JP2764887B2 - Method for recovering valuable materials from copper-containing ion solution - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for recovering valuable resources from a copper-containing ion solution.

[0002]

2. Description of the Related Art A large number of printed circuit boards are currently manufactured for mounting microelectronic elements which have been rapidly developed in recent years. Its applications cover a wide range of consumer products, are widely used in industrial equipment, and have a remarkable elongation.

[0003] The printed circuit board manufacturing process includes an etching process, from which a solution containing a large amount of copper salt is discharged. As an etching agent, a ferric chloride solution, a hydrogen peroxide-hydrochloric acid solution, a hydrogen peroxide-sulfuric acid solution, or the like is used. It is recovered as a copper salt or a copper compound by a treatment method, or is recovered as metallic copper by an electrode short circuit reaction due to a difference in ionization potential between steel and copper.

However, in the case of recovering copper from steel, as is apparent from the following formulas: Cu ⁺⁺⁺⁺ Fe → Cu + Fe ⁺⁺ , Cu ⁺⁺⁺ Fe ⁺⁺⁺ Fe → Cu + Fe ⁺⁺ , ferrous chloride having a chemical equivalent to the copper content is apparent. Is produced, and in the case of a copper-containing iron chloride solution, ferrous chloride equivalent to copper is produced. Therefore, in order to regenerate them as an etchant or a sewage treatment agent, there is a problem that they must be oxidized to ferric chloride by rechlorination with chlorine gas, which requires a high degree of skill in handling, and excessively. There is a problem that the ferric chloride solution to be produced has to be searched for a sales channel or separately treated as industrial waste.

[0005] Further, there is a problem that it is difficult to adjust the reaction conditions or the reaction time is long, there is a risk of iron being mixed into the recovered copper, and there is also a problem of the quality and evaluation as crude copper. There are also various problems, such as the labor-intensive process work.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and it is an object of the present invention to provide a method for producing high purity fine copper powder from an etching solution containing a large amount of copper salt by a simple industrial apparatus. And recovering a basic aluminum chloride solution having a predetermined basicity and other valuable resources.

The inventor of the present invention has conducted experiments and studies on the reaction between a copper salt solution and metallic aluminum in place of steel in order to solve the above-mentioned conventional problems and solve the above-mentioned problems. Confirmed such new facts.

1) The local battery short-circuiting reaction between a copper salt solution and metallic aluminum requires a reaction rate of 15 to 48 hours compared to the reaction between metallic aluminum and hydrochloric acid, metallic aluminum and sulfuric acid, or steel and copper salt solution. The reaction is extremely quick, and the reaction is completed in about 4 hours in a practical-scale reaction vessel, and the copper concentration in the reaction solution is 1 ppm or less.

2) The copper salt solution easily reacts with the metallic aluminum even at room temperature, and the heat of reaction causes a temperature rise exceeding 100 ° C., but the reaction temperature is from room temperature to 100 ° C.
It is desirable to keep the range.

3) Reaction between metallic aluminum and copper salt solution
Is the amount of excess aluminum over the amount of copper in the copper salt solution.
Progress easily. Of hydrogen gas generated by the reaction
As a result of measuring the amount and analyzing the composition of the reaction solution,
It is estimated that it is represented by the following equation. For cupric chloride:2 Al +(3-n / 2)CuCl₂+nH₂O=Al₂(OH)_nCl_6-n+(3-n / 2) Cu + n /2H₂  For copper sulfate:2OH ⁻ = SO ₄ ^-2 Considering the relationship 2 Al +(3-n / 2)CuSO₄+nH₂O=Al₂(OH)_n(SO₄)_{3 -N / 2} +(3-n / 2)Cu +n / 2H₂ Here Al₂(OH)_nCl_6-nN / 6 x 100%
Represents the basicity of basic aluminum chloride.
It can be controlled in the range of 0 to 80%.₂(O
H)_n(SO₄)_{3-n / 2}ofn / 2 ÷ 3= N / 2 × 3
= N / 6 × 100% is the basicity of basic aluminum sulfate
And can be controlled in the range of 0 to 80%.

[0011] produced in the reaction, a basic aluminum chloride solution, basic aluminum sulfate solution is widely used as a water treatment coagulant, it is important raw material for the poly aluminum chloride.

4) Copper precipitated by the reaction between metallic aluminum and a copper salt solution is agglomerated particles of dendritic copper powder in micron units, is easily separated from the product solution, and has a purity of 9%.
9% or more.

Based on the above facts, the inventor of the present invention has determined that high purity copper can be obtained from a copper salt or a solution containing a copper salt recovered in an etching step or the like discharged from the printed circuit board manufacturing step by using an ordinary industrial apparatus. In addition, it has been found that a basic aluminum chloride solution having a predetermined basicity and other valuable substances can be recovered.

[0014]

Means for Solving the Problems] To solve the above problems the present invention, a solution containing soluble copper salt or copper salt, copper
Of the basic aluminum salt which is the product relative to the abundance of
An excess amount of metallic aluminum having a desired basicity within a range of 0 to 80% is completely dissolved and reacted to precipitate copper aggregated particles in the reaction solution, and to precipitate copper from the reaction solution. In this method, powdery metallic copper is recovered by filtering the particles.

Further, by reacting a soluble copper salt or a solution containing a copper salt with a controlled excess amount of metallic aluminum, copper aggregated particles are precipitated in the reaction solution,
Collect the generated hydrogen gas, and also dilute the filtrate obtained by filtering the precipitated particles of copper from the reaction solution,
A basic aluminum salt solution having a basicity of 30 to 80% can be recovered, and all of these are valuable resources having commercial value.

[0016]

EXAMPLES [1] 100 per liter as copper ions
While stirring 1 liter of the cupric chloride solution containing gr at room temperature, 56.7 gr of metal aluminum having a purity of 99.9% was charged therein while monitoring the state of hydrogen gas foaming. The temperature of the reaction solution gradually rises, but when the temperature is maintained at about 75 ° C. by cooling and the reaction is continued, the metal aluminum completely dissolves after 2 hours, and the resulting solution becomes colorless and transparent. Aggregated copper particles precipitated.

After 4 hours, the precipitated copper particles were separated by filtration, washed with water and dried to obtain 98 gr of copper powder having a purity of 99.2%. The basicity of the basic aluminum chloride diluted so that the alumina concentration in the filtrate is 10.5% is 50%, and the liquid weight is 1%.
020 gr, and the copper concentration in the solution was 0.8 ppm. The amount of hydrogen gas generated during the reaction was about 34
Liters.

[2] 10 per 1 liter as copper ions
While stirring 0.5 liter of a copper sulfate solution containing 0 gr at room temperature, 21.3 gr of metal aluminum having a purity of 99.8% was charged therein while monitoring the state of hydrogen gas generation. The temperature of the reaction solution gradually rises, but when the solution temperature is kept at about 80 ° C. by cooling and the reaction is continued, the metal aluminum is completely dissolved after 1.5 hours, and the resulting solution becomes colorless and transparent. Agglomerated particles of copper were deposited therein.

After 3 hours, the precipitated copper particles were separated by filtration, washed with water and dried to obtain 48 gr of copper powder having a purity of 99.3%. The basicity of the basic aluminum sulfate diluted to a concentration of alumina of 10.5% in the filtrate is 33%, and the weight of the liquid is 7%.
60 gr, the copper concentration in the liquid was 0.6 ppm. The amount of hydrogen gas generated during the reaction was about 8.
It was 5 liters.

[0020]

Since the present invention is constructed as described above, high-purity fine copper powder or aluminum chloride having a predetermined basicity can be prepared by a simple industrial apparatus from an etching solution containing a large amount of copper salt. There is an effect that valuable resources such as a solution or hydrogen gas can be easily collected.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-61-205617 (JP, A) JP-A-53-63213 (JP, A) JP-A-62-13544 (JP, A) 68428 (JP, A) JP-A-59-190333 (JP, A) JP-A-51-59722 (JP, A) JP-A-61-9530 (JP, A) JP-A-50-84415 (JP, A) Japanese Patent Laid-Open No. Sho 50-2621 (JP, A)

Claims (3)

(57) [Claims] 1. A method according to claim 1, wherein the soluble copper salt or the solution containing the copper salt is mixed with the product basic aluminum based on the amount of copper present.
The desired basicity is obtained when the basicity of the salt is in the range of 0 to 80%.
An excess amount of metallic aluminum is completely dissolved and reacted to precipitate copper aggregated particles in the reaction solution, and the precipitated copper particles are filtered out of the reaction solution to recover powdered metallic copper. A method for recovering valuable resources from a copper-containing ion solution. 2. A solution containing a soluble copper salt or a copper salt, and a basic aluminum which is a product based on the amount of copper present.
The desired basicity is obtained when the basicity of the salt is in the range of 0 to 80%.
That excess by reacting a metal aluminum to precipitate agglomerated copper particles in the reaction solution, diluting the obtained filtrate by filtering off the precipitated particles of the copper from the reaction solution,
A method for recovering valuable resources from a copper-containing ion solution, comprising recovering a basic aluminum salt solution having a basicity of 30 to 80%. 3. A solution containing a soluble copper salt or a copper salt, and a basic aluminum which is a product based on the amount of copper present.
The desired basicity is obtained when the basicity of the salt is in the range of 0 to 80%.
A method for recovering valuable resources from a copper-containing ion solution, comprising recovering hydrogen gas by causing aggregated particles of copper to precipitate in a reaction solution by reacting with an excessive amount of metallic aluminum.