KR102216557B1 - Method and apparatus for measuring total organic carbon, total nitrogen and total phosphorous by using simultaneous oxidation - Google Patents
Method and apparatus for measuring total organic carbon, total nitrogen and total phosphorous by using simultaneous oxidation Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 85
- 230000003647 oxidation Effects 0.000 title claims abstract description 80
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 64
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 61
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 42
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 title description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 65
- 239000011574 phosphorus Substances 0.000 claims abstract description 65
- 238000004458 analytical method Methods 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 29
- 230000001678 irradiating effect Effects 0.000 claims abstract description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002835 absorbance Methods 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 14
- 238000005259 measurement Methods 0.000 claims abstract description 10
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 9
- 239000012159 carrier gas Substances 0.000 claims abstract description 8
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 230000003287 optical effect Effects 0.000 claims description 21
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 18
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 230000001590 oxidative effect Effects 0.000 claims description 16
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 10
- 239000007789 gas Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 238000009279 wet oxidation reaction Methods 0.000 abstract description 6
- 238000012423 maintenance Methods 0.000 abstract description 2
- 238000002485 combustion reaction Methods 0.000 description 16
- 229910017464 nitrogen compound Inorganic materials 0.000 description 10
- 150000002830 nitrogen compounds Chemical class 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 150000003018 phosphorus compounds Chemical class 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 4
- 150000001722 carbon compounds Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 nitrate ions Chemical class 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/14—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of an electrically-heated body in dependence upon change of temperature
- G01N27/16—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of an electrically-heated body in dependence upon change of temperature caused by burning or catalytic oxidation of surrounding material to be tested, e.g. of gas
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- 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
- G01N31/10—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using catalysis
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/1826—Water organic contamination in water
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/188—Determining the state of nitrification
Abstract
Description
본 발명은 수중에 함유되어 있는 총유기탄소, 총질소 및 총인을 측정함에 있어서 하나의 반응기에서 유기탄소화합물, 질소화합물, 인화합물을 동시에 산화시켜 총유기탄소, 총질소 및 총인을 하나의 측정기로 측정할 수 있는 수질 멀티측정 방법 및 장치에 관한 것이다.In the present invention, in measuring total organic carbon, total nitrogen and total phosphorus contained in water, by simultaneously oxidizing organic carbon compounds, nitrogen compounds, and phosphorus compounds in one reactor, total organic carbon, total nitrogen and total phosphorus are measured with one measuring instrument. It relates to a water quality multi-measurement method and apparatus that can be measured.
화학적산소요구량(COD), 생화학적산소요구량(BOD) 등과 함께 수질의 유기물 오염도를 판단할 수 있는 수질 오염지표의 대표적인 것으로는 총유기탄소(Total Organic Carbon; TOC), 총질소(Total Nitogen), 총인(Total Phosphorous)을 들 수 있다. Representative water pollution indicators that can determine the degree of organic matter pollution in the water along with chemical oxygen demand (COD) and biochemical oxygen demand (BOD) are total organic carbon (TOC), total nitrogen, and Total Phosphorous is mentioned.
총유기탄소는 유기물의 오염 정도를 나타내는 지표이고, 총질소와 총인은 영양염류에 의한 부영양화의 정도를 나타내는 지표인 것이다. 우리나라에서는 수질오염총량제가 시행되고 있으며, 하수처리장 및 폐수처리장에서는 방류수의 총유기탄소, 총질소 및 총인을 자동분석기로 분석하여 관리하고 있다.Total organic carbon is an indicator of the degree of contamination of organic matter, and total nitrogen and total phosphorus are indicators of the degree of eutrophication by nutrients. In Korea, the total water pollution rate system is implemented, and in sewage treatment plants and wastewater treatment plants, the total organic carbon, total nitrogen and total phosphorus of the effluent are analyzed and managed with an automatic analyzer.
총유기탄소, 총질소 및 총인은 각각의 다른 분석방법으로 분석되고 있는 상황인바, 이들 분석방법의 공통점은 모두 산화반응을 거쳐야 한다는 것이다.Total organic carbon, total nitrogen, and total phosphorus are analyzed by different analysis methods, and the common point of these analysis methods is that they all have to undergo an oxidation reaction.
총유기탄소 분석방법은 680℃ 이상의 고온에서 연소시켜 산화시키거나 UV를 조사하여 산화시키는 방법이 주로 이용되고 있으며, 총질소 및 총인 분석방법은 시료에 과황산칼륨을 첨가하여 120℃에서 반응시켜 산화시키는 방법이 주로 이용되고 있다.The total organic carbon analysis method is mainly used to oxidize by burning at a high temperature of 680℃ or higher, or to oxidize by irradiating UV. The analysis method for total nitrogen and total phosphorus is oxidized by adding potassium persulfate to the sample and reacting at 120℃. The method of making is mainly used.
총유기탄소 측정방법은, 시료가 산화반응을 거치면 시료중의 유기물이 이산화탄소로 산화되고, 발생된 이산화탄소는 캐리어가스에 실려 비분산적외선센서로 이송되어 정량되며, 정량된 이산화탄소의 농도를 이용하여 계산함으로써 총유기탄소 농도가 측정되는 것이다.In the method of measuring total organic carbon, when the sample undergoes an oxidation reaction, organic matter in the sample is oxidized to carbon dioxide, and the generated carbon dioxide is carried on a carrier gas and transferred to a non-dispersive infrared sensor to be quantified, and calculated using the quantified concentration of carbon dioxide. By doing so, the total organic carbon concentration is measured.
총질소 측정방법은, 질소화합물이 알칼리성 물질 및 과황산칼륨의 존재 하에서 120℃에서 분해되어 질산이온으로 산화된 다음에 산성조건에서 자외선 흡광도를 측정하여 총질소가 정량되는 방법이 많이 사용된다.As for the method of measuring total nitrogen, a method in which a nitrogen compound is decomposed at 120°C in the presence of an alkaline substance and potassium persulfate to be oxidized to nitrate ions, and then the absorbance of ultraviolet rays is measured under acidic conditions, and total nitrogen is quantified is widely used.
총인의 측정방법은, 유기물 형태의 모든 인화합물을 인산이온 형태로 분해시킨 후, 인산 이온을 아스코르빈산 환원법으로 정량하는 분석법이 널리 이용된다. 총인 측정시에도 과황산칼륨을 시료에 첨가한 후 120℃에서 반응시키는 방법이 통상적으로 이용되고 있다.As a method of measuring total phosphorus, an analysis method in which all phosphorus compounds in the form of organic substances are decomposed into the form of phosphate ions and then the phosphate ions are quantified by the ascorbic acid reduction method is widely used. In the measurement of total phosphorus, a method of reacting at 120°C after adding potassium persulfate to a sample is commonly used.
현재 통용되고 있는 자동분석기는 상기의 분석방법이 구현된 것이다. 또한 한 대의 분석기에서 2항목 이상을 분석하고자 하는 수질멀티분석기의 개발이 다양하게 시도되고 있었으며, 현재 개발되어 판매되고 있는 상황이다. 한 대의 측정기에서 2항목 이상의 측정이 가능할 경우, 측정기의 가격도 절감할 수 있으며 설치 공간 또한 줄일 수 있는 등 여러 가지 장점이 있다.The automatic analyzer currently in use implements the above analysis method. In addition, various attempts have been made to develop a water quality multi-analyzer to analyze more than two items in one analyzer, and it is currently being developed and sold. If more than two items can be measured with a single measuring device, there are several advantages, such as reducing the price of the measuring device and reducing the installation space.
독일의 LAR사는 QuickTOC라는 모델의 멀티자동측정기를 판매하고 있다. 동사는 연소산화방식의 TOC자동분석기에서 사용되는 연소산화반응기에 시료를 주입하여 시료를 산화시킨 후 비분산적외선센서로 총유기탄소를 측정하며 또한 질소화합물로부터 산화되어 발생한 질소계열 가스를 CLD(Chemiluminescence detector)를 이용하여 측정함으로써 총인을 제외한 총유기탄소와 총질소를 하나의 장치에서 측정하고 있다.Germany's LAR company sells a multi-automatic meter called QuickTOC. The company oxidizes the sample by injecting the sample into the combustion oxidation reactor used in the TOC automatic analyzer of the combustion oxidation method, and then measures total organic carbon with a non-dispersive infrared sensor. Also, the nitrogen-based gas generated by oxidation from nitrogen detector) to measure total organic carbon and total nitrogen, excluding total phosphorus, in one device.
대한민국등록특허 10-1528126호는 상기의 측정원리와 유사한 방법의 연소산화방식에 의하여 총유기탄소와 총질소를 측정하는 장치에 관한 것이며, 또한 대한민국 등록특허 10-1581230호는 통상적인 분석방법의 총질소와 총인 자동측정기를 하나의 산화반응기에서 산화시킨 후 총질소와 총인을 하나의 측정기에서 분석하는 장치에 관한 것이다.Korean Patent Registration No. 10-1528126 relates to a device for measuring total organic carbon and total nitrogen by a combustion oxidation method similar to the above measurement principle, and Korean Patent Registration No. 10-1581230 relates to an apparatus for measuring total organic carbon and total nitrogen. It relates to an apparatus that analyzes total nitrogen and total phosphorus in one measuring instrument after oxidizing the automatic nitrogen and total phosphorus meter in one oxidation reactor.
그러나, 위와 같은 연소산화방식은 산화율이 높은 장점이 있는 반면에 시료의 양이 적어 시료의 대표성을 나타내기 어려우며, 또한 연소산화반응기는 고온으로 유지되어야 하므로 관리가 어려운 단점이 있을 뿐 아니라, 질소화합물을 연소산화시켜 총질소를 측정하기 위해서는 추가적으로 고가의 CLD센서를 이용하여 산화된 질소가스를 분석해야 하는 단점이 있다.However, while the above combustion oxidation method has the advantage of high oxidation rate, it is difficult to represent the representativeness of the sample due to the small amount of the sample. Also, since the combustion oxidation reactor must be kept at a high temperature, it is difficult to manage, as well as nitrogen compounds. In order to measure total nitrogen by combustion and oxidation, there is a disadvantage of having to analyze the oxidized nitrogen gas by using an expensive CLD sensor.
위와 같은 연소산화방식의 단점을 극복하기 위하여 미국 Hach사는 오존을 이용하여 산화시키는 방식을 활용하고 있는바, Hach사는 BioTector B7000라는 모델의 총유기탄소, 총질소 및 총인을 동시에 측정할 수 있는 멀티자동분석기를 개발하여 판매하고 있다. In order to overcome the shortcomings of the combustion oxidation method as described above, Hach of the United States uses a method of oxidizing using ozone.Hach is a multi-automatic system that can simultaneously measure total organic carbon, total nitrogen and total phosphorus of a model called BioTector B7000. It develops and sells analyzers.
종래의 연소산화방식을 이용하는 총유기탄소를 포함하는 멀티자동분석 기술과 달리, Hach사의 기술은 오존을 이용하여 유기물과 질소화합물을 산화시키고 추가적으로 열반응을 이용하여 인화합물을 산화시키는 기술이다. Unlike the conventional multi-automatic analysis technology including total organic carbon using a combustion oxidation method, Hach's technology is a technology that oxidizes organic substances and nitrogen compounds using ozone, and further oxidizes phosphorus compounds using thermal reaction.
구체적으로는 오존을 이용하여 수질시료를 산화시킨 후에 총유기탄소는 비분산적외선센서를 이용하여 분석하며, 남은 시료에 대해 총질소와 총인을 분석하는 기술인바, 총질소와 총인의 분석방법은 전술하였던 통상의 방법인 자외선흡광도법과 아스코르빈산환원법을 이용하여 분석하는 것이다. 그러나 이 경우 총인을 측정하기 위하여 추가적으로 90℃ 이상의 온도에서 가열하여 산화반응을 시켜야 하는 단점이 있으며, 더욱 치명적인 단점으로는 인체에 치명적으로 유해한 오존 가스가 누출될 위험이 상존한다는 것이다.Specifically, after oxidizing a water sample using ozone, total organic carbon is analyzed using a non-dispersive infrared sensor, and it is a technology that analyzes total nitrogen and total phosphorus for the remaining samples.The method for analyzing total nitrogen and total phosphorus is described above. It is analyzed using the conventional methods of ultraviolet absorbance and ascorbic acid reduction. However, in this case, there is a disadvantage that the oxidation reaction must be performed by heating at a temperature of 90°C or higher in order to measure total phosphorus, and a more fatal disadvantage is that there is a risk of leakage of ozone gas, which is fatally harmful to the human body.
한편, 본 발명자들은 대한민국 등록특허 10-1740013 ‘습식산화 방식의 총 유기탄소 측정방법 및 장치’를 통하여 UV를 조사하여 수질 시료를 산화시키는 기술을 개발한바 있다.On the other hand, the present inventors have developed a technology for oxidizing a water quality sample by irradiating UV through the Korean Patent Registration No. 10-1740013'Method and apparatus for measuring total organic carbon of a wet oxidation method'.
본 발명은, 종래기술인 연소산화방식의 문제점인 시료의 양이 적어 시료의 대표성을 나타내기 어려운 단점과 연소산화반응기가 고온으로 유지되어야 하므로 관리가 어려운 단점 및 질소화합물을 연소산화시켜 총질소를 측정하기 위해서는 추가적으로 고가의 CLD센서를 이용해야 하는 단점을 해결하기 위한 것이다.The present invention is a problem of the conventional combustion oxidation method, which is difficult to represent the representativeness of the sample due to the small amount of sample, and the disadvantage that it is difficult to manage because the combustion oxidation reactor must be maintained at a high temperature, and the total nitrogen is measured by burning and oxidizing nitrogen compounds. This is to solve the disadvantage of additionally using an expensive CLD sensor.
또한, 본 발명은 연소산화방식의 단점을 해결하기 위하여 개발된 오존을 이용하여 유기물과 질소화합물을 산화시키고 추가적으로 열반응을 이용하여 인화합물을 산화시키는 기술에 따른 문제점인 총인을 측정하기 위하여 추가적으로 90℃ 이상의 온도에서 가열하여 산화반응을 시켜야 하는 단점 및 인체에 치명적으로 유해한 오존 가스가 누출될 위험이 상존한다는 단점 또한 해결하기 위한 것이다.In addition, the present invention uses ozone developed to solve the disadvantages of the combustion oxidation method to oxidize organic matter and nitrogen compounds, and additionally to measure total phosphorus, which is a problem with the technique of oxidizing phosphorus compounds using thermal reaction. It is also to solve the disadvantages that the oxidation reaction must be carried out by heating at a temperature higher than °C and the danger of leakage of ozone gas, which is fatally harmful to the human body, is present.
본 발명은 위와 같은 연소산화방식에 따른 문제점 및 오존산화방식에 따른 문제점을 해결하기 위한 것으로서, 수질시료의 총유기탄소, 총질소 및 총인을 분석하는데 있어서 비교적 안전하며, 측정 장치의 가격이 저렴하고 유지관리가 용이한 측정 방법 및 장치를 제공하기 위한 것이다.The present invention is to solve the problems caused by the combustion oxidation method and the ozone oxidation method as described above, it is relatively safe in analyzing total organic carbon, total nitrogen and total phosphorus of a water quality sample, and the price of the measuring device is inexpensive. It is to provide a measurement method and apparatus that are easy to maintain.
또한, 본 발명은 유기탄소화합물, 질소화합물 및 인화합물이 함유되어 있는 수질시료를 동시 산화시켜 하나의 측정기로 3가지 항목을 측정하는 방법을 제공하기 위한 것이다.In addition, the present invention is to provide a method of simultaneously oxidizing a water sample containing organic carbon compounds, nitrogen compounds and phosphorus compounds to measure three items with one measuring instrument.
그리고, 본 발명은 UV습식산화방식의 산화방법을 이용하여 총유기탄소, 총질소 및 총인을 동시에 분석하는 기술을 확립하여 제공하기 위한 것이며, 특히 UV습식산화방식의 산화방법을 채택할 때 산화촉매제로 시료에 첨가되는 과황산나트륨 등이 산화 후 시료내에 잔존하여 총질소와 총인 측정값에 미치는 영향을 최소화하기 위하여 최적의 분석조건을 확립하여 제공하기 위한 것이다.In addition, the present invention is to establish and provide a technique for simultaneously analyzing total organic carbon, total nitrogen, and total phosphorus using the UV wet oxidation method, and in particular, when adopting the UV wet oxidation method, an oxidation catalyst This is to establish and provide optimal analysis conditions in order to minimize the effect of sodium persulfate added to the furnace sample on the measurement values of total nitrogen and total phosphorus by remaining in the sample after oxidation.
본 발명자들은 위와 같은 목적을 달성하기 위하여, 다양한 방법을 적용하여 연구를 진행한 결과 본 발명에 이르게 된 것인바, 본 발명에 따른 동시 산화를 이용한 총유기탄소, 총질소 및 총인 멀티분석 방법은 아래의 단계들로 이루어지는 것이다. In order to achieve the above object, the present inventors have applied various methods to achieve the present invention, and the multi-analysis method of total organic carbon, total nitrogen and total phosphorus using simultaneous oxidation according to the present invention is as follows. It consists of steps of.
즉, 본 발명의 동시 산화를 이용한 총유기탄소, 총질소 및 총인 멀티분석 방법은, 측정시료를 UV산화반응기에 주입하는 단계, 1차로 산을 투입하여 무기탄소를 제거하는 단계, 산화촉매제를 주입하는 단계, UV를 조사하여 산화시키는 단계, 2차로 산을 투입하여 pH를 산성으로 부여하는 단계, 캐리어가스를 UV산화반응기에 흘려 이산화탄소를 비분산적외선센서로 주입하여 총유기탄소를 측정하는 단계, UV산화반응기에 남아 있는 시료를 광계측조로 이송하는 단계, 광계측조에 자외선을 조사하여 흡광도를 측정하여 총질소를 정량하는 단계, 광계측조에 총인분석시약을 주입하는 단계, 및 광계측조에 빛을 조사하여 흡광도를 측정하여 총인을 정량하는 단계를 포함하는 동시 산화를 이용한 총유기탄소, 총질소 및 총인을 멀티측정하기 위한 방법으로 구성되는 것이다.That is, the multi-analysis method of total organic carbon, total nitrogen and total phosphorus using the simultaneous oxidation of the present invention includes the steps of injecting a measurement sample into a UV oxidation reactor, firstly adding an acid to remove inorganic carbon, and injecting an oxidation catalyst. The step of oxidizing by irradiating UV, step of adding acid to give acidity, and measuring total organic carbon by injecting carbon dioxide into a non-dispersive infrared sensor by flowing a carrier gas into a UV oxidation reactor, Transferring the sample remaining in the UV oxidation reactor to an optical measuring tank, measuring the absorbance by irradiating ultraviolet rays in the optical measuring tank to quantify total nitrogen, injecting a total phosphorus analysis reagent into the optical measuring tank, and applying light to the optical measuring tank. It consists of a method for multi-measurement of total organic carbon, total nitrogen, and total phosphorus using simultaneous oxidation including the step of measuring the absorbance by irradiation and quantifying total phosphorus.
그리고, 상기 1차로 산을 투입하여 무기탄소를 제거하는 단계에서는, 산으로서 황산, 인산 등 여러 가지 산을 사용할 수 있으나, 본 발명에서는 황산을 사용하여 무기탄소를 제거하는 것이 가장 바람직한 것으로 확인되었다.And, in the step of removing inorganic carbon by first introducing an acid, various acids such as sulfuric acid and phosphoric acid may be used as the acid, but it was confirmed that the most preferable removal of inorganic carbon using sulfuric acid in the present invention.
또한, UV산화반응조의 온도는 50 내지 95 ℃인 것이 바람직한 것으로 나타났으며, 산화촉매제를 주입하는 단계에서는, 산화촉매제로는 과황산나트륨 및 수산화나트륨(NaOH)을 함께 사용하는 것이 바람직한 것으로 확인되었다.In addition, it was found that the temperature of the UV oxidation reactor was preferably 50 to 95°C, and in the step of injecting the oxidation catalyst, it was confirmed that it is preferable to use sodium persulfate and sodium hydroxide (NaOH) as the oxidation catalyst.
그리고, 시료 총부피에 대하여 NaOH를 30 내지 120 v/v% 투여하는 것이 바람직한 것으로 확인되었다.And, it was confirmed that it is preferable to administer 30 to 120 v/v% NaOH with respect to the total volume of the sample.
또한, 과황산나트륨은 시료 총부피에 대하여 과황산나트륨을 12 내지 60 v/v% 투여하는 것이 바람직한 것으로 확인되었다.In addition, it was confirmed that sodium persulfate is preferably administered in an amount of 12 to 60 v/v% of sodium persulfate based on the total volume of the sample.
또한, 상기 UV를 조사하여 산화시키는 단계에서는, UV의 조사시간이 20 내지 40 분 조사하는것이 바람직한 것으로 확인되었다.In addition, in the step of oxidizing by irradiating with UV, it was confirmed that it is preferable to irradiate the UV irradiation time for 20 to 40 minutes.
또한, 상기 2차로 산을 투입하여 pH를 산성으로 부여하는 단계에서는, 산으로서 여러 가지 산을 사용할 수 있으나, 황산을 사용하여 유기탄소를 발생시키는 것이 가장 바람직한 것으로 확인되었다.In addition, in the step of adding acid to the second acid to give the pH as acid, various acids may be used as the acid, but it was found that it is most preferable to generate organic carbon using sulfuric acid.
한편, 상기 광계측조에 자외선을 조사하여 흡광도를 측정하여 총질소를 정량하는 단계에서는, 자외선의 파장이 220nm인 것이 가장 바람직한 것으로 확인되었다.On the other hand, in the step of quantifying total nitrogen by irradiating ultraviolet rays to the optical measuring tank to measure absorbance, it was confirmed that the wavelength of ultraviolet rays is most preferably 220 nm.
그리고, 상기 광계측조에 총인분석시약을 주입하는 단계에서는, 총인분석시약이 몰리브덴산암모늄과 아스코빈산의 혼합용액인 것이 가장 바람직한 것으로 확인되었다.In addition, in the step of injecting the total phosphorus analysis reagent into the optical measuring tank, it was confirmed that the total phosphorus analysis reagent is a mixed solution of ammonium molybdate and ascorbic acid.
또한, 상기 광계측조에 빛을 조사하여 흡광도를 측정하여 총인을 정량하는 단계에서는, 빛의 파장이 880nm인 것이 가장 바람직한 것으로 확인되었다.In addition, in the step of quantifying total phosphorus by irradiating light to the optical measuring tank to measure absorbance, it was confirmed that the wavelength of light is most preferably 880 nm.
본 발명에 따른 동시 산화를 이용한 총유기탄소, 총질소 및 총인 멀티분석 방법 및 장치는, 유기탄소화합물, 질소화합물 및 인화합물이 함유되어 있는 수질시료를 동시 산화시켜 하나의 장치로 총유기탄소, 총질소 및 총인의 3항목을 측정할 수 있어 장비가격을 대폭 낮출 수 있으며 또한 연소산화방식의 총유기탄소 측정기에 비하여 측정장치의 유지관리가 용이해지는 효과를 나타내는 것이다.The method and apparatus for multi-analysis of total organic carbon, total nitrogen and total phosphorus using simultaneous oxidation according to the present invention is to simultaneously oxidize a water sample containing organic carbon compounds, nitrogen compounds and phosphorus compounds. As it can measure three items of total nitrogen and total phosphorus, it can significantly reduce the cost of equipment, and it has the effect of making the maintenance of the measuring device easier compared to the total organic carbon meter of the combustion oxidation method.
그리고, 본 발명은, 종래기술인 연소산화방식의 문제점인 시료의 양이 적어 시료의 대표성을 나타내기 어려운 단점, 연소산화반응기가 고온으로 유지되어야 하므로 관리가 어려운 단점 및 질소화합물을 연소산화시켜 총질소를 측정하기 위해서는 추가적으로 고가의 CLD센서를 이용해야 하는 단점을 모두 해결하는 효과를 나타내는 것이다.In addition, the present invention is a disadvantage of the conventional combustion oxidation method, which is difficult to represent the representativeness of the sample due to the small amount of sample, the disadvantage that it is difficult to manage because the combustion oxidation reactor must be maintained at a high temperature, and the total nitrogen by combustion and oxidation of nitrogen compounds It shows the effect of solving all the disadvantages of having to use an additionally expensive CLD sensor to measure.
또한, 본 발명은, 종래기술인 오존을 이용하여 유기물과 질소화합물을 산화시키고 추가적으로 열반응을 이용하여 인화합물을 산화시키는 기술에 따른 문제점인 총인을 측정하기 위하여 추가적으로 90℃ 이상의 온도에서 가열하여 산화반응을 시켜야 하는 단점 및 인체에 치명적으로 유해한 오존 가스가 누출될 위험이 상존한다는 단점 또한 해결하는 효과를 나타내는 것이다.In addition, in order to measure total phosphorus, which is a problem with the technique of oxidizing organic materials and nitrogen compounds using ozone, which is a prior art, and oxidizing phosphorus compounds using additional thermal reaction, the oxidation reaction is further heated at a temperature of 90°C or higher. It also shows the effect of solving the disadvantages of having to do so and the danger of leakage of ozone gas that is fatally harmful to the human body.
그리고, 본 발명은, 수질시료의 총유기탄소, 총질소 및 총인을 분석하는데 있어서 비교적 안전하며, 측정 장치의 가격이 저렴하고 유지관리가 용이한 측정 방법 및 장치를 제공하는 효과를 나타내는 것이다.In addition, the present invention is relatively safe in analyzing the total organic carbon, total nitrogen and total phosphorus of a water quality sample, the price of the measuring device is inexpensive, and the present invention shows the effect of providing a measuring method and apparatus easy to maintain.
또한, 본 발명은, UV습식산화방식의 산화방법을 이용하여 총유기탄소, 총질소 및 총인을 동시에 분석하는 기술을 확립하여 제공하는 효과를 나타내는 것이며, 특히 UV습식산화방식의 산화방법을 채택할 때 산화촉매제로 시료에 첨가되는 과황산나트륨 등이 산화 후 시료내에 잔존하여 총질소와 총인 측정값에 미치는 영향을 최소화하기 위하여 최적의 분석조건을 확립하여 제공하는 효과를 나타내는 것이다.In addition, the present invention shows the effect of establishing and providing a technique for simultaneously analyzing total organic carbon, total nitrogen, and total phosphorus using the UV wet oxidation method, and in particular, the UV wet oxidation method is adopted. When sodium persulfate, etc. added to the sample as an oxidation catalyst remains in the sample after oxidation, the optimum analysis conditions are established and provided to minimize the effect on the total nitrogen and total phosphorus measurement values.
도 1은 본 발명의 동시 산화를 이용한 총유기탄소, 총질소 및 총인 멀티측정 방법 및 장치를 설명하기 위한 측정 장치의 개략도이다.1 is a schematic diagram of a measuring apparatus for explaining a multi-measuring method and apparatus for total organic carbon, total nitrogen and total phosphorus using the simultaneous oxidation of the present invention.
이하 첨부한 도면을 참조하여 본 발명의 동시 산화를 이용한 총유기탄소, 총질소 및 총인 멀티측정 방법 및 장치에 관하여 상세히 설명한다. Hereinafter, a method and apparatus for multi-measuring total organic carbon, total nitrogen and total phosphorus using simultaneous oxidation of the present invention will be described in detail with reference to the accompanying drawings.
다음에 소개되는 도면은 당업자에게 본 발명의 사상이 충분히 전달될 수 있도록 하기 위해 예로서 제공되는 것이다.The drawings introduced below are provided as examples in order to sufficiently convey the spirit of the present invention to those skilled in the art.
따라서 본 발명은 아래에서 제시되는 도면에 한정되지 않고 다른 형태로 구체화될 수도 있으며, 이하 제시되는 도면은 본 발명의 사상을 명확히 하기 위해 과장되어 도시될 수 있다. Accordingly, the present invention is not limited to the drawings presented below and may be embodied in other forms, and the drawings presented below may be exaggerated to clarify the spirit of the present invention.
이때, 사용되는 기술 용어 및 과학 용어에 있어서 다른 정의가 없다면 이 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 통상적으로 이해하고 있는 의미를 가지며, 하기의 설명 및 첨부 도면에서 본 발명의 요지를 불필요하게 흐릴 수 있는 공지 기능 및 구성에 대한 설명은 생략한다.At this time, if there is no other definition in the technical terms and scientific terms used, they have the meanings commonly understood by those of ordinary skill in the technical field to which the present invention belongs, and the gist of the present invention is unnecessary in the following description and accompanying drawings. Descriptions of known functions and configurations that may be blurred will be omitted.
본 발명의 일 실시예에 따른, 총유기탄소, 총질소 및 총인 멀티분석 방법은,According to an embodiment of the present invention, the total organic carbon, total nitrogen and total phosphorus multi-analysis method,
1) 측정시료를 UV산화반응기에 주입하는 단계;1) injecting the measurement sample into a UV oxidation reactor;
2) 1차로 산을 투입하여 무기탄소를 제거하는 단계;2) firstly adding an acid to remove inorganic carbon;
3) 산화촉매제를 주입하는 단계;3) injecting an oxidation catalyst;
4) UV를 조사하여 산화시키는 단계;4) oxidizing by irradiating UV;
5) 2차로 산을 투입하여 pH를 산성으로 부여하는 단계;5) secondly adding an acid to give acidic pH;
6) 캐리어가스를 UV산화반응기에 흘려 이산화탄소를 비분산적외선센서로 주입하여 총유기탄소를 측정하는 단계;6) measuring total organic carbon by flowing a carrier gas into a UV oxidation reactor and injecting carbon dioxide into a non-dispersive infrared sensor;
7) UV산화반응기에 남아 있는 시료를 광계측조로 이송하는 단계;7) transferring the sample remaining in the UV oxidation reactor to an optical measuring tank;
8) 광계측조에 자외선을 조사하여 흡광도를 측정하여 총질소를 정량하는 단계;8) quantifying total nitrogen by measuring absorbance by irradiating ultraviolet rays to the photometric tank;
9) 광계측조에 총인분석시약을 주입하는 단계; 및9) injecting a total phosphorus analysis reagent into the optical measuring tank; And
10) 광계측조에 빛을 조사하여 흡광도를 측정하여 총인을 정량하는 단계;를 포함하는 동시 산화를 이용한 총유기탄소, 총질소 및 총인 멀티분석 방법인 것이다.10) It is a multi-analysis method of total organic carbon, total nitrogen and total phosphorus using simultaneous oxidation including; 10) measuring the absorbance by irradiating light to the optical measuring tank to quantify total phosphorus.
여기서, 2) 1차로 산을 투입하여 무기탄소를 제거하는 단계에서, 산으로서 여러 가지 산을 사용할 수 있으나, 황산을 사용하여 무기탄소를 제거하는 것이 가장 바람직한 것으로 확인되었다.Here, 2) In the step of removing inorganic carbon by first adding an acid, various acids may be used as the acid, but it was confirmed that it is most preferable to remove inorganic carbon using sulfuric acid.
또한, 하기 실시예 및 비교예에 의하여 확인되는 것 같이, UV산화반응조의 온도는 50 내지 95 ℃인 것이 바람직한 것으로 나타났다.In addition, as confirmed by the following Examples and Comparative Examples, the temperature of the UV oxidation reactor was found to be preferably 50 to 95 ℃.
그리고, 3) 산화촉매제를 주입하는 단계에서, 산화촉매제로는 과황산나트륨과 NaOH를 함께 사용하는 것이 바람직한 것으로 확인되었는바, 하기 실시예 및 비교예에 의하여 확인되는 것 같이, 시료 총부피에 대하여 NaOH를 30 내지 120 v/v% 투여하는 것이 바람직한 것으로 나타났다.And, 3) In the step of injecting the oxidation catalyst, it was confirmed that it is preferable to use sodium persulfate and NaOH together as the oxidation catalyst, as confirmed by the following Examples and Comparative Examples, with respect to the total volume of the sample It was found to be preferred to administer 30 to 120 v/v% of
또한, 이때 하기 실시예 및 비교예에 의하여 확인되는 것 같이 총부피에 대하여 과황산나트륨을 12 내지 60 v/v% 투여하는 것이 바람직한 것으로 나타났다.In addition, at this time, as confirmed by the following Examples and Comparative Examples, it was found that it is preferable to administer 12 to 60 v/v% of sodium persulfate with respect to the total volume.
또한, 4) UV를 조사하여 산화시키는 단계에서, UV의 조사시간은 20 내지 40 분 조사하는것이 바람직한 것으로 확인되었다.In addition, 4) in the step of oxidizing by irradiating UV, it was confirmed that the irradiation time of UV is preferably 20 to 40 minutes.
또한, 5) 2차로 산을 투입하여 pH를 산성으로 부여하는 단계에서, 산으로서 여러 가지 산을 사용할 수 있으나, 황산을 사용하여 이산화탄소를 발생시키는 것이 가장 바람직한 것으로 확인되었다. In addition, 5) in the step of adding acid to the second acid to give the pH to acidity, various acids can be used as the acid, but it has been confirmed that it is most preferable to generate carbon dioxide using sulfuric acid.
한편, 8) 광계측조에 자외선을 조사하여 흡광도를 측정하여 총질소를 정량하는 단계에서, 자외선의 파장은 220nm인 것이 가장 바람직한 것으로 확인되었다.On the other hand, 8) in the step of quantifying total nitrogen by measuring the absorbance by irradiating ultraviolet rays to the optical measuring tank, it was confirmed that the wavelength of ultraviolet rays is most preferably 220 nm.
그리고, 9) 광계측조에 총인분석시약을 주입하는 단계에서, 총인분석시약은 몰리브덴산암모늄과 아스코빈산의 혼합용액인 것이 가장 바람직한 것으로 확인되었다.And, 9) In the step of injecting the total phosphorus analysis reagent into the optical measuring tank, it was confirmed that the total phosphorus analysis reagent was most preferably a mixed solution of ammonium molybdate and ascorbic acid.
또한, 10) 광계측조에 빛을 조사하여 흡광도를 측정하여 총인을 정량하는 단계에서, 빛의 파장은 880nm인 것이 가장 바람직한 것으로 확인되었다.In addition, 10) In the step of quantifying total phosphorus by measuring absorbance by irradiating light on an optical measuring tank, it was confirmed that the wavelength of light is most preferably 880 nm.
총유기탄소 20mg/L, 총질소 5mg/L, 인 2mg/L인 혼합 표준용액을 시료로 준비하였다. 이송펌프(2)를 가동하여 시료 2mL를 UV산화반응조(3)로 주입하고 산 주입펌프(5)를 이용하여 1.5노르말 황산용액 0.4mL를 UV산화반응조(3)에 주입하였다. 가스유량조절기(8)을 이용하여 캐리어가스로 질소가스를 분당 250mL의 유량으로 UV산화반응조(3)에 3분간 흘려 무기탄소를 제거하였다. A mixed standard solution containing 20 mg/L of total organic carbon, 5 mg/L of total nitrogen, and 2 mg/L of phosphorus was prepared as a sample. The transfer pump 2 was operated to inject 2 mL of the sample into the UV oxidation reactor 3, and 0.4 mL of a 1.5 normal sulfuric acid solution was injected into the UV oxidation reactor 3 using the acid injection pump 5. Inorganic carbon was removed by flowing nitrogen gas as a carrier gas as a carrier gas through the UV oxidation reactor 3 for 3 minutes at a flow rate of 250 mL per minute using the gas flow controller 8.
이후 NaOH 주입펌프(6)과 촉매체주입펌프(7)을 가동하여 시약을 첨가하였다.Thereafter, the NaOH injection pump 6 and the catalyst injection pump 7 were operated to add a reagent.
1노르말 NaOH용액을 시료 총부피에 대해 30, 80, 120 v/v% 첨가하면서, 과황산나트륨을 시료량에 대해 12, 30, 60 v/v% 첨가하였으며 UV산화반응조(3) 온도를 50, 60, 70, 80, 90 및 95 ℃로 하여 30분간 UV를 조사하여 산화시켰다. 1Normal NaOH solution was added to 30, 80, 120 v/v% of the total volume of the sample, sodium persulfate was added 12, 30, 60 v/v% of the sample volume, and the UV oxidation reactor (3) temperature was 50, 60 , 70, 80, 90 and 95°C were oxidized by irradiation with UV for 30 minutes.
이후 UV산화반응조(3)에 캐리어가스로 질소가스를 분당 250mL의 유량으로 흘리면서 발생하는 이산화탄소 가스를 비분산적외선 센서(13)로 측정하여 총유기탄소를 정량하였다. Thereafter, carbon dioxide gas generated by flowing nitrogen gas as a carrier gas into the UV oxidation reactor 3 at a flow rate of 250 mL per minute was measured with a non-dispersive
남은 시료는 이송펌프(15)를 이용하여 총질소/총인 분석 광학계(14)로 이송하였다. 이송된 시료는 220nm에서 흡광도를 측정하여 총질소를 정량하였다.The remaining sample was transferred to the total nitrogen/total phosphorus analysis
이후 총인 분석시약 주입펌프(16)를 가동하여 총인 분석시약인 몰리브덴산암모늄과 아스코빈산의 혼합용액을 총질소/총인 분석 광학계(14)로 주입하였다. 5분간 정치하여 발색시킨 후 흡광도를 측정하여 총인을 정량하였다. 측정농도/표준농도의 비율을 계산하여 산화율을 계산하였다. 측정결과모든 조건에 산화율이 90%이상인 것을 확인하였다. Thereafter, the total phosphorus analysis
산화율 결과를 표 1에 나타냈다.Table 1 shows the oxidation rate results.
(℃)Temperature
(℃)
실시예 1에서 UV산화반응조(3) 온도를 60 ℃로 하여 20, 30, 40 분간 UV를 조사하는 것을 제외하고는 실시예 1과 동일한 방법으로 시험하였다. 모든 조건에서 산화율이 90% 이상이었다. In Example 1, the UV oxidation reactor 3 was tested in the same manner as in Example 1, except that the temperature was set to 60° C. and UV was irradiated for 20, 30, and 40 minutes. The oxidation rate was more than 90% under all conditions.
산화율 결과를 표2에 나타내었다.Table 2 shows the oxidation rate results.
(분)UV irradiation time
(minute)
[비교예 1][Comparative Example 1]
실시예 1에서 UV산화반응조(3)의 온도를 30 ℃ 및 40 ℃로 한 것을 제외하고는 실시예 1과 동일한 방법으로 시험하였다. UV산화반응조(3)의 온도를 30 ℃ 및 40 ℃로 하는 경우 산화율이 70% 이하였다. In Example 1, except that the temperature of the UV oxidation reactor 3 was set to 30 ℃ and 40 ℃ was tested in the same manner as in Example 1. When the temperature of the UV oxidation reactor 3 was set to 30°C and 40°C, the oxidation rate was 70% or less.
산화율 결과를 표3에 나타내었다.Table 3 shows the oxidation rate results.
[비교예 2][Comparative Example 2]
1 노르말 NaOH용액을 시료 총부피에 대하여 20 및 130 v/v% 첨가하며, 과황산나트륨을 시료량에 대해 10 및 70% 첨가한 것을 제외하고는 실시예 1과 동일한 방법으로 시험하였다.1 Normal NaOH solution was added in the same manner as in Example 1, except that 20 and 130 v/v% were added to the total volume of the sample, and 10 and 70% sodium persulfate were added to the sample amount.
NaOH용액의 첨가량이 130 v/v%, 과황산나트륨용액이 70 v/v% 첨가된 경우 총질소의 농도가 표준농도보다 매우 높으며 총인은 50% 이하 수준으로 측정되어 방해요인으로 작용하는 것으로 확인되었다. NaOH용액의 첨가량이 20 v/v%이하이거나 과황산나트륨용액이 10 v/v%이하인 경우 총질소 및 총인의 농도가 낮게 측정되었다.When the NaOH solution was added at 130 v/v% and the sodium persulfate solution at 70 v/v% was added, the total nitrogen concentration was much higher than the standard concentration, and the total phosphorus was measured to be less than 50%, and it was confirmed that it acts as a disturbing factor. . When the added amount of NaOH solution was less than 20 v/v% or sodium persulfate solution was less than 10 v/v%, the concentrations of total nitrogen and total phosphorus were measured to be low.
산화율 결과를 표4에 나타내었다.Table 4 shows the oxidation rate results.
[비교예 3][Comparative Example 3]
실시예 1에서 UV산화반응조(3) 온도를 60 ℃로 하여 5, 10, 15분간 UV를 조사하는 것을 제외하고 실시예 1과 동일한 방법으로 시험하였다. 모든 조건에서 산화율이 80% 이하로 낮았다. In Example 1, the UV oxidation reactor 3 was tested in the same manner as in Example 1, except that UV irradiation was performed for 5, 10, and 15 minutes at a temperature of 60°C. The oxidation rate was as low as 80% or less under all conditions.
산화율 결과를 표5에 나타내었다.Table 5 shows the oxidation rate results.
(분)UV irradiation time
(minute)
이상, 실시예를 기반으로 하여 본 발명을 상술하였으나, 본 발명의 사상은 설명된 실시예에 국한되어 정해져서는 아니 되며, 후술하는 청구범위뿐 아니라 이 청구범위와 균등하거나 등가적 변형이 있는 모든 것들은 본 발명 사상의 범주에 속한다고 할 것이다.As described above, the present invention has been described above based on the embodiments, but the spirit of the present invention is limited to the described embodiments and should not be defined, as well as the claims to be described later, as well as all equivalent or equivalent modifications to the claims. It will be said that it belongs to the scope of the inventive idea.
1 : 3방향 전동밸브
2 : 이송펌프
3 : UV산화반응조
4 : UV 램프
5 : 산 주입 펌프
6 : NaOH주입 펌프
7 : 촉매제 주입펌프
8 : 가스유량조절기
9 : 가스 공급장치
10 : 2방향 전동밸브
11 : 냉각기
12 : 스크러버
13 : 비분산적외선센서
14 : 총질소/총인 분석 광학계
15 : 이송펌프
16 : 총인 분석시약 주입펌프1: 3-way electric valve
2: transfer pump
3: UV oxidation reactor
4: UV lamp
5: acid infusion pump
6: NaOH injection pump
7: catalyst injection pump
8: gas flow controller
9: gas supply device
10: 2-way electric valve
11: cooler
12: scrubber
13: non-dispersive infrared sensor
14: Total nitrogen/total phosphorus analysis optical system
15: transfer pump
16: Total phosphorus analysis reagent injection pump
Claims (11)
1) 측정시료를 UV산화반응기에 주입하는 단계;
2) 1차로 산을 투입하여 무기탄소를 제거하는 단계;
3) 산화촉매제를 주입하는 단계;
4) UV를 조사하여 산화시키는 단계;
5) 2차로 산을 투입하여 pH를 산성으로 부여하는 단계;
6) 캐리어가스를 UV산화반응기에 흘려 이산화탄소를 비분산적외선센서로 주입하여 총유기탄소를 측정하는 단계;
7) UV산화반응기에 남아 있는 시료를 광계측조로 이송하는 단계;
8) 광계측조에 자외선을 조사하여 흡광도를 측정하여 총질소를 정량하는 단계;
9) 광계측조에 총인분석시약을 주입하는 단계; 및
10) 광계측조에 빛을 조사하여 흡광도를 측정하여 총인을 정량하는 단계;를 포함하는 동시 산화를 이용한 총유기탄소, 총질소 및 총인 멀티분석 방법에 있어서,
상기 2) 1차로 산을 투입하여 무기탄소를 제거하는 단계에서, 산은 황산인 것이고,
상기 3) 산화촉매제를 주입하는 단계에서, 산화촉매제로 과황산나트륨과 NaOH를 함께 첨가하되, 과황산나트륨을 시료 총부피에 대하여 12 내지 60 v/v% 투여하고, NaOH를 시료 총부피에 대하여 30 내지 120 v/v% 투여하는 것이고,
상기 4) UV를 조사하여 산화시키는 단계에서, UV산화반응기의 온도는 50 내지 95 ℃인 것이고, UV를 20 내지 40 분 조사하는 것이며,
상기 5) 2차로 산을 투입하여 pH를 산성으로 부여하는 단계에서, 산은 황산인 것을 특징으로 하는 총유기탄소, 총질소 및 총인 멀티분석 방법.
Total organic carbon, total nitrogen and total phosphorus multi-analysis method,
1) injecting a measurement sample into a UV oxidation reactor;
2) firstly adding acid to remove inorganic carbon;
3) injecting an oxidation catalyst;
4) oxidizing by irradiating UV;
5) secondly adding an acid to give acidic pH;
6) measuring total organic carbon by flowing a carrier gas into a UV oxidation reactor and injecting carbon dioxide into a non-dispersive infrared sensor;
7) transferring the sample remaining in the UV oxidation reactor to an optical measuring tank;
8) quantifying total nitrogen by measuring absorbance by irradiating ultraviolet rays to an optical measuring tank;
9) injecting a total phosphorus analysis reagent into the optical measuring tank; And
10) In the multi-analysis method of total organic carbon, total nitrogen and total phosphorus using simultaneous oxidation including;
In the step of removing inorganic carbon by 2) firstly introducing an acid, the acid is sulfuric acid,
In the step of injecting the 3) oxidation catalyst, sodium persulfate and NaOH are added together as an oxidation catalyst, but sodium persulfate is administered in an amount of 12 to 60 v/v% based on the total volume of the sample, and NaOH is added to the total volume of the sample. 120 v/v% is administered,
In the step 4) oxidizing by irradiating UV, the temperature of the UV oxidation reactor is 50 to 95 °C, and irradiating UV for 20 to 40 minutes,
The multi-analysis method of total organic carbon, total nitrogen and total phosphorus, characterized in that in the step of 5) adding an acid to give the pH to be acidic, the acid is sulfuric acid.
상기 8) 광계측조에 자외선을 조사하여 흡광도를 측정하여 총질소를 정량하는 단계에서, 자외선의 파장은 220nm인 것을 특징으로 하는 총유기탄소, 총질소 및 총인 멀티분석 방법.
The method of claim 1,
8) In the step of quantifying total nitrogen by measuring absorbance by irradiating ultraviolet rays to the optical measuring tank, the wavelength of ultraviolet rays is 220 nm.
상기 9) 광계측조에 총인분석시약을 주입하는 단계에서, 총인분석시약은 몰리브덴산암모늄과 아스코빈산의 혼합용액인 것을 특징으로 하는 총유기탄소, 총질소 및 총인 멀티분석 방법.
The method of claim 1,
9) In the step of injecting the total phosphorus analysis reagent into the photometric tank, the total phosphorus analysis reagent is a mixed solution of ammonium molybdate and ascorbic acid, wherein the total organic carbon, total nitrogen and total phosphorus multi-analysis method.
상기 10) 광계측조에 빛을 조사하여 흡광도를 측정하여 총인을 정량하는 단계에서, 빛의 파장은 880nm인 것을 특징으로 하는 총유기탄소, 총질소 및 총인 멀티분석 방법.The method of claim 1,
10) In the step of quantifying total phosphorus by measuring absorbance by irradiating light to the optical measuring tank, the wavelength of light is 880 nm.
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