KR100502589B1 - Method of regenerating effluent as washing liquid for metal products - Google Patents
Method of regenerating effluent as washing liquid for metal products Download PDFInfo
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- KR100502589B1 KR100502589B1 KR10-2001-0046708A KR20010046708A KR100502589B1 KR 100502589 B1 KR100502589 B1 KR 100502589B1 KR 20010046708 A KR20010046708 A KR 20010046708A KR 100502589 B1 KR100502589 B1 KR 100502589B1
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- hydrofluoric acid
- liquid
- waste liquid
- ion concentration
- fluorine ion
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- 239000007788 liquid Substances 0.000 title claims abstract description 120
- 238000005406 washing Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims description 43
- 229910052751 metal Inorganic materials 0.000 title claims description 14
- 239000002184 metal Substances 0.000 title claims description 14
- 230000001172 regenerating effect Effects 0.000 title description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 123
- 239000002699 waste material Substances 0.000 claims abstract description 95
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 43
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 14
- 239000011737 fluorine Substances 0.000 claims abstract description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 183
- 238000004519 manufacturing process Methods 0.000 claims description 46
- 238000004140 cleaning Methods 0.000 claims description 41
- 239000012535 impurity Substances 0.000 claims description 41
- 230000008929 regeneration Effects 0.000 claims description 14
- 238000011069 regeneration method Methods 0.000 claims description 14
- 239000012141 concentrate Substances 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 229960002050 hydrofluoric acid Drugs 0.000 description 83
- 239000000243 solution Substances 0.000 description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- 239000010436 fluorite Substances 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 7
- 239000003456 ion exchange resin Substances 0.000 description 7
- 229920003303 ion-exchange polymer Polymers 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000001223 reverse osmosis Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 239000000383 hazardous chemical Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- -1 fluorine ions Chemical class 0.000 description 4
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000003113 dilution method Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229940081735 acetylcellulose Drugs 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5036—Azeotropic mixtures containing halogenated solvents
- C11D7/5068—Mixtures of halogenated and non-halogenated solvents
- C11D7/5077—Mixtures of only oxygen-containing solvents
- C11D7/5086—Mixtures of only oxygen-containing solvents the oxygen-containing solvents being different from alcohols, e.g. mixtures of water and ethers
-
- C11D2111/16—
-
- C11D2111/48—
Abstract
본 발명은 본래 폐기처분에 따르는 폐액을 유효하게 이용하는 것으로 에너지를 다량으로 소비하거나, 환경악화의 원인이 되는 반응로를 사용하지 않고 세정액을 염가로 얻는다. 불소이온농도가 3% 이상의 불산폐액 1l에 대하여 초산을 10∼200ml의 비율로 첨가함으로써, pH값이 1.2∼5.0으로 조정된 재생세정액을 얻는다. The present invention effectively utilizes the waste liquid according to the disposal of wastes, and thus, the washing liquid is obtained at low cost without using a large amount of energy or using a reactor that causes environmental degradation. By adding acetic acid at a rate of 10 to 200 ml with respect to 1 liter of fluorine waste liquid having a fluorine ion concentration of 3% or more, a regenerated washing liquid whose pH value is adjusted to 1.2 to 5.0 is obtained.
Description
본 발명은 스테인리스 파이프 등의 금속제품을 세정하기 위해서 각종 공업제품의 제조공정에서 배출되는 불산폐액을 금속제품의 세정액으로서 재생시키는 방법에 관한 것이다. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of regenerating fluorinated waste liquid discharged from a manufacturing process of various industrial products as a cleaning liquid for metal products in order to clean metal products such as stainless steel pipes.
금속제품의 표면에는 제조공정의 열처리나 공기 중의 산소와 접촉함으로써 산화막이 생성된다. 이 산화막은 제품의 품질저하를 초래하기 때문에 세정제거하는 것이 행해지고 있다. 예컨대, 스테인리스 파이프를 예로 들어 설명하면 표면에 산화막이 생성된 복수개의 스테인리스 파이프를 와이어로 하나로 묶어 매달고, 이것을 희불산이 저류(貯溜)된 수조 안에 수분간 담가 산화막을 세정제거하여 표면에 광택이 있는 스테인리스 파이프로 하고 있다. On the surface of the metal product, an oxide film is formed by heat treatment in the manufacturing process or contact with oxygen in the air. Since the oxide film causes a deterioration of the quality of the product, cleaning and removal are performed. For example, in the case of the stainless steel pipe as an example, a plurality of stainless steel pipes having an oxide film formed on the surface thereof are bundled and suspended, and this is immersed for several minutes in a tank in which fluoric acid is stored, and the oxide film is washed and removed to obtain a polished stainless steel surface. I do it with a pipe.
이러한 스테인리스 파이프의 세정에 사용되는 희불산은 일반적으로는 도 7의 플로우차트에 나타내는 제조공정을 거쳐 제조된다. 즉, 우선, 형석·황산교반공정 S11에서 형석과 황산을 혼합교반하고, 이어서 이것을 반응로투입공정 S12에서 로터리 킬른 등의 반응로에 투입하여 600℃ 이상의 온도조건하에서 화학반응시켜 불화수소산을 생성하고, 그 후 흡수정제공정 S13을 거쳐 농도조정공정 S14에서 불화수소산에 순수(純水)를 다량 가하여 불소이온농도 3% 정도로 희석하는 것으로 희불산이 얻어진다. The dilute hydrofluoric acid used for cleaning such stainless steel pipe is generally manufactured through a manufacturing process shown in the flowchart of FIG. 7. That is, first, fluorspar and sulfuric acid are mixed and stirred in fluorspar and sulfuric acid stirring step S11, and then, these are added to a reactor such as a rotary kiln in a reactor input step S12 and chemically reacted under a temperature condition of 600 ° C or higher to generate hydrofluoric acid. After that, a large amount of pure water is added to the hydrofluoric acid in the concentration adjusting step S14 through the absorption purification step S13, and the dilute hydrofluoric acid is obtained by diluting the fluorine ion concentration to about 3%.
그렇지만, 상술한 바와 같이 제조되는 세정액으로서의 희불산은 세정에 제공되는 금속제품이 대형이 되면 될수록 사용량이 방대해지고, 희석용의 순수사용량은 더욱 방대한 양이 되기 때문에 희불산제조비용이 금속제품 세정공정에서 큰 비중을 차지해 어떠한 해결책이 기대되고 있다. However, the dilute hydrofluoric acid as the cleaning liquid prepared as described above is used more and more when the metal product provided for cleaning becomes large, and the pure water used for dilution becomes enormous. A large portion of the solution is expected.
또한, 상기의 희불산제조공정에서는 신액(新液)인 불화수소산을 얻는 데 반응로투입공정 S12를 거치기 때문에 에너지를 다량으로 소비하는 문제가 있고, 나아가서는 원료인 형석 및 황산이나 순수의 자원소비의 문제가 있다. 또한, 형석과 황산을 600℃ 이상의 온도조건하에서 화학반응시키기 때문에 매연이 발생하여 환경이 악화되는 문제도 있다. In addition, the above-mentioned rare hydrofluoric acid manufacturing process has a problem of consuming a large amount of energy since the reactor is fed into the reactor S12 in order to obtain new hydrofluoric acid. Furthermore, it consumes resources of fluorite, sulfuric acid and pure water as raw materials. There is a problem. In addition, since fluorspar and sulfuric acid are chemically reacted at a temperature of 600 ° C. or higher, soot is generated and the environment is deteriorated.
본 발명은 이러한 점을 감안해서 이루어진 것으로, 그 목적으로 하는 바는 본래 폐기처분에 따르는 폐액을 유효하게 이용하는 것으로 에너지를 다량으로 소비하거나, 환경악화의 원인이 되는 반응로를 사용하지 않고 세정액을 염가로 얻는 것이다. The present invention has been made in view of such a point, and an object thereof is to effectively use the waste liquid which is originally disposed of, and thus to reduce the cost of the cleaning liquid without consuming a large amount of energy or using a reactor that causes environmental degradation. Is to get.
상기의 목적을 달성하기 위해서, 이 발명은 반도체제조공정 등의 각종 공업제품의 제조공정에서 배출되는 폐액을 혼합조정하여 금속제품의 세정액으로서 재이용하는 것을 특징으로 하고, 구체적으로는 다음과 같은 해결수단을 강구하였다. In order to achieve the above object, the present invention is characterized in that the waste liquid discharged from the manufacturing process of various industrial products such as semiconductor manufacturing process is mixed and reused as a cleaning liquid for metal products. Was taken.
즉, 제 1의 발명은 불소이온농도가 3% 이상의 불산폐액 1l에 대하여 초산(硝酸)을 10∼200ml의 비율로 첨가함으로써, pH값이 1.2∼5.0으로 조정된 재생세정액을 얻는 것을 특징으로 한다. That is, the first invention is characterized in that a regenerating washing liquid having a pH value of 1.2 to 5.0 is obtained by adding acetic acid at a ratio of 10 to 200 ml to 1 liter of fluorine waste liquid having a fluorine ion concentration of 3% or more. .
상기의 구성에 의해, 제 1의 발명에서는 불소이온농도가 3% 이상의 불산폐액이 재생세정액으로서 재생된다. With the above arrangement, in the first invention, a hydrofluoric acid waste solution having a fluorine ion concentration of 3% or more is regenerated as a regeneration washing liquid.
이 재생세정액은 본래 폐기처분에 따르는 폐액으로부터 얻어지기 때문에 세정액을 제조하기 위한 형석이나 황산이 필요없고, 또한 세정액생성공정에서 반응로를 사용함에 따른 다량의 에너지소비의 문제가 없으며, 세정액이 염가로 얻어진다. 또한, 반응로를 사용함에 따른 매연발생에 의한 환경악화의 문제도 없다. Since the regenerated washing liquid is originally obtained from the waste liquid following disposal, no fluorite or sulfuric acid is required to prepare the washing liquid, and there is no problem of large energy consumption by using the reactor in the washing liquid generating process, and the washing liquid is inexpensive. Obtained. In addition, there is no problem of environmental deterioration due to soot generation by using the reactor.
더욱이, 상술과 같은 불산폐액과 초산과의 혼합비율에 의해 초산폐액의 첨가량과 pH와의 관계가 직선적으로 변화하고, 금속제품의 재질에 따른 pH조정이 용이하게 되어, 세정시간 및 세정능력이 요구에 따라 자유자재로 제어가능하게 된다. Moreover, the relationship between the addition amount of acetic acid waste fluid and pH is linearly changed by the mixing ratio of the hydrofluoric acid waste solution and acetic acid as described above, and the pH adjustment according to the material of the metal product can be easily adjusted, and the cleaning time and the cleaning ability are required. Therefore, it becomes freely controllable.
제 2의 발명은 제 1의 발명에 있어서, 초산을 첨가하기 전에 불소이온농도가 3% 이상의 불산폐액으로부터 불순물을 제거하는 것을 특징으로 한다. According to a second aspect of the invention, in the first aspect of the invention, impurities are removed from the fluorine waste liquid having a fluorine ion concentration of 3% or more before adding acetic acid.
상기의 구성에 의해 제 2의 발명에서는 불순물이 포함되어 있는 불소이온농도가 3% 이상의 불산폐액이 재생세정액으로서 재생된다. With the above arrangement, in the second invention, the hydrofluoric acid waste liquid having a concentration of 3% or more of fluorine ion containing impurities is regenerated as a regeneration washing liquid.
제 3의 발명은 제 2의 발명에 있어서, 불소이온농도가 3% 이상의 불산폐액으로부터 불순물을 제거하기 전에 이 불산폐액을 불소이온농도가 3% 미만이 되도록 희석하고, 이 희석불산폐액으로부터 불순물을 제거한 뒤의 희석불산폐액을 농축하여 불소이온농도가 3% 이상의 불산폐액으로 하는 것을 특징으로 한다. In the third invention, in the second invention, the fluorine waste liquid is diluted so that the fluorine ion concentration is less than 3% and the impurities are removed from the dilute hydrofluoric acid waste liquid before the fluorine ion concentration removes impurities from the hydrofluoric acid waste solution of 3% or more. The dilute hydrofluoric acid waste solution after removal is concentrated to have a fluorine ion concentration of 3% or more.
상기의 구성에 의해 제 3의 발명에서는 불순물이 포함되어 있는 불소이온농도가 3% 이상의 불산폐액이 일단 희석되어 이 희석불산폐액으로부터 불순물이 제거되기 때문에 재생세정액이 빠르게 재생된다. With the above arrangement, in the third invention, the hydrofluoric acid waste solution containing 3% or more of the fluorine ion concentration containing impurities is once diluted, and impurities are removed from the dilute hydrofluoric acid waste liquid, and thus the regeneration washing liquid is quickly regenerated.
제 4의 발명은 불소이온농도가 3% 미만의 불산폐액을 농축하여 불소이온농도가 3% 이상의 불산폐액으로 하고, 이 불소이온농도가 3% 이상의 불산폐액 1l에 대하여 초산을 10∼200ml의 비율로 첨가함으로써 pH값이 1.2∼5.0으로 조정된 재생세정액을 얻는 것을 특징으로 한다. In the fourth aspect of the present invention, a hydrofluoric acid solution having a fluorine ion concentration of less than 3% is concentrated to a hydrofluoric acid solution having a fluorine ion concentration of 3% or more, and a ratio of 10 to 200 ml of acetic acid is added to 1 l of hydrofluoric acid solution having a fluorine ion concentration of 3% or more. It is characterized by obtaining the regeneration washing liquid whose pH value was adjusted to 1.2-5.0 by adding to the.
상기의 구성에 의해 제 4의 발명에서는 불소이온농도가 3% 미만의 불산폐액이 재생세정액으로서 재생된다. With the above arrangement, in the fourth invention, a hydrofluoric acid waste liquid having a fluorine ion concentration of less than 3% is regenerated as a regeneration washing liquid.
제 5의 발명은 제 4의 발명에 있어서, 불소이온농도가 3% 미만의 불산폐액을 농축하기 전에 이 불산폐액으로부터 불순물을 제거하는 것을 특징으로 한다. In the fourth invention, the fourth invention is characterized in that impurities are removed from the waste fluoride before the fluorine ion concentration is less than 3%.
상기의 구성에 의해 제 5의 발명에서는 불순물이 포함되어 있는 불소이온농도가 3% 미만의 불산폐액이 재생세정액으로서 재생된다. With the above arrangement, in the fifth invention, the hydrofluoric acid waste liquid having a concentration of less than 3% of fluorine ion containing impurities is regenerated as a regeneration washing liquid.
(실시예) (Example)
이하, 본 발명의 실시예에 관한 금속제품의 재생세정액의 제조방법을 스테인리스 파이프를 예로 들어 설명하지만, 이들에 한하지 않고 다른 금속제품에도 적용할 수 있는 것이다. Hereinafter, although the manufacturing method of the regeneration washing | cleaning liquid of the metal product which concerns on the Example of this invention is demonstrated using a stainless steel pipe as an example, it is not limited to these, It is applicable to other metal products.
종래예에서 설명한 바와 같이, 스테인리스 파이프는 제조공정에서 공기 중의 산소와 접촉하는 것으로 표면에 산화막이 생성되기 때문에 세정액이 저류된 수조 안에 담겨져 산화막이 세정제거되어 광택을 되찾도록 되어 있다. As described in the prior art, since the stainless steel pipe is in contact with oxygen in the air in the manufacturing process, an oxide film is formed on the surface thereof, so that the cleaning liquid is contained in a tank in which the cleaning liquid is stored, and the oxide film is washed away to restore the gloss.
본 발명에서는 상기 산화막을 세정제거하기 위한 세정액으로서 각종 공업제품의 제조공정에서 배출되는 폐액을 이용하고 있는 것을 최대의 특징으로 하고있다. 구체예를 들면, 예컨대, In the present invention, the maximum feature is that the waste liquid discharged from the manufacturing process of various industrial products is used as the cleaning liquid for cleaning and removing the oxide film. For example, for example,
(1)반도체 제조공정에서는 실리콘 웨이퍼세정공정에서 순수로 희석되어 배출되는 희석불산폐액이다. (1) In the semiconductor manufacturing process, it is a dilute hydrofluoric acid liquid that is diluted with pure water and discharged in a silicon wafer cleaning process.
(2)액정패널 제조공정에서는 액정패널의 세정 및 에칭공정에서 배출되는 불산폐액이다. (2) In the liquid crystal panel manufacturing process, it is a hydrofluoric acid waste liquid discharged from the liquid crystal panel cleaning and etching process.
(3)태양전지제품 제조공정에서는 솔라 셀의 세정 및 에칭공정에서 배출되는 불산폐액이다. (3) In the manufacturing process of solar cell products, it is a hydrofluoric acid discharged from the cleaning and etching process of solar cells.
(4)유리제품 제조공정에서는 유리의 세정 및 에칭공정에서 배출되는 불산폐액이다. (4) In the glass product manufacturing process, it is a hydrofluoric acid discharged from the glass cleaning and etching process.
(5)전구제품 제조공정에서는 내면광택제거공정 및 세정공정에서 배출되는 불산폐액이다. (5) In the manufacturing process of bulb products, it is a hydrofluoric acid solution discharged from the inner gloss removal process and the cleaning process.
(6)텔레비전제품 제조공정에서는 브라운관내면 세정공정에서 배출되는 불산폐액이다.(6) In television product manufacturing process, it is hydrofluoric acid waste discharged from the inner surface cleaning process of CRT.
(7)석재제품 제조공정에서는 석재의 표면세정공정에서 배출되는 불산폐액이다. (7) In the stone product manufacturing process, it is a hydrofluoric acid waste discharged from the surface cleaning process of the stone.
(8)프린트기판제품 제조공정에서는 프린트기판표면세정 및 탈지공정에서 배출되는 불산폐액이다. (8) In the manufacturing process of printed board products, it is a hydrofluoric acid solution discharged from the printed board surface cleaning and degreasing process.
(9)자동차 제조공정에서는 자동차 몸체의 도장공정의 탈지공정에서 배출되는 불산폐액이다. (9) In the automobile manufacturing process, it is a hydrofluoric acid solution discharged from the degreasing process of the painting process of the car body.
(제 1 실시예) (First embodiment)
도 1은 본 발명의 제 1 실시예에 관한 재생세정액의 제조방법의 제조공정을 나타내는 플로우차트이다. 여기서는 반도체 제조공정의 석영유리세정공정을 예로 들어 설명한다. 1 is a flowchart showing a manufacturing process of the method for producing a regenerated washing liquid according to the first embodiment of the present invention. Here, the quartz glass cleaning process of the semiconductor manufacturing process will be described as an example.
상기 석영유리세정공정에서 1차 세정수로서 배출되는 불산폐액은 불순물을 함유하고 있지 않은 고농도의 불산폐액이다. 이하, 고농도 불산폐액이란 불소이온농도가 3% 이상의 불산폐액을 말한다. The hydrofluoric acid waste liquid discharged as primary washing water in the quartz glass cleaning process is a high concentration hydrofluoric acid liquid containing no impurities. Hereinafter, the high concentration hydrofluoric acid liquid refers to a hydrofluoric acid liquid having a fluorine ion concentration of 3% or more.
우선, 상기의 불순물을 함유하고 있지 않은 고농도 불산폐액을 수질간이검사공정(단계 S1-1)에 반입하고, 여기서, 검지제가 혼입된 스포이트식의 수질간이검사기를 사용해 상기 고농도 불산폐액에 대하여 로트마다 유해물질의 함유검사를 행한다. 단, 상술한 바와 같이 석영유리세정공정에서 배출되는 불산폐액은 불순물을 함유하고 있지 않기 때문에 통상은 유해물질이 검출되지 않고, 다음 공정인 초산폐액첨가공정(단계 S1-2)에 반입된다. First, the high concentration hydrofluoric acid waste solution containing no above impurity is introduced into the simple water quality test step (Step S1-1), where a dropper type water quality simple tester containing a detection agent is used for each lot of the high concentration hydrofluoric acid waste solution. Carry out inspection of the hazardous substances. However, as described above, since the hydrofluoric acid waste liquid discharged from the quartz glass cleaning process does not contain impurities, no hazardous substances are normally detected and brought into the next process, the acetic acid waste liquid adding process (step S1-2).
이어서, 초산폐액첨가공정(단계 S1-2)에서 상기 고농도 불산폐액 1l에 대하여 초산을 10∼200ml의 비율로 첨가함으로써, pH값이 1.2∼5.0의 산성도범위로 조정된 재생세정액을 얻는다. 여기서는 초산으로서 반도체 제조공정의 실리콘 웨이퍼의 메사에칭공정에서 배출되는 초산폐액을 사용하고, 이 초산폐액의 첨가량은 초산농도 100%로 환산하여 10∼200ml에 상당하는 양이다. Subsequently, acetic acid is added in the ratio of 10-200 ml with respect to 1 L of said high concentration hydrofluoric acid waste liquid in the acetic acid waste liquid addition process (step S1-2), and the regeneration wash liquid whose pH value was adjusted to the acidity range of 1.2-5.0 is obtained. Here, the acetate waste liquid discharged from the mesa etching process of the silicon wafer of a semiconductor manufacturing process as an acetic acid is used, and the addition amount of this acetate waste liquid is equivalent to 10-200 ml in conversion of 100% of acetic acid concentration.
이와 같이, 불소이온농도를 3% 이상으로 설정한 것은 3% 미만에서는 스테인리스 파이프의 표면으로부터 산화막을 세정제거하는 데에 시간이 걸리고, 빠르게 제거할 수 없기 때문이다.The reason why the fluorine ion concentration is set to 3% or more is that it takes time to clean and remove the oxide film from the surface of the stainless steel pipe at less than 3% and cannot be removed quickly.
또한, 불산폐액에 대하여 초산의 첨가량과 pH와의 관계를 상술한 바와 같이 설정한 것은 도 6의 데이터로부터 분명하듯이, 상기 설정범위에서 초산폐액의 첨가량과 pH와의 관계가 염산폐액 및 황산폐액에 비해 직선적으로 변화하기 때문에, 스테인리스 파이프의 재질에 따른 pH조정을 용이하게 행할 수 있고, 세정시간 및 세정능력을 요구에 따라서 자유자재로 제어할 수 있기 때문이다. In addition, it is clear from the data of FIG. 6 that the relation between the addition amount of acetic acid and pH for the hydrofluoric acid waste liquid was set as described above, and the relation between the addition amount and pH of the acetic acid waste liquid in the above-mentioned setting range was higher than that of the hydrochloric acid waste solution and the sulfate waste liquid. It is because it changes linearly, pH adjustment according to the material of a stainless steel pipe can be performed easily, and washing time and a washing | cleaning ability can be controlled freely as needed.
더욱이, 고농도 불산폐액 1l에 대하여 초산을 30ml 첨가함으로써, 불소이온농도를 3% 이상으로 유지한 채로 pH값을 3.0 이하로 저하시킬 수 있는 것을 도 5의 데이터로부터 알 수 있다. 이로 인해, 단시간에 세정처리를 행할 수 있다. Furthermore, it can be seen from the data in FIG. 5 that 30 ml of acetic acid was added to 1 L of high concentration hydrofluoric acid waste solution, thereby reducing the pH value to 3.0 or less while maintaining the fluorine ion concentration at 3% or more. For this reason, a washing process can be performed in a short time.
또, 종래예에 있어서의 형석과 황산으로 제조되는 희불산으로는 순수로 묽게 희석된 불산이기 때문에 pH값이 상승하여 산성도가 저하하고, 세정능력을 높일 수 없지만, 본 발명의 재생세정액은 불산폐액에 초산폐액을 첨가하여 pH값을 변화시킬 수 있기 때문에 불소이온농도를 상승시켜 산성도를 크게 취하는 조정을 하지 않아도, 불소이온농도를 일정하게 한 채로 산성도를 크게 취할 수 있다. 또한, 도 5의 데이터에 의하면, 염산폐액 및 황산폐액으로는 불소이온농도는 감소하는 경향을 나타내고 있기 때문에 불소이온농도를 3% 이상으로 유지하는데 있어서는 알맞지 않은 것을 알 수 있다.In addition, the dilute hydrofluoric acid prepared from fluorspar and sulfuric acid in the prior art is hydrofluoric acid diluted with pure water, so that the pH value is increased, the acidity is lowered, and the cleaning ability cannot be improved. Since the pH value can be changed by adding acetic acid waste liquid to the acid, the acidity can be largely taken while the fluorine ion concentration is kept constant without adjusting the fluorine ion concentration to increase the acidity. In addition, the data of FIG. 5 shows that the fluoride ion concentration tends to decrease in the hydrochloric acid waste liquid and the sulfuric acid waste liquid, and thus it is not suitable for maintaining the fluorine ion concentration at 3% or more.
이것들은 하기의 화학반응식에서도 알 수 있는 바와 같이, 염산폐액 및 황산폐액은 불소이온 이외에 불화수소 이온이 생성되는 것이 고려되기 때문에 불소이온이 감소하고 있는 것으로 생각된다. As can be seen from the following chemical reaction formulas, the hydrochloric acid waste liquid and the sulfuric acid waste liquid are considered to have decreased fluorine ions since it is considered that hydrogen fluoride ions are generated in addition to the fluorine ions.
<초산폐액과 불산폐액과의 반응><Reaction of Acetic Acid and Fluoride Wastes>
<염산폐액과 불산폐액과의 반응><Reaction of Waste Acid and Hydrofluoric Acid>
<황산폐액과 불산폐액과의 반응><Reaction of Sulfate and Fluoride>
이로 인해 초산폐액을 불산폐액에 가해도 불소이온농도를 거의 저하시키는 일없이 안정된 불소이온농도를 유지한 초산첨가의 불산폐액, 즉 스테인리스 파이프세정액을 얻을 수 있다. Therefore, even if the acetic acid waste liquid is added to the hydrofluoric acid waste liquid, the acetic acid-containing hydrofluoric acid liquid having a stable fluorine ion concentration, that is, stainless steel pipe cleaning liquid, can be obtained without substantially decreasing the fluorine ion concentration.
이와 같이, 본래 폐기처분에 따르는 불산폐액을 재이용하는 것만으로 좋기 때문에 종래 필요로 했던 형석이나 황산이 필요없고, 또한 세정액생성과정에서 반응로를 사용함에 따른 다량의 에너지소비의 문제가 없으며, 세정액을 염가로 제조할 수 있다. 또한, 반응로를 사용함에 따른 매연발생에 의한 환경악화의 문제도 일어나지 않도록 할 수 있다. In this way, it is only good to reuse the waste hydrofluoric acid in accordance with the original disposal, thus eliminating the need for fluorite or sulfuric acid, which is required in the past, and eliminating the problem of a large amount of energy consumption due to the use of a reactor in the cleaning liquid generation process. It can be manufactured at low cost. In addition, it is possible to prevent the problem of environmental degradation due to the generation of smoke by using the reactor.
(제 2 실시예) (Second embodiment)
도 2는 본 발명의 제 2 실시예에 관한 재생세정액의 제조방법의 제조공정을 나타내는 플로우차트이다. 여기서는 반도체 제조공정의 실리콘 웨이퍼세정공정을 예로 들어 설명한다. Fig. 2 is a flowchart showing the manufacturing process of the method for producing the regenerated washing liquid according to the second embodiment of the present invention. Here, the silicon wafer cleaning process of the semiconductor manufacturing process will be described as an example.
상기 실리콘 웨이퍼세정공정에서 배출되는 불산폐액은 불순물을 함유하고 있는 고농도의 불산폐액이다.The hydrofluoric acid waste liquid discharged from the silicon wafer cleaning process is a high concentration of hydrofluoric acid waste liquid containing impurities.
우선, 상기의 불순물을 함유하고 있는 고농도 불산폐액을 희석공정(단계 S2-1)에 반입하고, 여기서, 순수 또는 불순물을 거의 함유하고 있지 않은 불소이온농도가 3% 미만의 불산폐액을 첨가함으로써, 불소이온농도가 3% 미만이 되도록 희석한다. 이하, 불소이온농도가 3% 미만의 불산폐액을 저농도 불산폐액이라고 한다. First, the high concentration hydrofluoric acid waste liquid containing the above impurity is brought into the dilution step (step S2-1), where a pure hydrofluoric acid concentration containing almost no pure water or impurities is added by adding a hydrofluoric acid waste liquid having a concentration less than 3%, Dilute to less than 3% fluorine ion concentration. Hereinafter, the hydrofluoric acid liquid having a fluorine ion concentration of less than 3% is called a low concentration hydrofluoric acid liquid.
이와 같이, 고농도 불산폐액을 불소이온농도가 3% 미만이 되도록 희석하는 것은 다음공정(단계 S2-2)에서 불순물을 여과재로 제거할 때, 불산폐액이 고농도라면 점도가 높아져 여과 속도가 저하하기 때문이다. Thus, diluting the high concentration hydrofluoric acid waste liquid so that the fluorine ion concentration is less than 3% is because when the impurities are removed at high concentration in the next step (step S2-2), if the hydrofluoric acid liquid is high concentration, the viscosity increases and the filtration rate decreases. to be.
또, 상기 희석공정(단계 S2-1)에서 첨가하는 불순물을 거의 함유하고 있지 않은 저농도 불산폐액이란 불순물함유농도가 수질오탁방지법에 의한 배수기준치 이하(O.1mg/l 이하)의 것이다. In addition, the low concentration hydrofluoric acid waste liquid containing almost no impurities added in the dilution step (step S2-1) means that the impurity concentration is less than the drainage threshold value (0.11 mg / l or less) by the water pollution prevention method.
이어서, 상기 희석불산폐액을 불순물제거공정(단계 S2-2)에서 여과재에 통과시켜 이 희석불산폐액으로부터 불순물을 제거한다. 또, 여과재 이외에 특정의 이온을 선택적으로 흡착하는 킬레이트제를 사용해 불용해성의 유기물 및 무기물 등의 불순물을 제거하는 것도 채용할 수 있다. Subsequently, the dilute hydrofluoric acid waste liquid is passed through a filter medium in an impurity removal step (step S2-2) to remove impurities from the dilute hydrofluoric acid waste liquid. In addition to the filter medium, it is also possible to remove impurities such as insoluble organic and inorganic substances by using a chelating agent that selectively adsorbs specific ions.
그 후, 상기 여과재를 통과한 후의 희석불산폐액을 농축공정(단계 S2-3)에 반입하고, 이온교환수지 또는 역침투막에 통과시켜 고농도 불산용액으로 한다. Thereafter, the diluted hydrofluoric acid waste solution passed through the filter medium is brought into a concentration step (step S2-3), and passed through an ion exchange resin or a reverse osmosis membrane to obtain a high concentration hydrofluoric acid solution.
여기서, 이온교환수지는 예컨대 양이온교환수지 등을 사용해 용해성의 양이온(중금속류는 거의 양이온)을 수지내에 흡착시키고, 불소이온은 음이온이기 때문에 흡착하지 않고 그대로 수지내를 통과하여 불소이온만을 모으는 것으로 농축하는 것이 가능하다. 한편, 역침투막은 막에 침투압 이상의 압력을 걸어 물만 막을 투과시키는 것으로 농축하는 것이 가능하고, 흡착에 한계가 있는 이온교환수지에 비해 고농도 불산폐액의 농축에 적합하다. 따라서, 불순물함유량이 많은 고농도 불산폐액은 역침투막을 사용해 농축하는 한편, 불순물함유량이 적은 저농도 불산폐액은 이온교환수지로 농축하는 것이 바람직하지만, 이것에 한하는 것이 아니다. 또한, 일반적으로 아세틸 셀룰로오스계나 방향족 폴리아미드계 등을 소재로 하는 역침투막은 메타크릴산계나 아크릴계를 소재로 하는 이온교환수지에 비해 염가라는 이점을 갖는다. Here, the ion exchange resin is a cation exchange resin or the like to adsorb soluble cations (heavy metals are almost cations) in the resin, and the fluorine ions are anions. It is possible. On the other hand, the reverse osmosis membrane can be concentrated by applying a pressure above the permeation pressure to the membrane so that only water permeates the membrane, and is suitable for the concentration of the high concentration hydrofluoric acid waste liquid compared to the ion exchange resin having limited adsorption. Therefore, it is preferable to concentrate the high concentration hydrofluoric acid waste liquid having a high impurity content using a reverse osmosis membrane, while the low concentration hydrofluoric acid waste liquid having a low impurity content is concentrated with an ion exchange resin. In general, reverse osmosis membranes made of acetyl cellulose, aromatic polyamide, or the like have an advantage of being inexpensive compared to ion exchange resins made of methacrylic acid or acrylic.
그런 후, 농축한 고농도 불산폐액을 수질간이검사공정(단계 S2-4)에 반입하고, 여기서, 검지제가 혼입된 스포이트식의 수질간이검사기를 사용하고, 상기 농축한 고농도 불산폐액에 대하여 로트마다 유해물질의 함유검사를 행한다. 단, 불순물은 상기 불순물제거공정(단계 S2-2)에서 제거되어 함유하고 있지 않기 때문에, 통상은 유해물질이 검출되지 않고, 다음 공정인 초산폐액첨가공정(단계 S2-5)에 반입된다. Thereafter, the concentrated high concentration hydrofluoric acid waste solution was brought into a simple water quality test step (step S2-4), where a dropper-type water quality simple tester in which a detection agent was mixed was used, and each lot was harmful to the concentrated high concentration hydrofluoric acid waste solution. Inspect the content of the substance. However, since impurities are not removed and contained in the impurity removal step (step S2-2), no hazardous substances are usually detected and carried into the next step of the acetic acid waste addition step (step S2-5).
이어서, 초산폐액첨가공정(단계 S2-5)에서 상기 고농도 불산폐액 1l에 대하여 초산을 10∼200ml의 비율로 첨가함으로써, pH값이 1.2∼5.0의 산성도범위로 조정된 재생세정액을 얻는다. 이 때, 초산으로서 초산폐액을 사용하는 것은 제 1 실시예와 같다. Subsequently, acetic acid is added in the ratio of 10-200 ml with respect to 1 L of said high concentration hydrofluoric acid waste liquid in the acetic acid waste liquid addition process (step S2-5), and the regeneration wash liquid whose pH value was adjusted to the acidity range of 1.2-5.0 is obtained. At this time, the use of acetic acid waste liquid as acetic acid is the same as in the first embodiment.
따라서, 이 제 2 실시예에서는 제 1 실시예와 같은 작용효과를 얻을 수 있다. Therefore, in this second embodiment, the same operational effects as in the first embodiment can be obtained.
(제 3 실시예) (Third embodiment)
도 3은 본 발명의 제 3 실시예에 관한 재생세정액의 제조방법의 제조공정을 나타내는 플로우차트이다. 여기서는 반도체 제조공정의 석영유리세정공정을 예로 들어 설명한다. 3 is a flowchart showing the manufacturing process of the method for producing the regenerated washing liquid according to the third embodiment of the present invention. Here, the quartz glass cleaning process of the semiconductor manufacturing process will be described as an example.
상기 석영유리세정공정에서 배출되는 2차 세정수 이후의 불산폐액은 불순물을 함유하고 있지 않은 저농도의 불산폐액이다. The fluorine waste liquid after the secondary washing water discharged from the quartz glass cleaning process is a low concentration fluorine waste liquid containing no impurities.
우선, 이 저농도 불산폐액을 농축공정(단계 S3-1)에 반입하고, 이온교환수지 또는 역침투막에 통과시켜 고농도 불산폐액으로 한다. First, the low concentration hydrofluoric acid waste solution is carried into a concentration step (step S3-1), and passed through an ion exchange resin or a reverse osmosis membrane to obtain a high concentration hydrofluoric acid waste liquid.
이어서, 농축한 고농도 불산폐액을 수질간이검사공정(단계 S3-2)에 반입하고, 여기서 검지제가 혼입된 스포이트식의 수질간이검사기를 사용해 상기 농축한 고농도 불산폐액에 대하여 로트마다 유해물질의 함유검사를 행한다. 단, 상술한 바와 같이 석영 유리세정공정에서 배출되는 불산폐액은 불순물을 함유하고 있지 않기 때문에 통상은 유해물질은 검출되지 않고, 다음 공정인 초산폐액첨가공정(단계 S3-3)에 반입된다. Subsequently, the concentrated high concentration hydrofluoric acid waste solution is brought into a simple water quality test step (step S3-2), where the concentration of harmful substances for each lot is tested for the concentrated high concentration hydrofluoric acid waste solution using a dropper type water quality simple tester in which a detection agent is incorporated. Is done. However, as described above, since the hydrofluoric acid waste liquid discharged from the quartz glass cleaning process does not contain impurities, no hazardous substances are normally detected and brought into the next process, the acetic acid waste liquid adding process (step S3-3).
그 후, 초산폐액첨가공정(단계 S3-3)에서 상기 고농도 불산폐액 1l에 대하여 초산을 10∼200ml의 비율로 첨가함으로써, pH값이 1.2∼5.0의 산성도범위로 조정된 재생세정액을 얻는다. 이 때, 초산으로서 초산폐액을 사용하는 것은 제 1 실시예와 같다. Thereafter, acetic acid is added in a ratio of 10 to 200 ml with respect to 1 l of the high concentration hydrofluoric acid waste liquid in the acetic acid waste liquid addition step (step S3-3) to obtain a regeneration washing liquid whose pH value is adjusted to an acidity range of 1.2 to 5.0. At this time, the use of acetic acid waste liquid as acetic acid is the same as in the first embodiment.
따라서, 이 제 3 실시예도 제 1 실시예와 같은 작용효과를 얻을 수 있다. Therefore, this third embodiment can also obtain the same operational effects as the first embodiment.
(제 4 실시예) (Example 4)
도 4는 본 발명의 제 4 실시예에 관한 재생세정액의 제조방법의 제조공정을 나타내는 플로우차트이다. 여기서는 반도체 제조공정에서의 실리콘 웨이퍼의 산화막에칭공정 후의 세정공정을 예로 들어 설명한다. 4 is a flowchart showing the manufacturing process of the method for producing the regenerated washing liquid according to the fourth embodiment of the present invention. Here, the cleaning process after the oxide film etching process of a silicon wafer in a semiconductor manufacturing process is demonstrated as an example.
상기 세정공정에서 배출되는 불산폐액은 불순물을 함유하고 있는 저농도의 불산폐액이다. The hydrofluoric acid waste liquid discharged from the washing process is a low concentration hydrofluoric acid liquid containing impurities.
우선, 이 저농도 불산폐액을 불순물제거공정(단계 S4-1)에서 여과재에 통과시켜 이 저농도 불산폐액으로부터 불순물을 제거한다. 또, 여과재 이외에 특정한 이온을 선택적으로 흡착하는 킬레이트제를 사용해 불용해성의 유기물 및 무기물 등의 불순물을 제거하는 것도 채용할 수 있는 것은 제 2 실시예와 같다.First, the low concentration hydrofluoric acid waste fluid is passed through a filter medium in an impurity removal step (step S4-1) to remove impurities from the low concentration hydrofluoric acid waste liquid. In addition to removing the impurities such as insoluble organics and inorganics using a chelating agent that selectively adsorbs specific ions other than the filter medium, it is the same as in the second embodiment.
이어서, 농축공정(단계 S4-2)에 반입하고 이온교환수지 또는 역침투막에 통과시켜 고농도 불산용액으로 한다. 어떤 것을 사용할지는 작업효율 등을 고려하여 적당하게 선택하면 좋다. Subsequently, it carries out to a concentration process (step S4-2), and it passes through an ion exchange resin or a reverse osmosis membrane, and makes it the high concentration hydrofluoric acid solution. Which one to use should be properly selected in consideration of work efficiency.
그 후, 농축한 고농도 불산폐액을 수질간이검사공정(단계 S4-3)에 반입하고, 여기서 검지제가 혼입된 스포이트식의 수질간이검사기를 사용해 상기 농축한 고농도 불산폐액에 대하여 로트마다 유해물질의 함유검사를 행한다. 단, 불순물은 상기 불순물제거공정(단계 S4-1)에서 제거되어 함유하고 있지 않기 때문에 통상은 유해물질은 검출되지 않고, 다음 공정인 초산폐액첨가공정(단계 S4-4)에 반입된다. Thereafter, the concentrated high concentration hydrofluoric acid waste solution is brought into a simple water quality test step (step S4-3), wherein the concentrated high concentration hydrofluoric acid waste solution is contained for each lot in the concentrated high concentration hydrofluoric acid waste solution using a dropper-type water quality simple tester in which a detection agent is incorporated. Check However, since impurities are not removed and contained in the impurity removal step (step S4-1), no hazardous substances are normally detected and carried into the next step of acetic acid waste addition step (step S4-4).
그런 후, 초산폐액첨가공정(단계 S4-4)에서 상기 고농도 불산폐액 1l에 대하여 초산을 10∼200ml의 비율로 첨가함으로써, pH값이 1.2∼5.0의 산성도범위로 조정된 재생세정액을 얻는다. 이 때, 초산으로서 초산폐액을 사용하는 것은 제 1 실시예와 같다. Thereafter, acetic acid is added at a rate of 10 to 200 ml with respect to 1 l of the high concentration hydrofluoric acid waste liquid in the acetic acid waste liquid adding step (step S4-4) to obtain a regeneration washing liquid having a pH value adjusted to an acidity range of 1.2 to 5.0. At this time, the use of acetic acid waste liquid as acetic acid is the same as in the first embodiment.
따라서, 이 제 4 실시예도 제 1 실시예와 같은 작용효과를 얻을 수 있다.Therefore, this fourth embodiment can also obtain the same operational effects as the first embodiment.
이상 설명한 바와 같이, 제 1의 발명에 의하면 불소이온농도가 3% 이상의 불산폐액 1l에 대하여 초산을 10∼200ml의 비율로 첨가함으로써 pH값이 1.2∼5.0으로 조정된 재생세정액을 얻는다. 이 때, 불순물이 포함되어 있는 경우에는 불순물제거공정(제 2의 발명)을 거치고, 추가로 희석공정(제 3의 발명)을 거치는 것이 바람직하다. 한편, 불소이온농도가 3% 미만의 불산폐액의 경우는 제 4의 발명과 같이 불소이온농도가 3% 이상으로 농축된 뒤, 이 농축한 불산폐액 1l에 대하여 초산을 10∼200m1의 비율로 첨가함으로써, pH값이 1.2∼5.0으로 조정된 재생세정액을 얻는다. 이 때, 불순물이 포함되어 있는 경우에는 불순물제거공정(제 5의 발명)을 거친다. 따라서, 세정액을 형석, 황산 및 반응로를 사용하는 일없이 염가로 또한 환경악화를 초래하지 않고 제조할 수 있는 동시에, 금속제품의 재질에 따른 용이한 pH조정에 의해 세정시간 및 세정능력을 자유자재로 제어할 수 있다. As described above, according to the first invention, a regeneration washing liquid having a pH value adjusted to 1.2 to 5.0 is obtained by adding acetic acid at a ratio of 10 to 200 ml to 1 liter of fluorine waste liquid having a fluorine ion concentration of 3% or more. At this time, when impurities are contained, it is preferable to go through an impurity removal process (second invention) and to carry out a dilution process (third invention) further. On the other hand, in the case of the fluorine waste liquid having a fluorine ion concentration of less than 3%, as in the fourth invention, the fluorine ion concentration is concentrated to 3% or more, and then acetic acid is added at a ratio of 10 to 200 m1 to 1 l of the concentrated fluorine waste liquid. As a result, a regeneration washing liquid whose pH value is adjusted to 1.2 to 5.0 is obtained. At this time, when impurities are contained, an impurity removal process (fifth invention) is performed. Therefore, it is possible to manufacture the cleaning liquid at low cost and without causing environmental degradation without using fluorite, sulfuric acid, and reactor, and at the same time, it is possible to freely adjust the cleaning time and washing ability by adjusting the pH according to the material of the metal product. Can be controlled by
도 1은 본 발명의 제 1 실시예에 관한 재생세정액의 제조방법의 제조공정을 나타내는 플로우차트1 is a flowchart showing a manufacturing process of the method for producing a regenerated washing liquid according to the first embodiment of the present invention.
도 2는 본 발명의 제 2 실시예에 관한 재생세정액의 제조방법의 제조공정을 나타내는 플로우차트Fig. 2 is a flowchart showing the manufacturing process of the method for producing the regenerated washing liquid according to the second embodiment of the present invention.
도 3은 본 발명의 제 3 실시예에 관한 재생세정액의 제조방법의 제조공정을 나타내는 플로우차트 Fig. 3 is a flowchart showing the manufacturing process of the method for producing the regenerated washing liquid according to the third embodiment of the present invention.
도 4는 본 발명의 제 4 실시예에 관한 재생세정액의 제조방법의 제조공정을 나타내는 플로우차트 4 is a flowchart showing a manufacturing process of the method for producing the regenerated washing liquid according to the fourth embodiment of the present invention.
도 5는 불산폐액에 초산, 염산 및 황산을 첨가한 경우의 pH와 불소 이온농도와의 관계를 나타내는 데이터5 is a data showing the relationship between pH and fluorine ion concentration when acetic acid, hydrochloric acid and sulfuric acid are added to a hydrofluoric acid waste liquid.
도 6은 불산폐액에 대한 초산, 염산 및 황산의 첨가량과 pH와의 관계를 나타내는 데이터6 is a data showing the relationship between the amount of acetic acid, hydrochloric acid and sulfuric acid added to the hydrofluoric acid and pH
도 7은 종래예의 세정액의 제조방법의 제조공정을 나타내는 플로우차트7 is a flowchart showing a manufacturing process of the manufacturing method of the cleaning liquid of a prior art example.
*도면의 주요부분에 대한 부호의 설명** Description of the symbols for the main parts of the drawings *
S1-1, S2-4, S3-2, S4-3 : 수질간이검사공정 S1-1, S2-4, S3-2, S4-3: Water Quality Simple Inspection Process
S1-2, S2-5, S3-3, S4-4 : 초산폐액첨가공정S1-2, S2-5, S3-3, S4-4: Acetic Acid Addition Process
S2-1 : 희석공정 S2-2, S4-1 : 불순물제거공정S2-1: Dilution process S2-2, S4-1: Impurity removal process
S2-3, S3-1, S4-2 : 농축공정S2-3, S3-1, S4-2: concentration process
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| KR970018267A (en) * | 1995-09-01 | 1997-04-30 | 모리 가즈히로 | Cleaning, etching, and drying apparatus for semiconductor wafers and methods of using the same |
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