KR100650232B1 - Device and method for extracting nickel from ferric chloride etchant - Google Patents

Abstract

The present invention relates to a device for extracting nickel ions in a corrosion solution of iron chloride, and monitors the corrosion capability of the corrosion solution with an RGB color sensor, and when the corrosion capability is below the threshold, DNNSA (dinonylnaphthalenesulphonic acid) and BAPP (2,6-bis -[5-alkylpyrazol-3-yl] pyridine) to a nickel ion extracting device in a corrosion solution of iron chloride which is intended to extract nickel. According to the device of the present invention, only nickel is removed without removing iron in advance. It can be selectively removed and semi-permanently recycled non-recovered and disposed of corrosive solutions to prevent environmental pollution problems and to reduce the human and material costs of solution replacement and control in off-line processes. The effect of increasing the productivity of can be obtained.

Iron Chloride Corrosion Solution, Nickel Ion, RGB Color Controller, DNNSA, BAPP, Inline

Description

DEVICE AND METHOD FOR EXTRACTING NICKEL FROM FERRIC CHLORIDE ETCHANT}             

1 is a schematic diagram of a nickel ion extracting apparatus according to an embodiment of the present invention.

* Description of the symbols for the main parts of the drawings *

1: Base material 2: Corrosion apparatus

3: injection nozzle 4: waste corrosion solution tank

5: first RGB color controller 6: discharge pump

7: nickel extraction tank 8: iron chloride recovery tank

9: carbon filter 10: pump

11: solenoid valve 12: solenoid valve

13 kerosene recovery pump 14 motor

15 kerosene recovery tank 16 second RGB color controller

17 pump 18 solenoid valve

19: storage tank 20: level sensor

21: control unit

The present invention relates to a device for extracting nickel ions in the corrosion solution of iron chloride, more specifically iron chloride corrosion to recover in-line nickel metal contained in the corrosion solution by using DNNSA (dinonylnaphthalenesulphonic acid) and BAPP It relates to a nickel ion extraction device in solution.

Nickel alloy (Ni-alloy) has been used as a material for semiconductor leadframe, cathode ray tube shadow mask, filter, mesh, spring, etc. due to the advantages of excellent corrosion resistance, strength, and ductility. These materials are subjected to a corrosion process to produce leadframes and shadow masks in the production of products for industrial use. Etching is a widely used method for the photochemical machining (PCM) of nickel, nickel alloys and stainless steels, and the suspension of lead frames, shadow masks, heating elements, and PC hard drives. It is applied to the production of suspension-arm. Ferric chloride corrosion solution is used a lot in this corrosion process. As the PCM etching process proceeds, iron ions are reduced, and metals such as nickel are oxidized and dissolved in the solution.As the amount of nickel in the solution increases, the etching rate decreases, resulting in decreased product production efficiency and roughness of the product surface. ) Increases the problem. When the concentration of nickel in the corrosion solution is 10-15 g / L, no further etching is possible and the solution must be regenerated or discarded. As such, nickel gradually acts as a material that interferes with the corrosion process as its amount gradually increases in the corrosion solution. In other words, if the amount of nickel is increased, the efficiency of the corrosion process decreases and product defects occur. Therefore, the entire amount of the corrosion solution must be discarded and replaced with a new corrosion solution.

Ni can be recovered from the recovered waste corrosion solution using an electrolysis method or a boiling extraction metod, but this treatment cost is enormous and impractical. In this way, it is not possible to recover the nickel in the waste corrosion solution, and it is common to dispose or discard the entire waste corrosion solution. For example, in the United States, waste corrosion solutions are known to be mixed with lime and landfilled. However, landfills can not recycle nickel, an expensive imported raw material, which can lead to waste of resources and serious environmental problems. Therefore, development of an effective nickel regeneration method is required.

Currently, various methods for recovering nickel in the waste corrosion solution have been developed, but most of them have disadvantages of going off-line. Also, some methods only partially oxidize iron without removing nickel, thereby partially increasing the etching rate. The method is limited in its application.

The off-line regeneration method is to recover the etched waste corrosion solution and then reprocess it. The regeneration process is performed off-line because there is a big difference between the production process of the product by etching and the chemical-physical state of the regeneration or nickel extraction process, and the two processes cannot be performed simultaneously. This off-line regeneration method is disadvantageous in that it takes a lot of human, time, and material costs to recover, reprocess, and replace the corrosion solution, and fundamentally solves the disadvantage that the etching rate decreases as the corrosion solution is used. I can't have a problem.

For example, one of the currently used nickel regeneration methods, the ion-exchange method, is capable of selectively removing nickel, but requires expensive ion exchange resins. There is a disadvantage that the recovery of nickel by the in-line method is difficult because recovery of nickel occurs under conditions different from the etching conditions. In addition, in general, since iron has a greater affinity than nickel, iron has to be removed beforehand to remove only nickel.

Electrodialysis uses a method in which iron reoxidation occurs at the anode and nickel is deposited at the cathode with a cation-permeable membrance in between. . This method has the advantage of being able to recover the corrosion solution on-site. However, in the cathode where the reduction of nickel occurs, not only nickel but also iron ions are precipitated together, and as a result, iron is gradually depleted in the corrosion solution, thereby making it impossible to etch, and recovered nickel has a problem of containing a large amount of impurities. .

The redox method using chemicals is possible in-line, but not fundamentally elimination of nickel; nickel recovery is only possible off-line by simply increasing the amount of oxidized Fe ³⁺ to maintain only instantaneous etching rates. Do.

Cementation is also called "reductive precipitation" and is a method obtained by reducing iron at high temperatures by adding a catalyst. This method is used a lot because of the simple process, but requires a large amount of electricity or fuel, there is a disadvantage that can not affect the etching rate by the off-line method.

The present invention is to overcome the problems of the prior art described above, one object of the present invention is to extract the nickel in-line so that the iron chloride corrosion solution can be recycled in the same system without discarding the waste corrosion solution It is to provide a nickel ion extraction apparatus and method.

Another object of the present invention is to provide an apparatus and method for extracting nickel ions in a corrosion solution of iron chloride which can reduce cost and prevent environmental pollution by regenerating and recycling Ni, an expensive metal.

One aspect of the present invention for achieving the above object is

A waste corrosion solution tank carrying waste corrosion solution containing iron chloride;

A first RGB color controller which monitors and controls the corrosion capability of the waste corrosion solution in the waste corrosion solution tank;

A nickel extraction tank including a kerosene layer for receiving the waste corrosion solution from the waste corrosion solution tank according to a control signal from the first RGB color controller and extracting nickel using BAPP and DNNSA;

An iron chloride recovery tank supporting the nickel chloride solution removed from the nickel extraction tank and circulating a corrosion solution to the waste corrosion solution tank;

A kerosene recovery tank for recovering kerosene from the nickel extraction tank;

A second RGB color controller for monitoring and controlling the nickel concentration in the kerosene in the kerosene recovery tank;

A storage tank for storing an aqueous hydrochloric acid solution containing nickel transferred from the kerosene recovery tank; And

Corrosion chloride including a control unit for outputting a control signal for the nickel extraction tank, kerosene recovery tank, iron chloride recovery tank after receiving and analyzing the RGB light data measured from the first RGB color controller and the second RGB color controller, respectively It relates to a nickel ion extraction device in solution.

Another aspect of the present invention for achieving the above object is a method for extracting nickel ions in the iron chloride corrosion solution, the method comprising the steps of: monitoring the corrosion capability of the corrosion solution using an RGB color controller; The monitoring result of the previous step relates to a method for extracting nickel ions in the corrosion solution of iron chloride which includes the step of regenerating the corrosion solution by adding BAPP and DNNSA when the corrosion capability of the corrosion solution is below a predetermined threshold.

Hereinafter, with reference to the accompanying drawings will be described in detail with respect to the present invention.

1 is a schematic view of a nickel ion extraction apparatus according to an embodiment of the present invention. The present invention is not necessarily limited to the embodiment shown in FIG. 1 and may be variously modified. Referring to Figure 1, the nickel ion extracting apparatus of the present invention is a waste corrosion solution tank (4) carrying a waste corrosion solution containing iron chloride, agent for monitoring and controlling the corrosion capability of the waste corrosion solution in the waste corrosion solution tank A nickel extraction tank including a kerosene layer for receiving 1 RGB color controller 5 and a waste corrosion solution from the waste corrosion solution tank according to a control signal from the first RGB color controller, and extracting nickel using BAPP and DNNSA ( 7) an iron chloride recovery tank (8) for carrying the nickel chloride solution removed from the nickel extraction tank and circulating a corrosion solution to the waste corrosion tank (8), kerosene recovery tank for recovering kerosene from the nickel extraction tank ( 15), a second RGB color controller 16 for monitoring and controlling the nickel concentration in the kerosene in the kerosene recovery tank, the hydrochloric acid containing nickel transferred from the kerosene recovery tank Storage tank (19) for storing the liquid and RGB optical data measured from the first RGB color controller and the second RGB color controller, respectively, after receiving and analyzing the control of the nickel extraction tank, kerosene recovery tank, iron chloride recovery tank And a control unit 21 for outputting a signal.

Specifically, the nickel extraction tank 7 includes a level sensor for detecting the height of the liquid in the tank and a motor for mixing the processing solution in the tank. In the nickel extraction tank 7, DNNSA (dinonylnaphthalenesulphonic acid) and BAPP (2,6-bis- [5-alkylpyrazol-3-yl] pyridine) are already quantitatively mixed and the composition is adjusted. BAPP in the extraction tank can be dissolved with DNNSA to selectively extract nickel.

Compared with conventional extraction reagents, BAPP forms an optimal metal complex with nickel in a very low pH range (pH = 0.1-0.5), making it very easy to apply to the etchant composition. This is expected to be due to the fact that the nitrogen groups included in BAPP act as better electron donors at lower pH. In addition, BAPP is about 50 times more separation factor (separation factor) than iron, so it can be selectively applied to the extraction of nickel.

The BAPP used as the complexing agent of the present invention has a structure represented by the following Chemical Formula 1, and has a structure in which pyrazol is connected to 2,6 positions using pyridine as a basic skeleton, and is formed by three nitrogens centrally located. It will form a chelate compound with the metal. These complexing agents selectively form only nickel prior to iron because they form stronger bonds to nickel than iron, in particular compared to conventional di-2-ethylhexyl phosphoric acid. Can be extracted.

In the above formula, R is a linear alkyl group or phenyl group having 2 to 18 carbon atoms.

In Formula 1, the substituent R is a major factor in determining the solubility between the water and the organic solvent of the complexing agent, and plays an important role in controlling the degree of bonding of nickel to nitrogen through the steric effect of R. will be. Substituent R can be adjusted according to the extraction solvent used, and is a C2-C18 linear alkyl group. Preferred examples of the substituent (R) are C ₂ -C ₁₈ alkyl or phenyl groups, which typically include octyl, nonyl, octadecyl, hexadecyl and the like. In addition, it is possible to adjust the bonding strength with the metal to be extracted according to the type of substituent, in order to selectively separate iron octyl substituent is suitable. Since such complexing agents do not decompose even at low pH and strong acid, the solvent composition to which they can be applied has a wide range of properties.

DNNSA used in the present invention has a structure of Formula 2, and acts as a modifier to help dissolution of BAPP of Formula 1.

Examples of the BAPP usable in the present invention is one or more selected from the group of formula (3).

The kerosene recovery tank 15 receives kerosene from the nickel extraction tank 7 to extract nickel in the kerosene and returns the purified kerosene to the nickel recovery tank 7 by the nickel recovery pump 13. In the kerosene recovery tank 15, sulfuric acid hydrochloric acid is representative as an acid which is applied as an aqueous solution containing a high concentration of acid, and the concentration range of these acids is 1.0-8.0M, and suitably 2-7M. Nickel, which forms a complex in the kerosene layer, is substituted with hydrogen ions in a strong acidic solution, and nickel is dissolved in an acid solution such as hydrochloric acid, so that the kerosene layer loses nickel and is regenerated in the form of hydrogen ions.

The first RGB color controller 5 is an RGB color controller which scans a specific light of RGB into the corrosion solution and senses RGB optical data through scattering of light. All metals and chemicals have their own colors. In the case of corrosion reactions, all metals and chemicals meet and the chemical reactions lead to the aging of the corrosion solution. The color changes the color of the corrosion solution. The first RGB color controller 5 detects this color change and monitors the corrosion capability of the corrosion solution. Therefore, the control of this function checks the correspondence with the data on the previously detected data through the operation of the microprocessor and adds a component for regeneration accordingly so that the solution of the corroded state can be normalized. The first RGB color controller 5 and the second RGB color controller 16 will each perform. According to the functions of the first RGB color controller 5 and the second RGB color controller 16, the change in chromaticity according to the nickel concentration in iron chloride and the amount of NiCl ₂ which is the extracted metal in hydrochloric acid is adjusted.

The nickel ion extracting apparatus of the present invention may further include a carbon filter 9 for purifying a solution from which nickel is removed connected to the iron chloride solution recovery tank 8. This carbon filter 9 functions to remove traces of kerosene that may be included in the extraction process in the iron chloride recovery tank and the kerosene removed iron chloride solution is returned to the waste corrosion tank 4 again. The carbon filter 9 performs a function of supplying a pure corrosion solution by removing not only general kerosene but also foreign substances generated in an existing corrosion process.

Here, the first RGB color controller 5 and the second RGB color controller 16 perform their respective functions, and when the signal indicating that the corrosion capability of the iron chloride etching solution is lower than the threshold is detected, the first RGB color controller 5 and the second RGB color controller 16 transmit the same to the controller 21. .

The second RGB color controller 16 scans RGB specific light to kerosene in the kerosene recovery tank 15 to detect RGB light data for the color of nickel through scattering of light, and compares it with a reference table to Detects the concentration of nickel chloride (NiCl ₂ ). When the concentration of nickel reaches an appropriate value, the solenoid valve 18 and the pump 17 are operated to transfer to the storage tank 19.

The control unit 21 is mounted on the nickel extraction tank 7, the iron chloride recovery tank 8, and the kerosene recovery tank 15 according to the control signals of the first RGB color controller 5 and the second RGB color controller 16. The control signals for the solenoid valve 11, the pumps 12 and 13, the motors 22 and 14, and the level sensor 20 are output, and the control signals for the carbon filter 9 are also output.

The operation of the nickel ion extraction device in the iron chloride compound of the present invention will be described.

Referring to FIG. 1, the base material 1 may be formed by spraying nozzles when materials including nickel alloy components, such as alloy leadframes, shadow masks, stainless steel, etc., enter the corrosion device 2. Corrosion begins by ferric chloride (FeCl ₃ ) sprayed in ₃ ). As the corrosion progresses, the corrosion solution begins to age. When the nickel content in the corrosion solution exceeds 10-15 g / L, the nickel component acts as a blocker and no longer has a corrosion ability.

Therefore, when the concentration of nickel in the corrosion solution is increased in this way, the RGB color controller 5 detects this, and the color controller 5 signals the discharge pump 6 to reduce the excessive nickel concentration, so that the valve opens and the nickel concentration. Is sent to the nickel extraction tank (7). The nickel extraction tank 7 has already been quantitatively mixed with DNNSA (dinonylnaphthalenesulphonic acid) and BAPP in a primary stirring tank, and the composition is adjusted. In kerosene in the nickel extraction tank 7 BAPP dissolves with DNNSA to selectively extract nickel.

BAPP, which is a complexing agent usable in the present invention, is a novel compound developed by the present inventors based on the pyridine ring, and since nickel forms a stronger bond with nickel, nickel can be extracted without the influence of iron. . In addition, the extraction conditions are the same as the conditions of the corrosion solution has the advantage that the extraction can be carried out without special chemical conditions.

When the level sensor 20 in the nickel extraction tank is activated, this signal is signaled to the agitation motor 22 so that agitation according to the PLC program by the time value already set is started. At the end of the stirring time, the electronic control valve 11 is operated to transfer the nickel-free solution to the iron chloride recovery tank 8. This ferric chloride solution becomes a solution that can be reused as a nickel-free solution to finish purification of the solution through a carbon filter (9) and then transferred to an initial waste corrosion tank (4) by a pump (10) to continue. Continuous operation is achieved.

  In this way, the kerosene layer in which nickel is sucked through repeated rotational circulation becomes a kerosene layer having a nickel concentration of a predetermined amount or more.

After the repetitive collection of the set value or more is made, the kerosene is transferred to the kerosene recovery tank 15 under the control of the solenoid valve 12 to remove nickel ions dissolved in the kerosene. The kerosene recovery tank 15 is combined with the hydrochloric acid solution and the motor 14 is operated by the control of the controller 21. This repetition is carried out continuously in the kerosene recovery tank 15, and the finishing of this repetition is performed by the second RGB color controller 16 with the table to be compared based on the color of nickel in hydrochloric acid in the kerosene recovery tank 15. Comparing with the data value input through the comparison verification and reaches the appropriate value, the solenoid valve 18 and the pump 17 is operated to transfer to the storage tank (19).

Another aspect of the invention relates to a method for extracting nickel ions in an iron chloride corrosion solution. In the case of extracting nickel in the iron chloride corrosion solution according to the present invention, first, the corrosion capability of the corrosion solution is monitored by using an RGB color controller, and when the result of the monitoring determines that the corrosion capability of the corrosion solution is below a predetermined threshold, BAPP and DNNSA Add the corrosion solution to regenerate. In the monitoring of the iron chloride corrosion solution, the iron chloride corrosion solution is measured with an RGB color controller to obtain RGB optical data, and the obtained RGB optical data is compared with the preset color pattern data of the corrosion solution in which the corrosion capability is not impaired. Determine whether the solution is regenerated. When reclaiming the waste corrosion solution, mix BAPP and DNNSA in the corrosion solution.

According to the present invention, it is possible to selectively remove only nickel without removing iron in advance, and to prevent the environmental pollution problem by semi-permanently recycling the corrosion solution, which is not recovered and disposed of in the past, and was required for solution replacement and control. It has the effect of increasing the productivity of the entire process by reducing human and material costs. In addition, it is possible to remove nickel by in-line to increase production efficiency and to homogenize the product.

Claims (10)

A waste corrosion solution tank carrying waste corrosion solution containing iron chloride; A first RGB color controller which monitors and controls the corrosion capability of the waste corrosion solution in the waste corrosion solution tank; A nickel extraction tank including a kerosene layer for receiving the waste corrosion solution from the waste corrosion solution tank according to a control signal from the first RGB color controller and extracting nickel using BAPP and DNNSA; An iron chloride recovery tank (8) for supporting the nickel chloride solution removed from the nickel extraction tank and circulating a corrosion solution to the waste corrosion solution tank; A kerosene recovery tank for recovering kerosene from the nickel extraction tank; A second RGB color controller for monitoring and controlling the nickel concentration in the kerosene in the kerosene recovery tank; A storage tank for storing an aqueous hydrochloric acid solution containing nickel transferred from the kerosene recovery tank; And Corrosion chloride including a control unit for outputting a control signal for the nickel extraction tank, kerosene recovery tank, iron chloride recovery tank after receiving and analyzing the RGB light data measured from the first RGB color controller and the second RGB color controller, respectively Nickel ion extraction device in solution. The method of claim 1, wherein the nickel extraction tank A level sensor for sensing the height of the corrosion solution in the tank; An apparatus for extracting nickel ions in an iron chloride corrosion solution including a stirring motor for mixing the corrosion solution in a tank. The method of claim 1, wherein the BAPP and DNNSA is a nickel ion extracting device in the iron chloride corrosion solution, characterized in that the compound having the structures of formulas (1) and (2), respectively. [Formula 1]

In the above formula, R is a linear alkyl group or phenyl group having 2 to 18 carbon atoms. [Formula 2]

[4] The apparatus for extracting nickel ions in the corrosion solution of iron chloride according to claim 3, wherein the BAPP has a structure represented by the following Chemical Formula 3. [Formula 3]

2. The apparatus for extracting nickel ions in the corrosion solution of iron chloride according to claim 1, wherein the kerosene recovery tank receives kerosene from a nickel extraction tank to extract nickel in the kerosene and return the purified kerosene to a nickel recovery tank. 2. The apparatus of claim 1, wherein the first and second RGB color controllers are RGB color controllers that scan RGB light to detect RGB light data by scattering light. The apparatus of claim 1, wherein the apparatus further comprises a carbon filter for purifying the nickel depleted solution connected to the iron chloride solution recovery tank. As a method of extracting nickel ions in the iron chloride corrosion solution, Monitoring the corrosion capability of the corrosion solution using the RGB color controller; A method for extracting nickel ions from the corrosion solution of iron chloride, comprising the step of regenerating the corrosion solution by adding BAPP and DNNSA when the corrosion capability of the corrosion solution is less than the threshold value as a result of the previous step. The method of claim 8, wherein said monitoring step Measuring the iron chloride corrosion solution with an RGB color controller to obtain RGB optical data; The method of extracting nickel ions in the iron chloride corrosion solution comprising comparing the RGB light data with the predetermined color pattern data to determine whether or not the corrosion solution. 9. The method of extracting nickel ions in the iron chloride corrosion solution according to claim 8, wherein the threshold of nickel concentration is 10-15 g / L.

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