out of component standard for Al alloy. Therefore, the only way to reduce the amounts of these elements to be within the standards is to dilute them by using a large amount of expensive Al metal. However, such a method increases the melting cost, and the significance of recycling itself is impaired.

Next, as shown in Table 1, foreign matter (iron, brass, copper) was removed from the heat exchanger and the refrigerant piping member.
(Brazing material, oil, gas), and the mixed crushed pieces of the heat exchanger are mixed crushed pieces in which the resin flakes and copper flakes are separated and mixed. Copper strip
(No.A in Table 1) is as shown in Table 3 by carrying out alkali washing for removal of Al and oil, oxidizing treatment during dissolution, and reducing treatment, and as in Invention Examples 1 to 3 shown in Table 4. Satisfies the component standard as phosphorous deoxidized copper. Therefore, Examples 1 to 3 of the present invention can be used as they are as dephosphorized copper for copper tubes of heat exchangers. It also shows that it can be used (recycled) as various copper alloys by adding alloying elements.

On the other hand, as shown in Comparative Example 4 in Table 3, foreign matter (iron, brass, brazing material,
(Oil and gas components) and the resin was separated as shown in Table 1.
Even if the copper strip of A is used, and even if the alkali cleaning is further performed, the oxidation treatment at the time of dissolution, without performing the reduction treatment, when dissolved in an inert gas atmosphere, even by the foreign matter removal Fe, Pb, inevitably mixed without being removed
Ni, Sn, Zn, etc. are high, which deviates from the component specification as phosphorus deoxidized copper. If the amount of impurities that are inevitably mixed is small, there is a possibility that the content will be within the component standard, so it is not possible to say unconditionally, but as the preferred conditions for dissolving copper in the present invention, oxidation treatment and This shows the effectiveness of the reduction process.

Even when the copper strip A in Table 1 was used, among the inventive examples 1, 2, 3, and 5, the inventive example 5 in which alkali washing was not performed had a relatively high amount of Al. Yes,
In Invention Example 3 in which the reduction treatment was not performed, the amount of oxygen was relatively high. The results show the effectiveness of alkali washing and reduction treatment as preferred conditions for dissolving copper in the present invention.

Further, foreign matter from the heat exchanger and the refrigerant piping member
(Iron, brass, brazing)
(Nos.B to E in Table 1), even after removal, the mixed crushed pieces of the refrigerant pipe member are not mixed crushed pieces in which the resin pieces and the copper pieces are separated and mixed (No.F in Table 1). In Comparative Examples 6 to 10 using the same, even when alkali washing, oxidation treatment and reduction treatment were respectively performed as preferred conditions for dissolving copper in the present invention, they were derived from each foreign matter and Al fins. Fe,
Pb, Ni, Sn, Zn, etc. are high, the purity of Cu is low,
JIS with Cu purity of 99.90% or more (P is 0.015 to 0.040%)
Phosphorus deoxidized copper Deviates from 1B class component standard. Therefore, the only way to reduce the amounts of these elements to be within the standards is to dilute them with expensive Cu metal. However, such a method increases the melting cost, and the significance of recycling itself is impaired. In Comparative Example 10, the mixed crushed pieces were not mixed crushed pieces in which the resin pieces and the copper flakes were separately separated and mixed (No.F in Table 1). Smoke increased during the dissolution test operation, and the dissolution operation itself was stopped halfway.

Thus, the above results support the critical significance of the requirements of the present invention and the effectiveness of the preferred conditions.

[0059]

[Table 1]

[0060]

[Table 2]

[0061]

[Table 3]

[0062]

[Table 4]

[0063]

As described above, according to the recycling method of the present invention, the efficiency of separating the resin-coated copper material from the resin can be improved, and the Al material and the copper material in the waste air conditioner can be efficiently separated. By enabling separation, it is also possible to separate other iron materials and the like, and it is possible to provide a recycling method with high processing efficiency of the entire waste air conditioner. Therefore, it has great social and industrial value in enabling recycling of the entire waste air conditioner used in large quantities throughout society.

 ──────────────────────────────────────────────────の Continued on the front page (72) Mamoru Ishikawa 65, Hirasawa, Hadano-shi, Kanagawa Prefecture Inside Hadano Plant, Kobe Steel Co., Ltd. (72) Inventor Saeki Main Tax 65 Hirasawa, Hadano-shi, Kanagawa F-term in Hadano Plant, Kobe Steel Co., Ltd.F-term (reference) EA13 HA12 JA02 JA10

Claims (8)

[Claims] 1. A recycling method in which aluminum and copper are separated from a waste air conditioner to be used as respective melting raw materials, wherein foreign matter used as a melting material from the waste air conditioner is removed in advance, and then the waste air conditioner is separated from the waste air conditioner. The heat exchanger is subjected to a crusher in a state where the copper material and the aluminum material are still joined, and crushed until the aluminum flakes and the copper flakes are separated and mixed into mixed crushed pieces. While aluminum and copper strips are separated and separated from the mixed crushed pieces, the refrigerant pipe members including the in-machine pipe members of the waste air conditioner are crushed in a state where the copper material and the resin material are still joined. By crushing while raising the temperature to the softening temperature of the resin pieces, the copper fine pieces and the resin pieces are crushed until they become separated mixed crushed pieces, and the copper fine pieces are separated from the mixed crushed pieces. Separation and sorting A method for recycling a waste air conditioner, wherein the obtained aluminum strip and copper strip are used as raw materials for dissolving each of aluminum and copper. 2. The method according to claim 1, wherein the separation and sorting are performed by wind sorting and / or magnetic sorting. 3. The recycling method of a waste air conditioner according to claim 1, wherein the foreign matter when used as the raw material for melting is selected from oil, refrigerant gas, iron material, brass material and brazing material. . 4. The waste air conditioner according to claim 1, wherein the separated and sorted copper strip is used as a raw material for dissolving copper after cleaning and removing foreign substances adhering to the surface. Recycling method. 5. When the copper strip after the separation and sorting is used as a raw material for dissolving copper, oxidation treatment of the molten copper is performed to oxidize and remove metal impurities contained in the molten copper. The recycling method of a waste air conditioner according to any one of the above. 6. The recycling method of a waste air conditioner according to claim 5, wherein the oxidation treatment is performed by dissolving the copper strip in an air atmosphere. 7. The method according to claim 5, wherein the molten copper after the oxidation treatment is reduced to reduce oxygen contained in the molten copper. 8. The aluminum strip is used as a raw material for dissolving aluminum material for heat exchanger fins, and the copper strip is used as a raw material for dissolving phosphorus deoxidized copper for heat exchanger copper tubes. The method for recycling a waste air conditioner according to any one of claims 1 to 7.