JP3018019B2 - High quality recovery of valuable metals from acid waste liquor - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to copper chloride or copper chloride.
The present invention relates to a method for recovering valuable metals in a continuous process by adding spherical iron powder (for example, iron powder generated from a converter) to an acid waste liquid containing nickel or the like.

[0002]

2. Description of the Related Art Ferric chloride having high purity is used as a reagent used for photoetching of a lead frame or the like used for an IC. The components of the lead frame material are eluted into the used reagent, and the concentration of ferric chloride is reduced to deteriorate the etching efficiency. Therefore, the reagent is replaced. This used reagent contains, in addition to the high concentration of iron ions,
Contains significant amounts of valuable copper and nickel ions. Therefore,
As described in JP-A-1-167235, there is a method in which iron waste is added to an etching waste liquid to control the pH in a tank, copper and Ni are recovered, and the liquid is regenerated and used for etching. .

[0003]

However, in this method, the quality of the recovered copper or Ni is low, and the value of the valuable metal is low. In addition, as a means for improving the quality of recovered metal from the past, a powder containing a valuable metal is converted into a slurry as in the method of treating a metal-containing carbon-containing powder described in JP-A-51-120902. There is a method of flotation after classification, but it is difficult to perform flotation if the specific gravity of the impurities to be separated is large because of the physical beneficiation. The present invention has been made in view of such circumstances, and it is intended to positively cause a chemical reaction and further actively use a wet cyclone to circulate collected solids to recover high-quality valuable metals. With the goal.

[0004]

According to the present invention, there is provided a semiconductor device comprising:
The high-quality recovery method of valuable metals from acid waste liquids is to supply a certain amount of acid waste liquid in which valuable metals are dissolved to the reaction tank,
A predetermined amount of spherical iron powder is added to cause a valuable metal generation reaction, and the overflow of the reaction tank is sent to a wet cyclone with a slurry pump, and the cyclone underflow containing collected solids is subjected to the reaction. After returning to the tank, after a predetermined time has passed in the reaction tank, the high-concentration slurry is taken out of the system as a cyclone underflow to recover high-grade metal with a small amount of unreacted iron powder, and the cyclone overflow is transferred to another liquid processing system. It is configured to feed liquid.

According to a second aspect of the present invention, there is provided a method for recovering valuable metals from an acid waste solution of high quality, wherein the acid waste solution containing copper and nickel is put into a first reaction tank and spherical iron powder is added. Then, the solution after recovering the copper was further added with spherical iron powder in the second reaction tank to cause a valuable metal generation reaction, and the outlet effluent of the reaction tank was continuously put into a wet cyclone. ,
The unreacted iron powder and the reactive metal powder are separated, and the separated unreacted iron powder and the reactive metal powder are returned to the reaction tank, and the cyclone overflow solution from which the unreacted iron powder and the reactive metal powder have been removed is treated with chloride. The liquid is sent to the ferrous product process, and when the solids in the reaction tank rise to a predetermined concentration, the reaction metal slurry is discharged out of the system to collect valuable metals.

[0006]

According to the method for recovering valuable metals from acid waste liquid of high quality according to the first aspect of the present invention, an acid waste liquid containing valuable metals is put into a reaction tank, and a predetermined amount of spherical iron powder is added and stirred. Therefore, when the valuable metal is copper, the following reaction occurs. 2FeCl ₃ + Fe → 3FeCl ₂ (1) CuCl ₂ + Fe → FeCl ₂ + Cu (2) In the reaction, (1) takes precedence, and then the reaction of (2) is performed. As a result, the surface of the iron powder is activated, and the substitution reaction between Fe and Cu proceeds easily. The reaction starts from the surface of the iron and proceeds to the inside sequentially, and the central part of the iron powder is eluted to terminate the reaction of the iron powder. Here, in the present invention, since spherical iron powder is used as iron powder, generated copper precipitates on the surface and the apparent particle size increases. Therefore, the iron powder that has become fine particles due to the reaction and the spherical iron powder to which the generated copper adheres are separated by a wet cyclone, but the spherical iron powder to which copper adheres is returned to the reaction tank again, so the treatment is performed. By repeating, there is no unreacted iron. Therefore, high-quality copper is recovered by collecting the solid content in the reaction tank after a predetermined time has elapsed. The above operation is also applied to a metal having a higher ionization tendency than iron.

According to a second aspect of the present invention, there is provided a method for recovering valuable metals from an acid waste solution of high quality, wherein an acid waste solution containing copper and nickel is put into a first reaction tank, and spherical iron powder is added. The solution after recovering the copper is further added with spherical iron powder in a second reaction tank to cause a valuable metal generation reaction. Accordingly, nickel is adhered around the spherical iron powder by the reaction, and the fine iron powder produced by the reaction is further removed by the wet cyclone. By repeatedly performing the returning process to the reaction tank, the fine iron powder contained therein is removed, and only nickel particles having a small amount of iron are obtained. By collecting the nickel particles after a predetermined time, high-grade nickel is recovered.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments embodying the present invention will now be described with reference to the accompanying drawings to provide an understanding of the present invention. Here, FIG. 1 is a schematic process diagram showing a method for recovering valuable metals from an acid waste solution with high quality according to one embodiment of the present invention.
First, a base solution such as ferric chloride is previously placed in a 4 m ³ first reaction tank 10, and a converter-generated iron powder, which is an example of a spherical iron powder, is placed in the first reaction tank 10. A waste liquid tank 1 containing an approximately equivalent amount of the copper content to be treated from the iron powder hopper 11 and storing used acid waste liquid in photoetching or the like.
The acid waste liquid is gradually supplied at a rate of about 2 to 1 m ³ / sec. The particle size of the converter-produced iron powder is about 100 to 500 μm. Further, the pH of the first reaction tank 10 is set to 1 or less, but when the PH is greater than 1, pH control is performed by adding hydrochloric acid or the like, and the oxidation-reduction potential (ORP) of the first reaction tank is further reduced. The temperature is adjusted to −300 to 350 mV, and a heater is provided to adjust the liquid temperature to 70 to 80 ° C. As a result, the reactions (1) and (2) described above actively occur, and copper precipitates around the spherical iron powder.

A stirrer 13 is provided in the first reaction tank 10 and is driven to rotate by a motor (not shown). Slurry pump 1
5 to be supplied to the upper wet cyclone 16. Since the wet cyclone 16 has a trapping particle size of +20 μm or more, the unreacted spherical iron powder, the spherical iron powder to which the reaction-produced copper particles are adhered, and the large-grown copper particles are separated, and the lower first iron particles are separated. It is returned to the reaction tank 10. Then, the mixed solution containing the small fine solids is sent to the centrifugal separator 17 to remove the fine solids contained therein, and then supplied to the cushion tank 18. Since the spherical iron powder to which the copper particles have adhered and the generated copper particles having a large particle size are returned to the first reaction tank 10 again, the above (1) and (2)
Is promoted, and the treatment step is continuously continued for about 10 hours (preferably 6 hours or more), whereby spherical iron powder is almost completely eliminated, and large-grain copper is generated.

If the above treatment is performed for about 10 hours, copper grains of sufficient quality will be produced. Thereafter, the pipe connected from the wet cyclone 16 to the first reaction tank 10 is rotated. Then, it is connected to a drainer Akins 19, and the produced copper particles are collected and put into a pit 20, and are appropriately dried and shipped as a product. As a result, copper having a purity of 92% or more is recovered. The amount of the spherical iron powder to be supplied is equivalent to or less than the amount of copper generated during 10 hours. This improves the purity of the produced copper.

Next, the solution stored in the cushion tank 18 is put into a second reaction tank 21. The second reaction tank 21 is provided with a stirrer 22 so that the internal solution can be sufficiently mixed, and a heater is provided so that the liquid temperature can be maintained at 70 to 90 ° C. Has become. Further, the second reaction tank 21 is provided with a heater so that the internal temperature becomes 70 to 90 ° C., a base solution is previously put inside, and the second reaction tank 21 is contained in a container which is put in for 10 hours simultaneously with the start of the reaction. Nickel-equivalent spherical iron powder is gradually added, and the pH is adjusted to between 1 and 2 to adjust the oxidation-reduction potential to -450 mV or less.

Therefore, the following reaction occurs in the second reaction tank 21 to precipitate Ni. NiCl ₂ + Fe → FeCl ₂ + Ni (3) Since the precipitated nickel adheres to the periphery of the spherical iron powder, the overflow liquid is once put into the cone tank 23,
Wet cyclone 2 pumped up by slurry pump 24
Put in 5. The wet cyclone 25 separates a solution containing a large spherical iron powder and a spherical iron powder to which nickel is attached, and a solution containing fine iron powder, so that the large spherical iron powder and the spherical iron powder to which nickel is attached are separated. The solution is drained to a certain extent through the lower solid-liquid separation akins 26 and then re-entered into the second reaction tank 21.

The wet cyclone 25 and Ekins 2
The supernatant solution of No. 6 is placed in another Akins separation device 27, and the large particles having a fast precipitation time are separated from the Akins 26.
, Is returned to the second reaction tank 21 again. on the other hand,
The supernatant liquid of the Akins separator 27 is subjected to a centrifugal separator 28 to remove fine trace iron powder, then put into a cushion tank 29 and reduced by chlorine sent from a chlorine gas tank 30 to FeCl ₃ to produce a product. It is stored in the tank 31.

After the stirring reaction in the second reaction tank 21 has been performed for a predetermined time (6 to 10 hours), the particles from the liquid draining Akins 26 are not allowed to flow into the lower second reaction tank 21. And the pits 32, the nickel particles are recovered. This is dried and shipped as a product. In addition, iron hydroxide is generated when PH rises in the above reaction, iron loss occurs, and if there is air entrainment during stirring, goethite, iron oxyoxide, etc. are generated, so that air is not entrained, It is necessary to keep the oxidation-reduction potential at a predetermined value.

[0015]

According to the first and second aspects of the present invention, the high-quality recovery method of valuable metals from acid waste liquids, as is clear from the above description, causes a chemical reaction to actively occur, and furthermore, a wet cyclone is actively used. Since the collected solids are circulated and used, high-quality valuable metals having a pure content of 90% or more can be recovered.

[Brief description of the drawings]

FIG. 1 is a schematic process diagram of a high-quality recovery method of valuable metals from an acid waste solution according to one embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 1st reaction tank 11 Iron powder hopper 12 Waste liquid tank 13 Stirrer 14 Cone tank 15 Slurry pump 16 Wet cyclone 17 Centrifuge 18 Cushion tank 19 Drain drainer Akins 20 Pit 21 Second reaction tank 22 Stirrer 23 Cone Tank 24 Slurry pump 25 Wet cyclone 26 Ekins 27 Ekins separator 28 Centrifuge 29 Cushion tank 30 Chlorine gas tank 31 Product tank 32 Pit

Continuing from the front page (72) Inventor Masatake Nagashima 1-1, Hibata-cho, Tobata-ku, Kitakyushu-shi, Fukuoka Nippon Steel Corporation Yawata Works (72) Inventor Hironobu Active No. 1 Tobita-cho, Tobata-ku, Kitakyushu-shi, Fukuoka No. 1 Inside Nippon Steel Corporation Yawata Works (72) Inventor Yonejiro Nagaoka 1-1, Tobata-cho, Tobata-ku, Kitakyushu-shi, Fukuoka Prefecture Inside Nippon Steel Corporation Yawata Works (56) References JP 59-157283 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C23F 1/46 C02F 1/62 C22B 7/00

Claims (2)

(57) [Claims] 1. An acid waste solution in which a valuable metal is dissolved is supplied to a reaction tank in a fixed amount, and a predetermined amount of spherical iron powder is added to cause a valuable metal generation reaction. The liquid is sent to a wet cyclone in the above, and the cyclone underflow containing the collected solids is returned to the reaction tank,
After the elapse of a predetermined time in the reaction tank, the high-concentration slurry is taken out of the system as a cyclone underflow to recover a high-grade metal with a small amount of unreacted iron powder, and the cyclone overflow is sent to another liquid processing system. A high-quality recovery method for valuable metals from an acid waste liquid, characterized by the following: 2. An acid waste solution containing copper and nickel components is put into a first reaction tank, and a solution obtained by adding spherical iron powder to recover copper is further subjected to a second reaction tank to further remove spherical iron powder. The reaction tank is added to cause a valuable metal generation reaction, and the outlet effluent of the reaction tank is continuously put into a wet cyclone to separate unreacted iron powder and reactive metal powder, and separate the unreacted iron powder and reactive metal. The powder is returned to the reactor, and the cyclone overflow solution from which the unreacted iron powder and the reactive metal powder have been removed is sent to the ferrous chloride product process, and the solids in the reactor rise to a predetermined concentration. A high-quality recovery method for valuable metals, wherein the valuable metal is recovered by discharging the reaction metal slurry to the outside of the system at the time of the recovery.