KR100923860B1 - Method of making portable analysis kit for rapid measurement of HF concentration in mixed solution - Google Patents

Method of making portable analysis kit for rapid measurement of HF concentration in mixed solution Download PDF

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KR100923860B1
KR100923860B1 KR1020070135666A KR20070135666A KR100923860B1 KR 100923860 B1 KR100923860 B1 KR 100923860B1 KR 1020070135666 A KR1020070135666 A KR 1020070135666A KR 20070135666 A KR20070135666 A KR 20070135666A KR 100923860 B1 KR100923860 B1 KR 100923860B1
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concentration
hydrofluoric acid
acid
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test tube
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KR20090067862A (en
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조윤현
최상교
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주식회사 포스코
재단법인 포항산업과학연구원
포스코신기술연구조합
포스코특수강 주식회사
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    • G—PHYSICS
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    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
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Abstract

본 발명은 불산이 포함된 혼합산 용액중에서 불산농도의 선택적 분석 및 불산분석을 위한 1회용 분석 Kit의 제조 방법에 관한 것으로, 불산이 다른 종류의 산이나 용액과 혼합되어 있을 때 유리불산의 농도만을 선택적으로 분석할 수 있는 방법과 이의 분석 절차를 대폭 감소시켜 분석하고자 하는 시료를 kit에 투입하여 발색시킨 다음 흡광도를 측정함으로써 즉시 그 결과를 확인할 수 있는 1회용 분석 Kit의 제조 방법이다. The present invention relates to a method for preparing a disposable assay kit for the selective analysis of hydrofluoric acid concentration and hydrofluoric acid in a mixed acid solution containing hydrofluoric acid, wherein the concentration of free hydrofluoric acid when hydrofluoric acid is mixed with another acid or solution It is a manufacturing method of disposable analysis kit which can confirm the result immediately by inserting the sample to be analyzed into the kit by greatly reducing the analysis procedure and its analysis procedure.

본 발명에 따르면 0~100g/L까지의 불산이 질산, 황산, 인산, 염산 등 다양한 혼합산에 공존할 때 불산만의 농도를 선택적으로 분석할 수 있어 스테인레스 산세공정, 반도체 세정공정, 유리식각 공정 등 다양한 공정의 불산농도를 정밀하게 측정할 수 있는 효과가 있으며, 1회용 분석 Kit를 제공함으로써 신속하게 농도분석 및 공정관리가 가능하다.According to the present invention, when hydrofluoric acid from 0 to 100 g / L coexists in various mixed acids such as nitric acid, sulfuric acid, phosphoric acid and hydrochloric acid, it is possible to selectively analyze the concentration of hydrofluoric acid. It is effective to precisely measure the concentration of hydrofluoric acid in various processes, and it is possible to quickly analyze concentration and process by providing disposable analysis kit.

불산, 분석, Kit, 흡광도, 아세틸아세톤 Folic Acid, Analysis, Kit, Absorbance, Acetyl Acetone

Description

불산이 포함된 혼합용액 중 불산 농도의 신속한 분석을 위한 1회용 분석 Ｋｉｔ의 제조방법 {Method of making portable analysis kit for rapid measurement of HF concentration in mixed solution}Method of making portable analysis kit for rapid measurement of HF concentration in mixed solution for rapid analysis of hydrofluoric acid concentration in mixed solution containing hydrofluoric acid

본 발명은 불산이 포함된 혼합산 용액중에서 불산농도의 선택적 분석 및 불산분석을 위한 1회용 분석 Kit의 제조 방법에 관한 것으로, 보다 자세하게는 불산이 다른 종류의 산이나 용액과 혼합되어 있을 때 유리불산의 농도만을 선택적으로 분석할 수 있는 방법과 이의 분석 절차를 대폭 감소시켜 분석하고자 하는 시료를 kit에 투입하여 발색시킨 다음 흡광도를 측정함으로써 즉시 그 결과를 확인할 수 있는 1회용 분석 Kit의 제조 방법을 제공하는 것이다. The present invention relates to a method for preparing a disposable assay kit for selective analysis of hydrofluoric acid concentration and hydrofluoric acid analysis in a mixed acid solution containing hydrofluoric acid, and more particularly, when hydrofluoric acid is mixed with another acid or solution. Provides a method of selectively analyzing the concentration of and a method of manufacturing a disposable analysis kit that can immediately confirm the results by adding a sample to be analyzed and developing the color of the sample to be analyzed by greatly reducing its analysis procedure. It is.

이를 위해 아세틸아세톤 용액과 Fe 3가 이온에 의해 착화합물을 형성하여 적갈색을 띤 용액을 제조하고 여기에 불산이 포함된 시료를 투입할 때, 불산이 Fe와 반응하여 아세틸 아세톤과의 착화합물을 파괴함으로써 발색된 색의 농도가 엷어지는 원리를 이용하여 혼합용액 중에서 불산농도를 선택적으로 분석하는 방법에 관한 것이다.To this end, a complex compound is formed by the acetylacetone solution and Fe trivalent ions to prepare a reddish brown solution. When a sample containing hydrofluoric acid is added thereto, the hydrofluoric acid reacts with Fe to destroy the complex compound with acetyl acetone. The present invention relates to a method for selectively analyzing hydrofluoric acid concentration in a mixed solution by using the principle of thinning of a concentrated color.

본 발명에 따르면 0~100g/L까지의 불산이 질산, 황산, 인산, 염산 등 다양한 혼합산에 공존할 때 불산만의 농도를 선택적으로 분석할 수 있어 스테인레스 산세공정, 반도체 세정공정, 유리식각 공정 등 다양한 공정의 불산농도를 정밀하게 측정할 수 있는 효과가 있으며, 1회용 분석 Kit를 제공함으로써 신속하게 농도분석 및 공정관리가 가능하다.According to the present invention, when hydrofluoric acid from 0 to 100 g / L coexists in various mixed acids such as nitric acid, sulfuric acid, phosphoric acid and hydrochloric acid, it is possible to selectively analyze the concentration of hydrofluoric acid. It is effective to precisely measure the concentration of hydrofluoric acid in various processes, and it is possible to quickly analyze concentration and process by providing disposable analysis kit.

불산이 포함된 혼합용액은 스테인레스강의 산세에 이용되는 질산, 불산 혹은 불산, 황산, 과산화수소 혹은 반도체 및 유리 식각 등에 사용하는 불산, 질살, 불화암모늄 등 다양한 공정에 사용된다. 이 공정에서는 제품의 품질 안정을 위해 용액중의 불산 농도를 일정하게 관리할 필요가 있는데, 이의 분석을 위해서는 세계적으로 몇 안 되는 분석법만 알려져 있다. 현재까지 알려진 방법은 다음과 같다.The mixed solution containing hydrofluoric acid is used in various processes such as nitric acid, hydrofluoric acid or hydrofluoric acid, sulfuric acid, hydrogen peroxide or hydrofluoric acid, nitrate, ammonium fluoride and the like used for pickling stainless steel. In this process, it is necessary to control the concentration of hydrofluoric acid in the solution in order to stabilize the quality of the product. Only a few analytical methods are known worldwide for its analysis. The methods known to date are as follows.

첫째, 불소선택적 전극과 수소선택적 전극을 이용하여 산용액중의 총산과 불산을 분리분석하는 방법 (US 4060717, Leco Corp or SCANACON)이 있는데, 이 방법으로는 불산과 다른 한 종류의 산이 혼합되어 있을 때만 분석기 가능하나, 그 장비가 고가이고 전극의 수명이 길지 않아 유지관리에 많은 비용이 소요된다.First, there is a method of separating and analyzing total acid and hydrofluoric acid in an acid solution using a fluorine selective electrode and a hydrogen selective electrode (US 4060717, Leco Corp or SCANACON). The analyzer can be used only when it is available, but the equipment is expensive and the life of the electrode is not long, so maintenance is expensive.

둘째, 가성소다에 의해 중화적정을 하면서 용액의 온도와 전기전도도를 동시에 모니터링하여 불산과 혼산 및 메탈의 농도를 결정하는 방법 (US 5518933)이 있으나, 역시 고가의 Thermo titrator가 필요한 단점이 있다.Second, there is a method of determining the concentration of hydrofluoric acid, mixed acid and metal by simultaneously monitoring the temperature of the solution and the electrical conductivity while neutralizing titration with caustic soda (US 5518933), but also has the disadvantage of requiring an expensive thermo titrator.

셋째, J.P. McKaveney 가 발표한 흡광도 분석방법 (Analytical Chemistry, Vol. 40, No. 8, 1968, "Spectrophotometric Method for Hydrofluoric Acid in Stainless Steel Pickling Batshs)"과 이 방법을 자동화시킨 사례 (Masahiko ITO et al., ISIJ, Vol 37., No. 1, pp. 47-54, 1997, "Development of an Automatic Analyzer for a Mixed Nitric Acid, Hydrofluoric Acid, and Iron Ion in the Pickling Process")가 있으나 자동화한 과정이 복잡하고 고가의 분석장비를 필요로 한다.Third, J.P. McKaveney published an absorbance analysis method (Analytical Chemistry, Vol. 40, No. 8, 1968, "Spectrophotometric Method for Hydrofluoric Acid in Stainless Steel Pickling Batshs") and an example of automating it (Masahiko ITO et al., ISIJ, Vol 37., No. 1, pp. 47-54, 1997, "Development of an Automatic Analyzer for a Mixed Nitric Acid, Hydrofluoric Acid, and Iron Ion in the Pickling Process", but the automated process is complex and expensive. Requires analytical equipment

그 외에도 다양한 시도가 있었으나, 대부분 실용적이지 못한 방법이며 실제로 사용되는 경우는 상기의 세 종류의 응용 정도가 전부이다.In addition, various attempts have been made, but most of them are not practical methods, and all of the above three kinds of applications are practically used.

공지기술인 흡광도 분석방법에 의한 불산농도 분석법은 과음과 같은 절차를 거친다. The hydrofluoric acid concentration method by the absorbance analysis method known in the art goes through the same procedure as heavy drinking.

1. 시약: 1. Reagents:

A. Iron Solution: 1g/L FeSO4.7H2O (4.9776g의 FeSO4.7H2O 시약을 200mL 증류수에 녹이고 여기에 농황산 1mL를 가한 다음 이 용액에 30% 과산화수소 4mL를 투입하고 끓인다. 끓인 다음 이를 다시 식혀 1L 용기에 옮긴 다음 증류수로 1L를 채워 준비한다)A. Iron Solution:. 1g / L FeSO 4 .7H 2 O ( dissolved in 4.9776g of FeSO 4 .7H 2 O reagent to 200mL of distilled water added to 30% aqueous hydrogen peroxide solution was added to concentrated sulfuric acid followed by 4mL in 1mL herein and simmer boiled Then cool it and transfer it to a 1L container and fill with 1L of distilled water to prepare)

B. Nitric Acid Medium: 0.1N HNO3 (12.5mL의 진한 질산 (70%)을 2L 용량 플라스크에 넣고 증류수로 채운다)B. Nitric Acid Medium: 0.1 N HNO 3 (12.5 mL concentrated nitric acid (70%) is placed in a 2 L flask and filled with distilled water)

C. Acetylacetone Solution: 1% Acetylacetone (10mL의 acetylaceton 용액을 1L 용기에 투입하고 여기에 600mL 증류수를 채워 충분히 용해시킨다. 그 다음 1L로 증류수를 채워 준비한다.)C. Acetylacetone Solution: 1% Acetylacetone (Place 10 mL acetylaceton solution in a 1 L container and add 600 mL distilled water to dissolve well. Then fill with 1 L distilled water.)

2. 분석 절차2. Analysis procedure

A. 시료조제: 5mL의 시료를 채취하여 용기에 넣고 증류수를 가하여 150mL로 한다.A. Sample preparation: Take 5 mL of sample, put it in the container and add 150 mL of distilled water.

B. 분석: 100mL 용량 플라스크에 질산용액 60mL 넣고, 다시 10mL의 Iron solution을 투입한 다음 5mL의 아세틸아세톤 용액을 투입한다. 여기에 5mL의 조제한 시료를 투입하여 100mL가 되도록 질산용액으로 맞춘다. 이를 잘 혼합하여 470nm 에서 흡광도를 측정한다.B. Analysis: Into a 100 mL flask, add 60 mL of nitric acid solution, add 10 mL of Iron solution, and then add 5 mL of acetylacetone solution. 5 mL of the prepared sample is added to this solution and the mixture is adjusted to nitric acid solution to make 100 mL. Mix it well and measure the absorbance at 470 nm.

C. 계산: 사전에 준비된 검량선을 통해 흡광도 값을 이용하여 불산의 농도를 측정한다. C. Calculation: Measure the concentration of hydrofluoric acid using absorbance values through a calibration curve prepared in advance.

상기 방법에서 보듯이 시료채취에서 측정까지 상당히 많은 절차가 필요하며, 숙련자가 아니면 쉽게 할 수 있는 분석방법이 아님을 알 수 있다.As shown in the above method, a lot of procedures are required from sampling to measurement, and it can be seen that it is not an analytical method that can be easily performed by an expert.

이에, 본 발명은 상술한 바와 같은 종래의 문제점을 개선시키기 위한 것으로 그 목적은, 1회용 분석 Kit를 제공함으로써 불산이 포함된 혼합 시료중의 불산 농도를 측정할 수 있는 신속하고 간단한 방법을 제공하는데 있다.Accordingly, the present invention is to improve the conventional problems as described above, the object is to provide a quick and simple method for measuring the concentration of hydrofluoric acid in the mixed sample containing hydrofluoric acid by providing a disposable analysis kit. have.

본 발명은 불산이 포함된 혼합용액에서의 불산의 선택적 분석방법에 있어서, 시약 A, B 및 C를 혼합하여 흡광도 직접 측정이 가능한 시험관에 분취하여 다수의 분석용 Kit를 제조하고, 이 시험관에 미지의 시료 적정량을 투입하여 사전에 준비된 검량선에 의하여 불산 (HF) 농도를 직접 측정할 수 있는 것이 특징이다.The present invention is a selective analysis method of hydrofluoric acid in a mixed solution containing hydrofluoric acid, by mixing reagents A, B and C in a test tube capable of directly measuring the absorbance to prepare a plurality of analysis kits, unknown to the test tube It is characterized in that the concentration of hydrofluoric acid (HF) can be directly measured by using a calibration curve prepared in advance by inputting an appropriate amount of the sample.

본 발명에 따르면, 혼합용액 중의 불산 농도 분석을 1회용 kit로 손쉽게 할 수 있음으로 인해, 스테인레스 산세공정, 반도체 식각공정 등과 같이 공정중의 불산농도를 지속적으로 분석하여야 하는 경우에 신속한 의사결정이 가능하고 비 숙련자도 분석이 가능하여 업무 효율을 매우 향상할 수 있는 효과가 있다.According to the present invention, it is possible to easily analyze the concentration of hydrofluoric acid in the mixed solution with a single-use kit, so that quick decision making is possible in the case of continuously analyzing the concentration of hydrofluoric acid in the process such as stainless pickling process and semiconductor etching process. In addition, it is possible to analyze even unskilled people, which can greatly improve work efficiency.

본 발명에서는 공지기술인 흡광도 분석방법을 응용하여 산세용액중의 불산농도를 신속하게 분석할 수 있는 1회용 분석 Kit를 제조하는 방법을 제공하는 것이다.The present invention is to provide a method for producing a disposable analysis kit that can quickly analyze the concentration of hydrofluoric acid in the pickling solution by applying a known absorbance analysis method.

즉, 본 발명은 하기 시약 A, B 및 C를 혼합하여 흡광도 직접 측정이 가능한 시험관에 분취하여 다수의 분석 Kit를 제조하고, 이 시험관에 미지의 시료 적정량을 투입하여 사전에 준비된 검량선에 의하여 티오시안(SCN) 농도를 직접 측정할 수 있는 불산이 포함된 혼합용액 중 불산 농도의 신속한 분석을 위한 1회용 분석 Kit의 제조방법이다.That is, the present invention is prepared by mixing the following reagents A, B and C in a test tube capable of directly measuring the absorbance to prepare a number of assay kits, and the appropriate amount of the unknown sample is added to the test tube by the previously prepared calibration curve (SCN) This is a method of preparing a disposable assay kit for the rapid analysis of hydrofluoric acid concentration in a mixed solution containing hydrofluoric acid that can directly measure the concentration.

- 시약 A: Iron Solution: 1g/L FeSO4.7H2O (4.9776g의 FeSO4.7H2O 시약을 200mL 증류수에 녹이고 여기에 농황산 1mL를 가한 다음 이 용액에 30% 과산화수소 4mL를 투입하고 끓인다. 끓인 다음 이를 다시 식혀 1L 용기에 옮긴 다음 증류수로 1L를 채워 준비한다)- Reagent A: Iron Solution: 1g / L FeSO 4 .7H 2 O ( dissolved in 4.9776g of FeSO 4 .7H 2 O reagent to 200mL of distilled water was added to concentrated sulfuric acid 1mL herein boil and then added 30% hydrogen peroxide was added 4mL Boil and cool it down, transfer to 1L container, and fill with 1L of distilled water.

- 시약 B: Nitric Acid Medium: 0.1N HNO3 (12.5mL의 진한질산 (70%)을 2L 용량 플라스크에 넣고 증류수로 채운다)Reagent B: Nitric Acid Medium: 0.1 N HNO 3 (12.5 mL concentrated nitric acid (70%) is placed in a 2 L flask and filled with distilled water)

- 시약 C: Acetylacetone Solution: 1% Acetylacetone (10mL의 acetylaceton 용액을 1L 용기에 투입하고 여기에 600mL 증류수를 채워 충분히 용해시킨다. 그 다음 1L로 증류수를 채워 준비한다.)Reagent C: Acetylacetone Solution: 1% Acetylacetone (Add 10 mL of acetylaceton solution to 1 L container, add 600 mL of distilled water to dissolve well. Then, fill with 1 L of distilled water.)

구체적으로 본 발명은, 흡광도 분석법에서와 동일한 농도의 시약을 준비한 다음 10mL 이상의 용량이 되는 시험관 중 시험관의 투입으로 흡광도가 즉시 측정될 수 있는 규격 (16mm이하 지름의 시험관)의 시험관을 준비하고 여기에 시약 A를 1mL, 시약 B를 8mL, 시약 C를 0.5mL를 투입하여 준비한다. 이렇게 할 경우 원래의 방법에서 시료를 제외한 모든 종류의 시약이 포함된 시험관을 준비한 것이며, 그 비율 역시 거의 동일한 상태가 된다. 이렇게 준비된 시험관을 이용하여 불산 1~5% 표준용액을 준비한 다음 이 표준액 100uL씩을 취하여 상기 준비된 시험관에 투입한다. 이 경우 시험관의 총 부피는 9.51mL 가 되며, 원래 방법의 100mL의 약 9.5%로 용액량이 감소한다. 이 시험관을 흡광도 직접 측정이 가능한 흡광광도계에 투입하여 증류수가 투입된 용액으로 0점 조절한 다음 검량선을 작성한다. 이후 미지의 시료 1mL를 시험관에 투입하여 흡광도를 측정한 다음 검량선에 의하여 농도를 계산한다. 준비된 시험관의 개수에 따라서 분석할 수 있는 시료의 양이 정해지게 되며, 1번 분석된 시험관은 폐기처분 할 수 있으며, 한번에 대량으로 만들어 놓을 경우 불산 분석을 시험관에 시료 100uL를 투입하고 흡광도를 측정하는 조작만으로 지속적인 농도 분석이 가능하여 1회용 분석 kit를 완성할 수 있다. 이 절차를 도 1에 자세하게 나타내었다. 또한 초기 시약의 농도를 더욱 묽은 용액이나 진한 용액을 만들어 그 채취량을 비율에 맞게 조절하여 사용할 수도 있다. 이렇게 제조된 Kit의 모습을 도 2에 사진으로 나타내었다. 도 3에는 본 발명에 의해 제조된 Kit를 이용하여 표준액의 흡광도와 불산 농도와의 상관관계를 나타내는 검량선의 작성 예를 나타내었다. 검량선은 직선관계에 있지 않으며, 지수함수적으로 흡광도가 감소하는 특징이 있다. 이 검량선을 이용하여 농도값을 계산할 수 있다.Specifically, the present invention, by preparing a reagent of the same concentration as in the absorbance analysis method and then prepare a test tube of the specification (test tube of 16mm or less diameter) that can be measured immediately by the input of the test tube in the test tube having a capacity of 10mL or more Prepare 1 mL of reagent A, 8 mL of reagent B, and 0.5 mL of reagent C. In this case, a test tube containing all kinds of reagents except the sample is prepared in the original method, and the ratio is almost the same. Prepare a 1-5% standard solution of hydrofluoric acid using the test tube thus prepared, and take 100 uL of this standard solution into the prepared test tube. In this case, the total volume of the test tube is 9.51 mL, and the solution amount is reduced to about 9.5% of 100 mL of the original method. The test tube is placed in an absorbance photometer that can directly measure absorbance. The test tube is adjusted to zero with distilled water. Then 1mL of unknown sample is added to the test tube to measure the absorbance and then the concentration is calculated by the calibration curve. The number of samples to be analyzed is determined according to the number of test tubes prepared, and the test tubes analyzed once can be discarded.If a large amount is made at a time, 100 μL of the sample is injected into the test tube and the absorbance is measured. Consistent concentration analysis is possible only by manipulation, thus completing the disposable analysis kit. This procedure is shown in detail in FIG. 1. In addition, the concentration of the initial reagent can be used to make a thinner or thicker solution and adjust the sampling rate accordingly. Figure 2 shows the state of the kit prepared as shown in FIG. 3 shows an example of preparation of a calibration curve showing a correlation between absorbance of a standard solution and hydrofluoric acid concentration using a kit prepared according to the present invention. The calibration curve is not in a straight line relationship and has an exponential decrease in absorbance. This calibration curve can be used to calculate concentration values.

본 발명에서와 같은 절차를 이용할 경우 문제가 될 수 있는 것은 장기간 보관하였을 경우의 변색이나 분석 오차가 발생할 수 있는 여지가 있다. 따라서 이에 대한 검토를 수행하였는데, 도 4에 그 결과를 나타내었다. 도 4에서 보는 바와 같이 약 10분 동안에는 반응에 의해 흡광도가 다소 상승하지만, 그 이후에는 2개월 이상 보관하였을 경우에도 흡광도의 변화가 거의 없는 것을 알 수 있다. 이하 본 발명의 효과를 실시 예를 통해 보다 자세하게 알아 본다.What may be a problem when using the procedure as in the present invention is that there is a possibility that discoloration or analysis error may occur when stored for a long time. Therefore, a review was performed, and the results are shown in FIG. 4. As shown in FIG. 4, the absorbance is slightly increased by the reaction for about 10 minutes, but thereafter, even when stored for two months or more, there is almost no change in absorbance. Hereinafter, the effects of the present invention will be described in more detail with reference to the following examples.

실시예Example

스테인레스강의 산세에서는 불산과 황산 및 과산화수소를 이용한 산세가 최 근 많이 행해지고 있으며, 일부는 질산과 불산의 혼합산에 의하여 주로 행해지고 있다. 이때 불산의 농도가 스테인레스강 산세속도에 매우 민감하게 영향을 끼치므로 농도 관리가 매우 중요하다. 그러나 종래 분석 방법에 의해서는 숙련된 분석자가 고급기기를 통해 분석해야 하므로 분석 시간이 많이 소요되고 시료를 분석을 위한 장소로 이송해야 하는 불편함이 있어 공정에서 직접 활용이 곤란하였다. 그러나 본 발명에 의한 kit의 제조로 누구라도 손쉽게 분석이 가능하게 된 것이다. 본 kit의 효과를 확인해 보기 위해 스테인레스강 산세공정에서 사용되는 혼합산 용액인 불산 4%, 황산 8%, 과산화수소가 포함된 용액을 이용하여 산세를 진행하면서 용액중의 농도 변화를 분석하여 보았다. 분석 결과는 SCANACON S50 자동 분석기와 그 결과를 함께 비교하였다. 그 결과를 표 1에 나타내었다. In the pickling of stainless steel, pickling using hydrofluoric acid, sulfuric acid, and hydrogen peroxide has recently been performed, and some of them are mainly performed by a mixed acid of nitric acid and hydrofluoric acid. At this time, the concentration of hydrofluoric acid is very sensitive to the pickling rate of stainless steel, so the concentration management is very important. However, the conventional analytical method requires a skilled analyst to analyze through an advanced device, which requires a lot of analysis time and the inconvenience of having to transfer a sample to a place for analysis. However, anyone can easily analyze the production of the kit according to the present invention. In order to verify the effectiveness of this kit, the concentration of the solution was analyzed while pickling using a solution containing 4% hydrofluoric acid, 8% sulfuric acid, and hydrogen peroxide, which were used in the stainless steel pickling process. The analysis results were compared with the SCANACON S50 automatic analyzer. The results are shown in Table 1.

본 발명에 의한 Kit로 분석한 스테인레스 산세용액의 불산 분석 결과Hydrofluoric acid analysis result of stainless pickling solution analyzed by Kit according to the present invention 시료번호Sample Number 본 발명에 의한 불산 농도 분석결과Hydrofluoric acid concentration analysis results according to the present invention 자동분석기Automatic analyzer 분석자 AAnalyst A 분석자 BAnalyst B 분석자 CAnalyst C 불산Foshan 황산Sulfuric acid 1One 4.114.11 4.024.02 4.134.13 4.214.21 8.38.3 22 3.363.36 3.383.38 3.413.41 3.423.42 6.36.3 33 2.172.17 2.212.21 2.052.05 2.342.34 5.75.7 44 1.651.65 1.541.54 1.681.68 1.821.82 4.14.1 55 0.980.98 0.940.94 1.011.01 1.211.21 3.23.2 66 0.840.84 0.860.86 0.880.88 1.041.04 2.22.2 77 0.820.82 0.790.79 0.750.75 0.740.74 1.61.6 88 0.670.67 0.640.64 0.620.62 0.650.65 1.51.5 평균 에러율 (%)Average error rate (%) 9.119.11 9.329.32 7.527.52 -- --

상기 표로부터, 분석 결과는 오차범위 10% 미만에서 비교적 잘 일치하고 있으며, 서로 다른 분석자가 분석하여도 분석오차가 크게 발생하지 않음을 잘 알 수 있다. 이 분석을 통해 산세가 진행되면서 불산의 농도와 황산농도의 변화를 잘 예측할 수 있다. 본 실시예에서 황산의 농도는 자동분석 장치를 이용한 값을 그대로 이용하였다. 한편, 황산의 농도에 따른 불산 분석 값의 변화가 있을 수 있으므로 이에 대한 영향을 살펴보았는데, 그 결과는 도 5에 나타내었다. 도면에서 보듯이 황산 농도가 2~8%까지 변함에 따라 분석된 불산 농도 (2% 표준액)는 1.93%~2.06 %까지 아주 미미하게 변화되어 황산농도에 크게 영향을 받지 않음을 알 수 있다.From the table, the analysis results are relatively well matched in the error range less than 10%, it can be seen that the analysis error does not occur significantly even if analyzed by different analysts. This analysis can predict the change in the concentration of hydrofluoric acid and sulfuric acid as the pickling progresses. In the present example, the concentration of sulfuric acid was used as it was using an automatic analyzer. On the other hand, since there may be a change in the hydrofluoric acid analysis value according to the concentration of sulfuric acid, the effect on this was examined, the results are shown in FIG. As shown in the figure, the hydrofluoric acid concentration (2% standard solution) analyzed as the sulfuric acid concentration changed from 2% to 8% was changed very slightly from 1.93% to 2.06%, indicating that the sulfuric acid concentration was not significantly affected.

도 1은 불산 농도 분석을 위한 1회용 분석 Kit의 제조 및 농도 분석 절차도1 is a manufacturing and concentration analysis procedure of the disposable assay kit for hydrofluoric acid concentration analysis

도 2는 본 발명에 의해 제조된 불산 농도 분석을 위한 1회용 분석 Kit의 사진Figure 2 is a photograph of a disposable assay kit for hydrofluoric acid concentration analysis prepared by the present invention

도 3은 본 발명에 의한 불산 농도 분석을 위한 1회용 분석 Kit를 이용한 불산 표준액에 의한 검량선 작성 결과 그래프3 is a graph of a calibration curve prepared by hydrofluoric acid standard solution using a disposable analysis kit for analyzing hydrofluoric acid concentration according to the present invention;

도 4는 본 발명에 의한 불산 농도 분석을 위한 1회용 분석 Kit의 장기간 보관시의 농도변화 측정 결과 그래프Figure 4 is a graph of the results of measurement of concentration change during long-term storage of the disposable assay kit for hydrofluoric acid concentration analysis according to the present invention

도 5는 황산과 불산의 혼합산에서 황산이 불산농도 분석에 미치는 영향을 나타내는 그래프5 is a graph showing the effect of sulfuric acid on the analysis of hydrofluoric acid concentration in the mixed acid of sulfuric acid and hydrofluoric acid

Claims (4)

하기 시약 A:0.5~1mL, B:5~10mL, C:0.1~1mL를 혼합하여 흡광도 직접 측정이 가능한 시험관에 분취하여 다수의 분석 Kit를 제조하고, 이 시험관에 미지의 시료 적정량을 투입하여 사전에 준비된 검량선에 의하여 티오시안(SCN) 농도를 직접 측정할 수 있는 불산이 포함된 혼합용액 중 불산 농도의 신속한 분석을 위한 1회용 분석 Kit의 제조방법.The following reagents A: 0.5 to 1 mL, B: 5 to 10 mL, and C: 0.1 to 1 mL are mixed and aliquoted into a test tube capable of directly measuring absorbance to prepare a plurality of assay kits, and an appropriate amount of unknown sample is added to the test tube in advance. Method for preparing a disposable assay kit for the rapid analysis of the concentration of hydrofluoric acid in the mixed solution containing hydrofluoric acid that can directly measure the thiocyanate (SCN) concentration by the calibration curve prepared in. - 시약 A: Iron Solution: 1g/L FeSO4.7H2OReagent A: Iron Solution: 1 g / L FeSO 4 .7H 2 O - 시약 B: Nitric Acid Medium: 0.1N HNO3 Reagent B: Nitric Acid Medium: 0.1 N HNO 3 - 시약 C: Acetylacetone Solution: 1% AcetylacetoneReagent C: Acetylacetone Solution: 1% Acetylacetone 삭제delete 삭제delete 하기 시약 A, B 및 C를 혼합하여 흡광도 직접 측정이 가능한 시험관에 분취하여 다수의 분석 Kit를 제조하고, 이 시험관에 미지의 시료 적정량을 투입하여 사전에 준비된 검량선에 의하여 티오시안(SCN) 농도를 직접 측정하되, 상기 시험관이 유리, 석영, 투명한 플라스틱 재질로 되어 있고, 용량이 5~20mL 크기로서 분광광도계에서 흡광도 측정이 직접 가능한 시험관을 사용하는 불산이 포함된 혼합용액 중 불산 농도의 신속한 분석을 위한 1회용 분석 Kit의 제조방법.The following reagents A, B, and C were mixed and aliquoted into a test tube capable of directly measuring absorbance to prepare a plurality of assay kits, and an appropriate amount of unknown sample was introduced into the test tube, and the concentration of thiocyan (SCN) was measured by a calibration curve prepared in advance. Direct measurement, but the test tube is made of glass, quartz, transparent plastic material, the capacity of 5 ~ 20mL, the rapid analysis of the hydrofluoric acid concentration in the mixed solution containing the hydrofluoric acid using a test tube that can directly measure the absorbance in the spectrophotometer Method of manufacturing a disposable assay kit for. - 시약 A: Iron Solution: 1g/L FeSO4.7H2OReagent A: Iron Solution: 1 g / L FeSO 4 .7H 2 O - 시약 B: Nitric Acid Medium: 0.1N HNO3 Reagent B: Nitric Acid Medium: 0.1 N HNO 3 - 시약 C: Acetylacetone Solution: 1% AcetylacetoneReagent C: Acetylacetone Solution: 1% Acetylacetone
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KR20190031141A (en) 2017-09-15 2019-03-25 주식회사 엘지화학 Nonaqueous electrolyte and lithium secondary battery comprising the same
WO2019054667A3 (en) * 2017-09-15 2019-05-09 주식회사 엘지화학 Nonaqueous electrolyte and lithium secondary battery comprising same
US11296359B2 (en) 2017-09-15 2022-04-05 Lg Energy Solution, Ltd. Non-aqueous electrolyte solution and lithium secondary battery including the same
WO2020022595A1 (en) * 2018-07-25 2020-01-30 주식회사 포스코 Apparatus for measuring concentrations of components in metal-pickling mixed acid solution
KR20200011755A (en) * 2018-07-25 2020-02-04 주식회사 포스코 Analytical apparatus of component concentration of mixed acid solution for pickling of metal
KR102131004B1 (en) 2018-07-25 2020-07-07 주식회사 포스코 Analytical apparatus of component concentration of mixed acid solution for pickling of metal

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