Patent ID: 12186786

DESCRIPTION OF EMBODIMENTS

Specific Description

A treating method according to the present invention is a method for treating waste printed circuit board including carbonizing waste printed circuit board together with a calcium compound at 400° C. to 600° C. in a non-oxidizing atmosphere to fix a halogen contained in the board as calcium halide to melt a solder of the board to allow mounted parts to be easily separated from the board, performing crushing after the carbonizing to obtain crushed materials, sieving the crushed materials into fine particles of less than 0.5 mm containing the calcium compounds, medium particles containing the mounted parts, and coarse particles containing board pieces such that the crushed materials are sorted into the calcium compounds, the mounted parts, and the board pieces.

“Crushing” (disintegrate) refers to an operation in which mechanical energy is applied to a solid (aggregate) in which various materials are composited to break the bond between the materials. Crushing differs from “pulverizing” in which the size of each material is reduced while a new surface of the solid is generated in that crushing involves almost no generation of a new surface of the solid.

By carbonizing the waste printed circuit board under the above conditions and then appropriately crushing the waste printed circuit board, a group of the crushed materials having a size depending on the material can be obtained.

“Containing a calcium compound” means that the particles after crushing contain 30% by mass or more of calcium.

An outline of the treating method according to the present invention is shown inFIG.1.

In the treating method according to the present invention, the waste printed circuit board is carbonized together with a calcium compound at 400° C. to 600° C. in the non-oxidizing atmosphere, a halogen contained in the board are fixed as calcium halide, and the solder of the board melts to allow the mounted parts (electronic components or the like) to be easily separated from the board.

As the calcium compound, slaked lime, quick lime, calcium carbonate, or the like can be used. This calcium compound acts as a halogen fixing agent and reacts with a halogen gas, such as a bromine gas or a chlorine gas, generated by carbonizing the board to generate calcium halide such as calcium bromide (CaBr2), calcium chloride (CaCl2)), or calcium chloride hydroxide (CaClOH) to fix the halogens.

An addition amount of the calcium compounds is preferably 1:0.05 or more, more preferably 1:0.5 or more in terms of weight ratio with respect to the board. In a case in which the addition amount of the calcium compounds is 1:0.5 or more with respect to the weight of the board, a Br removal rate of 80% or more can be obtained.

Although not particularly limited, the upper limit value of the addition amount of the calcium compounds is preferably 1:1.5 or less in terms of weight ratio from the viewpoint of economy.

The non-oxidizing atmosphere is, for example, a nitrogen atmosphere, a carbon dioxide gas atmosphere, or a superheated steam atmosphere. In a case in which combustion is performed in an oxidizing atmosphere such as an atmospheric air, a metal of the mounted parts and a metal such as aluminum and copper contained in the board are oxidized, so that the metal cannot be recovered as it is.

A carbonization temperature is preferably 400° C. to 600° C. At the temperature lower than 400° C., the solder that fixes the mounted parts to the board does not completely melt, which makes it difficult to separate the mounted parts from the board. In addition, an epoxy resin used for the board portion of the electronic board is not sufficiently decomposed, which makes it difficult to perform crushing of the subsequent stage. On the other hand, in a case in which the carbonization temperature is higher than 600° C., there is a concern that the temperature of the treated material exceeds a melting point (660° C.) of aluminum, and in that case, aluminum contained in the mounted parts melts, and the board and the mounted part are melt, which makes it difficult to separate the mounted parts from the board. By performing carbonization in the above temperature range, the solder that fixes the mounted parts to the board can melt to allow the mounted parts to be separated from the board and easily sorted, and the combustibles such as a resin component of the board can be thermally decomposed.

Although not particularly limited, the carbonization temperature is more preferably 450° C. to 580° C., and still more preferably 500° C. to 550° C.

As a carbonization device, for example, a heating device that can maintain the inside of the furnace, such as an externally heated rotary kiln, a stationary furnace, or a fluidized bed furnace, in the non-oxidizing atmosphere may be used. Further, a combustible gas generated during carbonizing has a very low halogen concentration, and thus it can be used as it is as a fuel gas. For example, the heat generated in a case in which the gas generated in the carbonization treatment is combusted can be used as a heating source of the carbonization device, and thus the heat energy required for the carbonization treatment can be supplied by self-combustion.

The waste printed circuit board is crushed after the carbonizing to obtain the crushed materials, and the crushed materials are sieved into the fine particles of less than 0.5 mm containing the calcium compounds, the medium particles containing the mounted parts, and the coarse particles containing board pieces such that the crushed materials are sorted into the calcium compounds, the mounted parts, and the board pieces. Specifically, for example, the crushed materials are sieved into the fine particles of less than 0.5 mm, the medium particles of 0.5 mm or more and 50 mm or less, and the coarse particles of more than 50 mm such that the crushed materials are sorted into the calcium compounds contained in the fine particles, the mounted parts contained in the medium particles, and the board pieces contained in the coarse particles. Since the calcium compounds are the fine particles having a size of less than 0.5 mm, the calcium compounds can be sorted by crushing to a size of less than 0.5 mm.

As for the ranges of the medium particles and the coarse particles, the particle size range for crushing need only be determined depending on the size of the board or the mounted part. For example, as for the board having the mounted parts having a typical size, in a case in which it is sieved into the medium particles of 0.5 mm or more and 50 mm or less and the coarse particles of more than 50 mm, the mounted parts contained in the medium particles and the board pieces contained in the coarse particles can be sorted.

The carbonized material generated by the carbonization treatment is brittle due to the carbonized resin of the board, and the mounted parts are also separated from the board, so that it can be easily crushed by applying vibration. Since the crushed materials are divided into sizes depending on its main components, and sieved into, for example, the fine particles of less than 0.5 mm, the medium particles of 0.5 mm or more and 50 mm or less, and the coarse particles of more than 50 mm by using a vibrating sieve or the like.

The calcium halide generated by carbonization and the unreacted calcium compound added during carbonizing are mainly fine grains of less than 0.5 mm, while the mounted parts separated from the board are mainly the medium particles of 0.5 mm or more and 50 mm or less, and the board pieces are the coarse particles of more than 50 mm. Therefore, by sieving the crushed materials into the fine particles of less than 0.5 mm, the medium particles of 0.5 mm or more and 50 mm or less, and the coarse particles of more than 50 mm, the crushed materials can be sorted into the calcium compounds, the mounted parts, and the board pieces.

The SUS-based material and the aluminum-based material can be sorted by physically sorting the sieved and recovered mounted parts by any one of sorting methods such as magnetic force sorting, eddy current sorting, and color sorting or a combination thereof. Since SUS and aluminum adversely affect the copper refining process, by sorting and removing the SUS-based material and the aluminum-based material, the crushed materials after the carbonizing can be used as a copper feed. Specifically, for example, since a copper plate, a copper circuit, or the like is embedded in the board, crushed pieces of the board can be used as the copper raw materials. Further, since the copper circuit or the like is incorporated in the electronic components of the mounted parts, the crushed pieces of the mounted parts can be used as the copper feed by sorting and removing the SUS-based material and the aluminum-based material.

In the specification of the present application, the SUS-based material (stainless steel-containing material) and the aluminum-based material (aluminum-containing material) are particles having a certain composition among the particles (coarse particles, medium particles, and fine particles) of different sizes which are obtained as the crushed materials.

The SUS-based material contains 50% by mass or more of iron and 10% by mass or more of chromium with respect to the total metal elements contained in the particles.

The aluminum-based material contains 60% by mass or more of aluminum with respect to the total metal elements contained in the particles.

Among the calcium compounds sieved and recovered, the components that react with the halogens are water-soluble, and thus the halogens can be removed from the calcium compounds by washing with water. The halogen-removed calcium compounds can be reused as a calcium compound at the time of carbonization, and can also be used as the copper feed.

EXAMPLES

Hereinafter, examples of the present invention and comparative examples will be described together.

The concentrations of copper, iron, and aluminum contained in the recovered material were measured by using ICP-AES after dissolving the recovered material in aqua regia. The Br concentration inside a water trap solution and a washing solution of the powder in the subsequent stage of the rotary kiln was measured by using ion chromatography (IC), and the Br concentration remaining in the powder after washing was measured by using XRF. Based on these Br concentrations, the bromine removal rate (%) was determined by the following expression (1). The Fe recovery rate of the SUS feed was determined by the following expression (2). The Al recovery rate of the Al feed was determined by the following expression (3). The weight reduction rate (%) was determined by the following expression (4).
[Br removal rate (%)]=[amount of Br in washing solution of Ca compound]/[total amount of Br in electronic board]×100  (1)
[Fe recovery rate (%)]=[amount of Fe in recovered SUS feed]/[total amount of Fe in electronic board]×100  (2)
[Al recovery rate (%)]=[amount of Al in recovered Al feed]/[total amount of Al in electronic board]×100  (3)
[weight reduction rate (%)]=[reduction amount of weight of electronic board after treatment]/[weight of electronic board before treatment]×100  (4)

Example 1

The slaked lime was added to one (257 g) waste printed circuit board (waste printed circuit board) such that a weight ratio of the waste printed circuit board and the slaked lime was 1:1, and the waste printed circuit board with the slaked lime was put in the electronic externally heated rotary kiln and heated to 600° C. for 1 hour in the nitrogen atmosphere and to be subjected to the carbonization treatment. The combustible gas containing HBr generated during the carbonization treatment was treated in a secondary combustion furnace at 800° C. after trapping Br with a water trap in the subsequent stage of the kiln. After the carbonization, it was confirmed that the inside of the rotary kiln was cooled to 60° C. or lower, and the carbonized treated material was extracted.

The obtained treated material was input in the vibrating sieve having a two-stage sieve having a sieve mesh of 50 mm and 0.5 mm, and the board piece on a 50 mm sieve, the mounted part on a 0.5 mm sieve, and the powder under a 0.5 mm sieve were obtained.

The mounted part on a 0.5 mm sieve was recovered, the magnetized material was sorted by magnetic force sorting using a magnet having a magnetic flux density of 2000 G, and a white metal was further sorted by color sorting. The material from which the magnetized material and the white metal were removed was recovered as a sorted mounted part.

The powder under a 0.5 mm sieve was stirred and washed for 30 minutes by adding pure water having a weight 10 times the weight of the powder, the washing solution was filtered, and then the same amount of pure water was added to perform cake washing. The powder after washing was dried at 105° C. for 24 hours and recovered.

The board piece on a 50 mm sieve was defined as a recovered material A, the magnetized material was defined as a recovered material B, the white metal for color sorting was defined as a recovered material C, the sorted mounted part other than the recovered material B and the recovered material C was defined as a recovered material D, and the powder after washing and drying was defined as a recovered material E. After acid-dissolving each of these recovered materials A to E, the Cu concentration, the Fe concentration, and the Al concentration were measured by using ICP-AES, and the recovery rate and grade of each element were obtained. The obtained results are shown in Table 1. In Table 1, the copper feed is the recovered material A, the recovered material D, and the recovered material E, the SUS feed is the recovered material B, and the Al feed is the recovered material C.

Examples 2 to 7

The weight reduction rate, the recovery rate, the grade, and the Br removal rate were obtained in the same manner as in Example 1 except that the carbonization temperature, the atmosphere, and the addition amount of the slaked limes (board: slaked lime weight ratio) were changed as shown in Table 1. The obtained results are shown in Table 1.

Comparative Examples 1 to 3

The weight reduction rate, the recovery rate, the grade, and the Br removal rate were obtained in the same manner as in Example 1 except that the carbonization temperature, the atmosphere, and the addition amount of the slaked limes (board: slaked lime weight ratio) were changed as shown in Table 1. The obtained results are shown in Table 1.

Comparative Example 4

5 kg of the waste printed circuit board was put into a continuous rotary kiln and heated to 1200° C. for 1 hour in an air atmosphere to be subjected to the melting treatment. The melt of the electronic board after the melting treatment was allowed to flow into water from the outlet portion of the kiln and rapidly cooled. The treated material after cooling was dried at 105° C. for 24 hours to obtain a recovered material F. The recovered material F was finely pulverized by using a hammer crusher, then acid-dissolved, and the Cu concentration, the Fe concentration, and the Al concentration were measured, respectively, by using ICP-AES and the recovery rate and the grade of Cu were obtained. The obtained results are shown in Table 1.

The Fe grade and the Al grade of the copper feed of Examples 1 to 7 are both 0.9% or less, most of which are 0.5% or less, and the copper feed containing less iron and aluminum can be obtained. On the other hand, the Fe recovery rate of the SUS feed is 90% or more, the Al recovery rate of the Al feed is almost 90% or more, and a high recovery rate can be obtained for iron and aluminum.

Further, as shown in Examples 1 to 3, in a case in which the carbonization temperature is high, the solder melts sufficiently and the mounted parts are easily separated, the sorting efficiency is improved, and the board resin is further thermally decomposed, so that the weight reduction rate is increased. As shown in Example 4, the treatment effect similar to that of the nitrogen atmosphere can be obtained even in the superheated steam atmosphere. On the other hand, as shown in Examples 5 to 7, in a case in which the addition amount of the slaked limes during carbonizing is reduced, there is a board portion that is not covered with the slaked lime, and the removal rate of Br is lowered. Therefore, the addition amount of the slaked limes is preferably 1:0.05 or more with respect to the weight of the board, and in a case in which the addition amount thereof is 1:0.5 or more, the Br removal rate is 80% or more.

On the other hand, in Comparative Examples 1, 2 and 4, the Fe grade of the copper feed was 3% or more, the Al grade thereof was 1.8% or more, and the amounts of iron and aluminum were much more than those of Examples 1 to 7. Further, as shown in Comparative Example 1, in a case in which the carbonization temperature is too low, the solder does not melt, so that the separation effect of the mounted parts is lowered and the thermal decomposition of the resin is not sufficient. Further, as shown in Comparative Example 2, in a case in which the carbonization temperature reaches 700° C., the melting point (660° C.) of aluminum is exceeded, so that aluminum melts and the separation effect of the mounted parts is lowered, and the Fe grade and the Al grade of the copper feed are increased, and the Fe recovery rate of the SUS feed and the Al recovery rate of the Al feed are significantly lowered. Further, as shown in Comparative Example 3, Br cannot be fixed unless the slaked lime is added at the time of carbonization, so that the Br removal rate is 19% and most of Br is gasified. Further, as shown in Comparative Example 4, iron and aluminum cannot be separated from the electronic board by the treating method in the related art in which heating and melting are performed at 1200° C. in the air atmosphere.

TABLE 1Recovered materialSlakedCopper feedSUS feedAl feedlimeWeightCuFeAlFeAlBrTemperatureweightreductionrecoverygradegraderecoveryrecoveryremoval(° C.)Atmosphereratiorate (%)rate (%)(%)(%)rate (%)rate (%)rate (%)Example 1600N21:117.893.70.110.3297.589.287.2Example 2500N21:114.291.70.220.8496.191.689.9Example 3400N21:111.694.60.130.2594.793.390.7Example 4600Superheated1:117.390.20.180.3497.692.190.5steamExample 5600N21:0.517.992.30.310.3794.593.581.6Example 6600N21:0.117.189.60.440.5498.394.677.3Example 7600N21:0.0517.683.70.430.7591.590.567.4Comparative350N21:15.398.95.741.848.111.474.3Example 1Comparative700N21:118.091.43.194.6941.93.185.1Example 2Comparative600N2—17.293.20.360.1798.194.519.2Example 3Comparative1200Air—20.210010.387.36———Example 4atmosphere(Note)The slaked lime weight ratio is an addition weight ratio of the slaked limes to the board (board: slaked lime), and no slaked lime is added in Comparative Examples 3 and 4.

INDUSTRIAL APPLICABILITY

Generation of the harmful halogen-containing gas can be avoided, the combustibles or the halogens can be removed without causing environmental pollution, and a metal such as aluminum and SUS that adversely affect the copper refining process can be separated to use the treated material of the waste printed circuit board as the copper feed.