KR100613257B1 - Recycling method of waste acid etching solution - Google Patents
Recycling method of waste acid etching solution Download PDFInfo
- Publication number
- KR100613257B1 KR100613257B1 KR1020010083423A KR20010083423A KR100613257B1 KR 100613257 B1 KR100613257 B1 KR 100613257B1 KR 1020010083423 A KR1020010083423 A KR 1020010083423A KR 20010083423 A KR20010083423 A KR 20010083423A KR 100613257 B1 KR100613257 B1 KR 100613257B1
- Authority
- KR
- South Korea
- Prior art keywords
- waste
- sulfuric acid
- etching solution
- aluminum
- acid etching
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/46—Regeneration of etching compositions
Abstract
본 발명은 폐황산에칭액 및 폐염산에칭액의 재생 방법에 관한 것으로서, 더욱 상세하게는 (a) 알루미늄을 포함하는 폐황산에칭액 및 알루미늄을 포함하는 폐염산에칭액의 혼합액을 진공증발시켜 염산을 회수하는 단계; (b) 진공증발 후 알루미늄을 포함하는 폐황산에칭액에 알루미늄을 첨가하는 단계; 및 (c) 상기 알루미늄이 첨가된 폐황산에칭액을 확산투석하여 황산 및 황산알루미늄 수처리응집제로 분리하는 단계를 포함하는 폐산에칭액의 재생 방법에 관한 것이다.The present invention relates to a method for regenerating waste sulfuric acid etchant and waste hydrochloric acid etchant, and more particularly, (a) recovering hydrochloric acid by vacuum evaporation of a mixed solution of waste sulfuric acid etchant containing aluminum and waste hydrochloric acid etchant containing aluminum. ; (b) adding aluminum to the spent sulfuric acid etchant containing aluminum after vacuum evaporation; And (c) diffusing dialysis of the waste sulfuric acid etching solution to which the aluminum is added to separate the sulfuric acid and aluminum sulfate water treatment coagulant.
본 발명의 폐황산에칭액 및 폐염산에칭액의 재생 방법은 환경친화적이고 폐황산에칭액 및 폐염산에칭액으로부터 황산알루미늄, 황산 및 염산을 고순도로 재생할 수 있다.The waste sulfuric acid etchant and waste hydrochloric acid etching solution recycling method of the present invention is environmentally friendly and can recycle aluminum sulfate, sulfuric acid and hydrochloric acid with high purity from the waste sulfuric acid etching solution and the waste hydrochloric acid etching solution.
폐황산에칭액, 폐염산에칭액, 진공증발, 확산투석, 이온교환막, 수처리응집제Waste sulfuric acid etching solution, waste hydrochloric acid etching solution, vacuum evaporation, diffusion dialysis, ion exchange membrane, water treatment coagulant
Description
도 1은 알루미늄이 첨가된 폐황산에칭액을 확산투석하여 황산알루미늄 수처리응집제 및 황산으로 분리하는 방법을 나타내는 도면이다.1 is a view showing a method of separating a waste sulfuric acid etching solution added with aluminum by diffusing dialysis into an aluminum sulfate water treatment coagulant and sulfuric acid.
도 2는 본 발명의 폐산에칭액의 재생 방법을 나타내는 도면이다.2 is a view showing a regeneration method of the spent acid etching liquid of the present invention.
[산업상 이용 분야][Industrial use]
본 발명은 폐황산에칭액 및 폐염산에칭액의 재생 방법에 관한 것으로서, 더욱 상세하게는 환경친화적이고 폐황산에칭액 및 폐염산에칭액으로부터 황산알루미늄 수처리응집제, 황산 및 염산을 고순도로 재생할 수 있는 폐산에칭액의 재생 방법에 관한 것이다.The present invention relates to a method for regenerating waste sulfuric acid etching solution and waste hydrochloric acid etching solution, and more particularly, to recycling waste acid etching liquid which is environmentally friendly and can recycle aluminum sulfate water treatment coagulant, sulfuric acid and hydrochloric acid with high purity from waste sulfuric acid etching liquid and waste hydrochloric acid etching solution. It is about a method.
[종래 기술][Prior art]
황산 및 염산은 공업용 금속 에칭액으로 광범위하게 사용되어 오고 있다. 그러나 상기 황산 및 염산은 pH가 매운 낮은 강산이므로 에칭 후 남는 폐황산에칭액 및 폐염산에칭액은 환경에 매우 유해한 물질이다.Sulfuric acid and hydrochloric acid have been widely used as industrial metal etching solutions. However, since the sulfuric acid and hydrochloric acid are strong acid having a very low pH, the waste sulfuric acid etching solution and the hydrochloric acid etching solution remaining after etching are very harmful to the environment.
상기 유해성 폐황산에칭액을 제거하기 위하여 가성소다, 탄산칼슘 또는 수산화칼슘 등으로 중화시켜 폐기하는 방법이 일반적으로 사용되어 오고 있다. 그러나 폐황산에칭액 제거 공정에서 비소, 구리, 철, 아연, 납, 카드뮴 등과 같은 새로운 2차 폐기물이 다량 생성되며, 그 중 비소, 납 등은 인체뿐만 아니라 자연계에 존재하는 모든 생물체에 매우 유해한 물질이다. In order to remove the hazardous waste sulfuric acid etchant, neutralizing with caustic soda, calcium carbonate or calcium hydroxide and the like has been generally used. However, a large amount of new secondary wastes such as arsenic, copper, iron, zinc, lead, and cadmium are generated in the waste sulfuric acid etching solution removal process, among which arsenic and lead are very harmful to humans as well as to all living organisms in nature. .
상기 폐황산에칭액을 중화시켜 제거하는 방법 대신 폐황산에칭액을 황산으로 재생하는 방법이 제안되었었다. 미국특허 제 4,547,353호에는 폐황산에칭액을 완전히 증발농축시킨 후 열분해하여 아황산가스로 만든 후 다시 촉매로 치환하고 물에 흡수시켜 고순도의 황산으로 재생시키는 방법에 관하여 기재되어 있다. 그러나 상기 황산의 재생 방법에는 황산의 분해에 다량의 에너지가 필요하고 또한 황산의 금속부식성으로 인하여 고온내식성 설비가 필요하며 대규모의 장치가 필요하다. 따라서 황산폐에칭액 재생시에 효율적으로 폐황산에칭액으로부터 황산을 재생할 수 없다는 문제점이 있었다.Instead of neutralizing and removing the waste sulfuric acid etching solution, a method of regenerating the waste sulfuric acid etching solution with sulfuric acid has been proposed. U.S. Patent No. 4,547,353 describes a method of completely evaporating a waste sulfuric acid etch solution, pyrolysing it into sulfurous acid gas, replacing it with a catalyst, absorbing it in water, and regenerating it with high purity sulfuric acid. However, the regeneration method of sulfuric acid requires a large amount of energy to decompose sulfuric acid, high temperature corrosion resistance facilities due to the metal corrosion of sulfuric acid, and a large-scale device is required. Therefore, there was a problem in that sulfuric acid can not be efficiently recovered from the waste sulfuric acid etching solution during the recovery of the waste sulfuric acid etching solution.
하기 표 1은 알루미늄 호일의 에칭공정 후 발생되는 폐황산에칭액 중의 여러 가지 불순물의 종류와 함량을 나타내었다.Table 1 below shows the types and contents of various impurities in the waste sulfuric acid etching solution generated after the etching process of aluminum foil.
상기 표 1에 나타난 바와 같이, 폐황산에칭액은 다량의 알루미늄 성분을 포함하고 있으므로 폐황산에칭액을 에칭액으로 재사용하기 위해서는 알루미늄 등의 불순물 성분을 제거하여 재생되는 황산의 순도를 높여야 한다는 문제점이 있다.As shown in Table 1, since the waste sulfuric acid etching solution contains a large amount of aluminum components, there is a problem in that the purity of sulfuric acid to be recovered by removing impurity components such as aluminum must be increased in order to reuse the waste sulfuric acid etching solution as an etching solution.
또한, 하기 표 2에는 일반적으로 사용되는 황산알루미늄 수처리응집제에 관한 내용을 나타내었다.In addition, Table 2 below shows the contents of the commonly used aluminum sulfate water treatment coagulant.
상기 표 2에서 중화용 NaOH 사용량(g/kg)은 황산알루미늄 수처리응집제 1kg을 중화하는데 필요한 NaOH 사용량이고, 금속수산화물 발생량(g/kg)은 황산알루미늄 수처리응집제 1kg에서 발생되는 금속수산화물 슬러지량이고, 용해성(g/100㎖)은 물 100㎖에 용해되는 황산알루미늄 수처리응집제의 량을 나타낸다.In Table 2, the amount of NaOH used for neutralization (g / kg) is the amount of NaOH used to neutralize 1 kg of aluminum sulfate water treatment coagulant, and the amount of metal hydroxide generated (g / kg) is the amount of metal hydroxide sludge generated in 1 kg of aluminum sulfate water treatment coagulant. Solubility (g / 100 mL) refers to the amount of aluminum sulfate water treatment coagulant dissolved in 100 mL of water.
상기 표 2에 나타난 바와 같이, 황산알루미늄 수처리응집제 사용시 적정 pH 범위는 3.5-8.5로 거의 중성에 가까우나, 폐황산에칭액에 포함되어 있는 황산의 함량이 지나치게 많아 폐황산에칭액을 황산알루미늄 수처리응집제로 사용하기 위하여 다량의 중화제로 폐황산에칭액을 중화하여야 한다는 문제점이 있다.As shown in Table 2, when the aluminum sulfate water treatment coagulant is used, the optimum pH range is 3.5-8.5, which is almost neutral. However, the amount of sulfuric acid contained in the waste sulfuric acid etching solution is too high, so the waste sulfuric acid etching solution is used as the aluminum sulfate water treatment coagulant. There is a problem in that the waste sulfuric acid etching solution must be neutralized with a large amount of neutralizing agent.
또한, 일반적인 폐황산에칭액 중의 알루미늄 농도는 9-11 g/ℓ로 황산알루미늄 수처리응집제로서 바람직한 알루미늄 농도인 30-50 g/ℓ에 비하여 농도가 매우 낮음을 알 수 있다. 따라서 폐황산에칭액을 황산알루미늄 수처리응집제로 사용하기에 부적합하다는 문제점이 있다.In addition, the aluminum concentration in the general waste sulfuric acid etching solution is 9-11 g / l, it can be seen that the concentration is very low compared to 30-50 g / l, which is a preferable aluminum sulfate water treatment coagulant. Therefore, there is a problem that the waste sulfuric acid etching solution is not suitable for use as the aluminum sulfate water treatment coagulant.
본 발명은 상술한 문제점을 해결하기 위한 것으로서, 본 발명의 목적은 환경친화적이고 폐황산에칭액 및 폐염산에칭액으로부터 황산알루미늄 수처리응집제, 황산 및 염산을 고순도로 재생할 수 있는 폐산에칭액의 재생 방법을 제공하기 위한 것이다.SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for regenerating waste acid etching liquid which is environmentally friendly and can regenerate aluminum sulfate water treatment coagulant, sulfuric acid and hydrochloric acid with high purity from waste sulfuric acid etching solution and waste hydrochloric acid etching solution. It is for.
상기 목적을 달성하기 위하여, 본 발명은 (a) 알루미늄을 포함하는 폐황산에칭액 및 알루미늄을 포함하는 폐염산에칭액의 혼합액을 진공증발시켜 염산을 회수하는 단계; (b) 진공증발 후 알루미늄을 포함하는 폐황산에칭액에 알루미늄을 첨가하는 단계; 및 (c) 상기 알루미늄이 첨가된 폐황산에칭액을 확산투석하여 황산 및 황산알루미늄 수처리응집제로 분리하는 단계를 포함하는 폐산에칭액의 재생 방법을 제공한다.In order to achieve the above object, the present invention comprises the steps of (a) recovering hydrochloric acid by vacuum evaporation of a mixed solution of waste sulfuric acid etching solution containing aluminum and waste hydrochloric acid etching solution containing aluminum; (b) adding aluminum to the spent sulfuric acid etchant containing aluminum after vacuum evaporation; And (c) diffusing dialysis of the waste sulfuric acid etching solution to which the aluminum is added, and separating the sulfuric acid etching solution into a sulfuric acid and aluminum sulfate water treatment coagulant.
이하 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명의 황산폐에칭액의 재생 방법은 The regeneration method of the sulfated etching solution of the present invention
(a) 알루미늄을 포함하는 폐황산에칭액 및 알루미늄을 포함하는 폐염산에칭액의 혼합액을 진공증발시켜 염산을 회수하는 단계;(a) recovering hydrochloric acid by vacuum evaporating a mixed solution of waste sulfuric acid etching solution containing aluminum and waste hydrochloric acid etching solution containing aluminum;
(b) 상기 진공증발 후 알루미늄을 포함하는 폐황산에칭액에 알루미늄을 첨가하는 단계; 및(b) adding aluminum to the spent sulfuric acid etching solution containing aluminum after the vacuum evaporation; And
(c) 상기 알루미늄이 첨가된 폐황산에칭액을 확산투석하여 황산 및 황산알루미늄 수처리응집제로 분리하는 단계(c) separating the aluminum sulfate-added waste sulfuric acid etching solution into sulfuric acid and aluminum sulfate water treatment coagulant.
를 포함한다.It includes.
본 발명에서는 확산투석법을 이용하여 폐황산에칭액에 포함되어 있는 황산과 알루미늄 이온을 황산용액 및 알루미늄을 포함하는 폐금속액으로 분리하여 황산용액은 에칭액으로 재사용하고, 알루미늄 이온을 포함하는 폐금속액은 황산알루미늄 수처리응집제로 재사용한다는 것이 본 발명의 핵심이다. 또한, 폐염산에칭액을 진공증발시켜 회수되는 염산도 에칭액으로 유용하게 재사용할 수 있다는 것이 본 발명의 핵심이다.In the present invention, the sulfuric acid and aluminum ions contained in the waste sulfuric acid etching solution are separated into a waste metal solution containing sulfuric acid solution and aluminum by using diffusion dialysis, and the sulfuric acid solution is reused as an etching solution, and the waste metal solution containing aluminum ions. The reuse of silver as an aluminum sulfate water treatment coagulant is at the heart of the present invention. In addition, it is the core of the present invention that hydrochloric acid recovered by vacuum evaporation of waste hydrochloric acid etching solution can be usefully reused as an etching liquid.
폐황산에칭액 및 폐염산에칭액을 재생시키기 위하여 먼저 (a) 알루미늄을 포함하는 폐황산에칭액 및 알루미늄을 포함하는 폐염산에칭액의 혼합액을 진공증발시켜 염산을 회수한다.In order to regenerate the spent sulfuric acid etchant and the spent hydrochloric acid etchant, (a) a mixed solution of the spent sulfuric acid etchant containing aluminum and the spent hydrochloric acid etchant containing aluminum is vacuum-evaporated to recover hydrochloric acid.
황산 및 염산은 에칭액으로 많이 사용된다. 그러나 상기 황산 및 염산은 강산이므로 에칭공정 중에 알루미늄 등의 금속성분을 녹이기도 한다. 따라서 에칭공정 후 남는 폐에칭액에는 알루미늄 등의 금속성분이 포함되어 있다.Sulfuric acid and hydrochloric acid are widely used as etching solutions. However, since sulfuric acid and hydrochloric acid are strong acids, metal components such as aluminum may be dissolved during the etching process. Therefore, the waste etching solution remaining after the etching process contains metal components such as aluminum.
이 때 알루미늄을 포함하는 폐황산에칭액 및 알루미늄을 포함하는 폐염산에칭액의 혼합액을 진공에서 가열하면 염산이 증발하여 염산수용액으로 다시 회수된다. 이는 황산이 비휘발성인 점에 비하여 염산은 휘발성이므로 황산 및 염산의 혼합액을 가열하면 염산만 증발된다는 점을 이용한 것이다. 또한 알루미늄을 포함하는 폐황산에칭액 및 알루미늄을 포함하는 폐염산에칭액의 혼합액에 포함되어 있는 알루미늄은 금속이므로 증발하지 않고 당연히 상기 혼합액에 남아있게 된다.At this time, when the mixed solution of the waste sulfuric acid etching liquid containing aluminum and the waste hydrochloric acid etching liquid containing aluminum is heated in vacuo, hydrochloric acid evaporates and it collect | recovers again to aqueous hydrochloric acid solution. This is because hydrochloric acid is volatile in comparison with sulfuric acid is nonvolatile, so that only hydrochloric acid is evaporated when the mixture of sulfuric acid and hydrochloric acid is heated. In addition, the aluminum contained in the mixed solution of the waste sulfuric acid etching liquid containing aluminum and the waste hydrochloric acid etching liquid containing aluminum is, of course, a metal and thus remains in the mixed liquid without evaporation.
따라서 상기 염산이 증발된 혼합액은 고농도의 알루미늄을 포함하는 폐황산에칭액이 된다.Therefore, the mixed solution in which the hydrochloric acid is evaporated becomes a waste sulfuric acid etching solution containing a high concentration of aluminum.
폐황산에칭액 및 폐염산에칭액의 혼합액을 진공증발시킨 후 (b) 상기 진공증발 후 알루미늄을 포함하는 폐황산에칭액에 알루미늄을 첨가한다. 즉, 잔류 알루미늄을 포함하는 폐황산에칭액에 알루미늄을 더욱 첨가하여 수처리응집제로 바람직한 농도의 알루미늄을 포함하는 황산알루미늄 수처리응집제를 재생하기 위한 것이다. After vacuum evaporation of the mixed solution of the spent sulfuric acid etchant and the spent hydrochloric acid etchant, (b) aluminum is added to the spent sulfuric acid etchant containing aluminum after the vacuum evaporation. That is, the aluminum sulfate is further added to the waste sulfuric acid etching solution containing the residual aluminum to regenerate the aluminum sulfate water treatment coagulant containing aluminum in the concentration desired as the water treatment coagulant.
상기 알루미늄의 첨가량은 최종 생성되는 황산알루미늄 수처리응집제의 농도가 30-50g/ℓ가 되도록 첨가하는 것이 바람직하다. 또한 상기 폐황산에칭액 중 알루미늄의 농도를 황산알루미늄 수처리응집제로 사용하기 위해 요구되는 황산알루미늄 농도 이상으로 높인 다음 잔류 고형분을 여과하고 확산투석한다.The addition amount of the aluminum is preferably added so that the concentration of the final produced aluminum sulfate water treatment coagulant is 30-50 g / l. In addition, the concentration of aluminum in the spent sulfuric acid etching solution is increased to the aluminum sulfate concentration required for use as the aluminum sulfate water treatment coagulant, and the residual solids are filtered and diffused dialysis.
통상 폐에칭액 중 알루미늄의 농도는 약 9-11gℓ에 불과하며 확산투석 후 황산이 분리제거됨으로 알루미늄을 용해시킬 수 있는 강산인 황산의 폐에칭액 중의 함량이 적어 알루미늄 폐칩의 용해 속도가 느려진다는 문제점이 있다. 따라서 알루미늄의 농도를 황산알루미늄 수처리응집제로 사용가능한 농도인 30-50g/ℓ가 되도록 확산투석 전에 미리 폐에칭액에 알루미늄을 첨가하여 가열·용해시켜 폐황산에칭액 중 알루미늄의 농도를 높이는 것이 바람직하다.In general, the concentration of aluminum in the waste etching solution is only about 9-11 gℓ, and the sulfuric acid is separated and removed after diffusion dialysis, and thus, there is a problem in that the dissolution rate of the aluminum waste chip is slowed because the content of the sulfuric acid, a strong acid capable of dissolving aluminum, is small. . Therefore, it is preferable to increase the concentration of aluminum in the waste sulfuric acid etching solution by adding aluminum to the waste etching solution in advance before diffusion dialysis so that the concentration of aluminum is 30-50 g / l, which is the concentration usable as the aluminum sulfate water treatment coagulant.
이 때, 첨가되는 알루미늄으로는 폐자원인 알루미늄 폐칩를 사용하는 것이 환경친화적인 면에서나 경제적인 면에서나 바람직하다. 알루미늄 폐칩은 알카리 탈지액으로 완전히 탈지하여 불순물을 제거한 다음 사용하는 것이 바람직하다.At this time, it is preferable to use aluminum waste chips as waste resources in terms of environment friendliness and economics. Aluminum waste chips are preferably used after completely degreasing with alkaline degreasing liquid to remove impurities.
잔류 페황산에칭액에 알루미늄을 첨가한 후 (c) 상기 알루미늄이 첨가된 폐황산에칭액을 확산투석하여 황산 및 황산알루미늄 수처리응집제로 분리한다.After the aluminum is added to the residual sulphate etching solution, (c) the waste sulfuric acid etch solution to which the aluminum is added is subjected to diffusion dialysis to separate the sulfuric acid and the aluminum sulfate water treatment coagulant.
도 1은 알루미늄이 첨가된 폐황산에칭액을 확산투석하여 황산알루미늄 수처리응집제 및 황산으로 분리하는 방법을 나타내는 도면이다. 도 1에서 중앙의 이온교환막을 기준으로 좌측은 폐금속액 영역이고 우측은 회수 황산 영역을 나타낸다.1 is a view showing a method of separating a waste sulfuric acid etching solution added with aluminum by diffusing dialysis into an aluminum sulfate water treatment coagulant and sulfuric acid. In FIG. 1, the left side shows the waste metal liquid region and the right side shows the recovered sulfuric acid region based on the central ion exchange membrane.
도 1에 나타난 바와 같이, 중앙의 이온교환막을 경계로 한쪽은 물을 흘려주고 다른 한쪽은 폐에칭액을 서로 반대 방향으로 흘려주면 이온교환막 경계면에서 전해질의 농도 차로 인한 확산력에 차이가 생겨 황산은 이온교환막을 통과하여 물을 흘려주는 방향으로 이동하여 황산수용액으로 배출되고 황산을 포함하지 않는 잔류 폐에칭액은 이온교환막을 통과하지 않고 금속폐액으로 배출된다. 이와 같이 농도차이에 의한 확산을 통하여 어떤 물질을 투석하는 방법을 확산투석법이라 칭한다.As shown in FIG. 1, when one side flows water at the boundary of the central ion exchange membrane and the other side flows waste etchant in the opposite direction, the diffusion force is different due to the difference in concentration of the electrolyte at the interface of the ion exchange membrane. It moves in the direction of flowing water through the membrane and is discharged into the aqueous sulfuric acid solution, and residual waste etching solution containing no sulfuric acid is discharged into the metal waste liquid without passing through the ion exchange membrane. As described above, a method of dialysis of a substance through diffusion due to concentration difference is called diffusion dialysis.
상기 이온교환막은 알루미늄 이온은 통과하지 못하고 황산만 통과하게 된다. 그러나 상기의 확산투석반응이 진행됨에 따라 이온교환막의 좌·우측의 황산농도가 거의 동일해지면 그 시점부터는 농도차에 의한 확산은 일어나지 않게 된다. 도 1에서 물이 투입되는 지점은 황산농도가 0이며 회수 황산으로 되어 빠져나가는 지점에서 황산의 농도는 거의 잔류 폐황산에칭액과 동일하다.The ion exchange membrane does not pass aluminum ions, only sulfuric acid passes. However, as the diffusion dialysis reaction proceeds, when the sulfuric acid concentrations on the left and right sides of the ion exchange membrane become almost the same, diffusion due to the difference in concentration does not occur from that time point. In FIG. 1, the water is introduced at the point where sulfuric acid concentration is 0 and the concentration of sulfuric acid at the point of exiting as recovered sulfuric acid is almost the same as the residual waste sulfuric acid etching solution.
반대로, 알루미늄을 포함하는 폐금속액이 빠져나가는 지점은 순수한 물이 투입되는 지점이므로 이온교환막의 좌·우측이 농도평형에 이를 경우 알루미늄을 포함하는 금속폐액 중의 황산농도는 거의 0이고 알루미늄 이온만을 포함한 폐액이 배출된다.On the contrary, the point where the waste metal liquid containing aluminum exits is pure water. Therefore, when the left and right sides of the ion exchange membrane reach an equilibrium concentration, the sulfuric acid concentration in the metal waste liquid containing aluminum is almost 0 and only aluminum ions are included. Waste fluid is discharged.
이 때, 확산투석의 효율을 높이고 설비의 안정성을 확보하기 위하여 또한 회수되는 황산수용액 및 알루미늄 함유 폐금속액을 각각 에칭액 및 황산알루미늄 수처리응집제로 사용하기 위하여 회수 황산 영역의 유속이 알루미늄 폐액 영역의 유속보다 크거나 같게하는 것이 바람직하다. At this time, in order to increase the efficiency of diffusion dialysis and to ensure the stability of the equipment, and to use the recovered sulfuric acid aqueous solution and the aluminum-containing waste metal liquid as the etching solution and the aluminum sulfate water treatment coagulant, respectively, the flow rate of the recovered sulfuric acid region is the flow rate of the aluminum waste liquid region. It is desirable to be greater than or equal to.
따라서 확산투석기 내부의 회수 황산 영역의 유속이 폐금속액 영역의 유속보다 낮을 경우 폐금속액 중에 황산이 다량 포함되어 있어 황산알루미늄 수처리응집제로 사용하기에 부적합하다는 문제점이 있다. 이는 폐금속액을 황산알루미늄 수처리응집제로 사용하기위해서는 상기 황산알루미늄 수처리응집제의 pH가 거의 중성이어야 하기 때문이다.Therefore, when the flow rate of the recovered sulfuric acid region in the diffusion dialysis machine is lower than the flow rate of the waste metal liquid region, a large amount of sulfuric acid is contained in the waste metal liquid, which is not suitable for use as an aluminum sulfate water treatment coagulant. This is because in order to use the waste metal liquid as the aluminum sulfate water-coagulant, the pH of the aluminum sulfate water-coagulant should be almost neutral.
이온교환막을 기준으로 회수 황산 영역 및 폐금속액 영역의 유속은 모두 600-1200㎖/m2hr로 제어하는 것이 바람직하다. 유속이 1200 ㎖/m2hr를 초과하면 이온교환막 째짐 현상이 일어나 확산투석기를 안정적으로 운전할 수 없다는 문제점이 있다. It is preferable to control the flow rates of the recovered sulfuric acid region and the waste metal liquid region to 600-1200 ml / m 2 hr based on the ion exchange membrane. If the flow rate exceeds 1200 ml / m 2 hr, there is a problem that the ion exchange membrane slit occurs and the diffusion dialysis machine cannot be operated stably.
회수 황산 영역 및 폐금속액 영역의 유속을 모두 1200 ㎖/m2hr를 초과하게 제어하면 이온교환막째짐 현상을 방지할 수는 있으나 회수되는 황산의 농도가 낮아진다는 문제점이 있어 바람직하지 않다. Controlling the flow rates of the recovered sulfuric acid region and the waste metal liquid region in excess of 1200 ml / m 2 hr can prevent ion exchange membrane slit, but it is not preferable because there is a problem that the concentration of sulfuric acid to be recovered is lowered.
또한, 회수 황산 영역의 유속 및 폐금속액 영역의 유속이 600 ㎖/m2hr 미만일 경우에는 이온교환막 접촉 현상이 발생하여 확산투석기 운전이 곤란해진다는 문제점이 있다.In addition, when the flow rate of the recovered sulfuric acid region and the flow rate of the waste metal liquid region are less than 600 ml / m 2 hr, an ion exchange membrane contact phenomenon occurs, which makes it difficult to operate the diffusion dialysis machine.
상기 확산투석에 의하여 얻어진 회수 황산의 농도를 확인한 후, 회수 황산에서의 황산농도가 에칭액으로 사용하기에 부적절한 고농도의 황산이면 물을 첨가하여 농도를 낮춘다. 또한 회수 황산에서의 황산농도가 에칭액으로 사용하기에 부적절한 저농도의 황산이면 황산을 더욱 첨가하여 에칭액으로 사용하기에 적당한 고농도의 황산용액으로 농도를 높인다.After confirming the concentration of the recovered sulfuric acid obtained by the diffusion dialysis, if the sulfuric acid concentration in the recovered sulfuric acid is a high concentration of sulfuric acid which is inappropriate for use as an etching solution, water is added to lower the concentration. In addition, if the sulfuric acid concentration in the recovered sulfuric acid is a low concentration of sulfuric acid which is inappropriate for use as an etching solution, further sulfuric acid is added to increase the concentration to a high concentration of sulfuric acid solution suitable for use as an etching solution.
또한, 폐금속액의 농도를 확인한 후 폐금속액에서의 알루미늄 농도를 35-45g/ℓ로 조절하여 알루미늄 함유 폐금속액을 황산알루미늄 수처리응집제로 재사용한다.Also, after confirming the concentration of the waste metal liquid, the aluminum concentration in the waste metal liquid is adjusted to 35-45 g / L, and the aluminum-containing waste metal liquid is reused as an aluminum sulfate water treatment coagulant.
상기에서 살펴본 바와 같이, 본 발명의 본 발명의 폐황산에칭액 및 폐염산에칭액의 재생 방법은 환경친화적이고 폐황산에칭액 및 폐염산에칭액으로부터 황산알루미늄 수처리응집제, 황산 및 염산을 고순도로 재생할 수 있다.As described above, the waste sulfuric acid etchant and waste hydrochloric acid etching solution recycling method of the present invention is environmentally friendly, and can be recycled aluminum sulfate water treatment coagulant, sulfuric acid and hydrochloric acid from waste sulfuric acid etching solution and waste hydrochloric acid etching solution with high purity.
이하, 본 발명의 바람직한 실시예 및 비교예를 기재한다. 하기 실시예 및 비교예는 본 발명을 보다 명확히 표현하기 위한 것으로서 본 발명의 내용이 하기 실시예에 한정되는 것은 아니다.Hereinafter, preferred examples and comparative examples of the present invention are described. The following examples and comparative examples are intended to express the present invention more clearly, and the content of the present invention is not limited to the following examples.
[실시예 1-9 및 비교예 1-11][Example 1-9 and Comparative Example 1-11]
폐황산에칭액을 진공에서 가열하여 염산을 분리·회수하여 400g/ℓ의 고농도의 황산폐에칭액을 제조하였다. 그 다음 알루미늄 선반 가공공정에서 생성된 두께 0.1 ㎜의 얇은 나선형 알루미늄 폐칩을 잘게 잘라 에틸알코올에 담근 후 10 분간 초음파로 탈지한 다음 잔류 폐황산에칭액에 용해시켰다.The waste sulfuric acid etching solution was heated in vacuo to separate and recover hydrochloric acid, thereby preparing a high concentration of sulfuric acid etching solution of 400 g / L. Then, a thin spiral aluminum waste chip having a thickness of 0.1 mm produced in an aluminum lathe processing process was finely chopped, soaked in ethyl alcohol, degreased by ultrasonic wave for 10 minutes, and then dissolved in the residual waste sulfuric acid etching solution.
그 다음 실험용 카트리지 필터를 사용하여 상기 알루미늄이 첨가된 잔류 폐황산에칭액에서 잔류 고형물을 여과하였다. A residual solid was then filtered from the aluminum spent sulfuric acid etchant using an experimental cartridge filter.
확산투석기로 일본 주식회사 도꾸야마 소다 주식회사(Tokuyama Soda)의 의 모델명 TDS-2를 사용하였다. 또한 이온교환막으로 네오셉타 에이에프엑스(NEOSEPTA AFX)를 사용하여 상기 폐황산에칭액을 회수 황산 영역 및 폐금속액 영역에서의 유속을 변화시켜가며 확산투석하였으며, 그 결과를 하기 표 3에 나타내었다.As a diffusion dialysis machine, the model name TDS-2 of Tokuyama Soda Co., Ltd., Japan, was used. In addition, the waste sulfuric acid etch solution was diffused dialysis with varying flow rates in the recovered sulfuric acid region and the waste metal liquid region using Neocepta AFX as an ion exchange membrane, and the results are shown in Table 3 below.
표 3에 나타난 바와 같이, 회수 황산 영역의 유속이 금속폐액 영역의 유속과 같거나 더 크고 또한, 회수 황산 영역 및 금속폐액 영역의 유속이 모두 600-1200 (㎖/㎡hr)인 경우에 해당하는 실시예 1-9의 경우에 재생된 황산 및 폐금속액의 농도가 에칭액 및 황산알루미늄 수처리응집제로서의 바람직한 농도범위에 해당하여 에칭액 및 황산알루미늄 수처리응집제로 사용될 수 있다.As shown in Table 3, the flow rate of the recovered sulfuric acid zone is equal to or greater than that of the metal waste zone, and the flow rates of the recovered sulfuric acid zone and the metal waste zone are both 600-1200 (ml / m 2 hr). In the case of Example 1-9, the concentration of the regenerated sulfuric acid and the waste metal liquid may be used as the etching liquid and the aluminum sulfate water treatment coagulant, corresponding to the preferred concentration ranges as the etching solution and the aluminum sulfate water treatment coagulant.
본 발명의 폐산에칭액의 재생 방법은 환경친화적이고 폐황산에칭액 및 폐염산에칭액으로부터 황산알루미늄 수처리응집제, 황산 및 염산을 고순도로 재생할 수 있다.The regeneration method of the waste acid etching solution of the present invention is environmentally friendly and can regenerate the aluminum sulfate water treatment coagulant, sulfuric acid and hydrochloric acid from the waste sulfuric acid etching solution and the waste hydrochloric acid etching solution with high purity.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020010083423A KR100613257B1 (en) | 2001-12-22 | 2001-12-22 | Recycling method of waste acid etching solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020010083423A KR100613257B1 (en) | 2001-12-22 | 2001-12-22 | Recycling method of waste acid etching solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20030053247A KR20030053247A (en) | 2003-06-28 |
| KR100613257B1 true KR100613257B1 (en) | 2006-09-25 |
Family
ID=29577844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020010083423A KR100613257B1 (en) | 2001-12-22 | 2001-12-22 | Recycling method of waste acid etching solution |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100613257B1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100440469B1 (en) * | 2001-12-22 | 2004-07-14 | 삼성전기주식회사 | Recycling method of waste sulfuric acid etching solution, waste chloric acid etching solution and waste nitric acid etching solution |
| KR101009026B1 (en) * | 2005-12-26 | 2011-01-17 | 대일개발 주식회사 | Method for recovering acid from mixed waste acid occupied in preparing process of liquid crystal display |
| KR100813111B1 (en) * | 2006-10-23 | 2008-03-17 | (주) 에코솔루텍 | The preparation method of poly aluminium chloride from waste acid |
| CN114314526B (en) * | 2021-12-24 | 2023-06-27 | 山东久日化学科技有限公司 | Recovery method of waste sulfuric acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05228471A (en) * | 1992-02-18 | 1993-09-07 | Nittetsu Mining Co Ltd | Treatment of aluminum phosphate-containing monobasic acid waste liquid |
| JPH06173048A (en) * | 1992-12-04 | 1994-06-21 | Daido Chem Eng Kk | Method for recovering waste metal surface treating acid |
-
2001
- 2001-12-22 KR KR1020010083423A patent/KR100613257B1/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05228471A (en) * | 1992-02-18 | 1993-09-07 | Nittetsu Mining Co Ltd | Treatment of aluminum phosphate-containing monobasic acid waste liquid |
| JPH06173048A (en) * | 1992-12-04 | 1994-06-21 | Daido Chem Eng Kk | Method for recovering waste metal surface treating acid |
Non-Patent Citations (2)
| Title |
|---|
| 05228471 |
| 06173048 |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20030053247A (en) | 2003-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3671644B2 (en) | Photoresist developing waste liquid recycling method and apparatus | |
| EP2397444A1 (en) | Method for processing waste water containing fluorine and silicon, method for producing calcium fluoride, and facility for processing fluorine-containing waste water | |
| CN105502782A (en) | Technology for recovering water resources and salt from coking wastewater in coal chemical industry | |
| CN102633398A (en) | Method for recovering organic effluent brine | |
| JP2001026418A (en) | Recovering method of industrially useful inorganic material and industrially useful inorganic material recovered by the same | |
| US5281318A (en) | Process for processing a waste etching solution containing a fluorine component and an ammonia component to recover valuables therefrom | |
| CN105906127A (en) | Desulfurization wastewater near-zero release treatment system and method | |
| KR100613257B1 (en) | Recycling method of waste acid etching solution | |
| JP2009023847A (en) | Method for producing hydriodic acid | |
| KR20200013522A (en) | Ammonia collection apparatus and method for collecting ammonium sulfate from waste water using the same | |
| JP2013010988A (en) | Method for regenerating waste liquor containing tetraalkylammonium hydroxide | |
| US5433936A (en) | Flue gas desulfurization process | |
| US6936177B2 (en) | Method for removing metal from wastewater | |
| CN101993380B (en) | Equipment and method for recovering tetramethylammonium hydroxide | |
| KR100758461B1 (en) | Method for reuse of wastewater in continuous electroplating lines | |
| KR100440469B1 (en) | Recycling method of waste sulfuric acid etching solution, waste chloric acid etching solution and waste nitric acid etching solution | |
| CN112573745B (en) | SCR catalyst regeneration pickling wastewater treatment method | |
| JPH01130783A (en) | Treatment of alkaline waste liquid of fluorinated product containing metal ion and oil | |
| JP3519112B2 (en) | Method and apparatus for treating liquid to be treated such as waste liquid containing ammonia compound | |
| JPH07204457A (en) | Desulfurization of exhaust gas | |
| KR100790370B1 (en) | Recycling method and apparatus of waste etching solution | |
| KR20060081730A (en) | Method for treating waste etching solution using an ion-exchange membrane module | |
| KR100201179B1 (en) | Process for valorizing a liquid acid effluent containing heavy metals | |
| JPH08224572A (en) | Ultra pure water production and wastewater treatment in closed system | |
| JP2011125812A (en) | Method for treating wastewater containing fluorine and silicon, method for producing calcium fluoride, and apparatus for treating fluorine-containing wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20120824 Year of fee payment: 7 |
|
| FPAY | Annual fee payment |
Payment date: 20130704 Year of fee payment: 8 |
|
| LAPS | Lapse due to unpaid annual fee |