TWI647441B - Analysis equipment and analysis method of total organic carbon content in water - Google Patents
Analysis equipment and analysis method of total organic carbon content in water Download PDFInfo
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Abstract
一種水樣總有機碳含量分析設備及其分析方法，可以透過UV光的光照與催化劑的催化，讓氧氣與水樣反應生成氫氧自由基，而透過氫氧自由基氧化水樣中的有機物，藉以準確分析水樣中總有機碳的含量。The invention relates to a water sample total organic carbon content analysis device and an analysis method thereof, which can illuminate a water and a water sample to generate a hydroxyl radical through the illumination of the UV light and the catalyst, and oxidize the organic substance in the water sample through the hydroxyl radical, To accurately analyze the total organic carbon content of the water sample.
Description
本發明係有關於一種分析設備及其分析方法，更詳而言之，是一種可針對水樣總有機碳含量進行分析的分析設備及其分析方法。The present invention relates to an analytical device and an analytical method thereof, and more particularly to an analytical device and an analytical method thereof for analyzing the total organic carbon content of a water sample.
隨著人們對環境的重視，各國政府對污廢水等水樣的總有機碳(TotalOrganicCarbon，簡稱TOC)含量都進行規範，以減少污廢水對環境的污染，也因此業界的總有機碳分析設備被廣泛使用，以對水樣中的總有機碳含量進行分析。總有機碳分析設備，通常會將水樣中的有機物氧化，而利用非分散式紅外線分析儀(Non-Dispersion Infrared Analyzer，簡稱NDIR)，測得水樣中的總有機碳濃度。With the emphasis on the environment, governments of all countries regulate the total organic carbon (Total Organic Carbon) (TOC) content of sewage and other water samples to reduce the pollution of sewage to the environment, so the industry's total organic carbon analysis equipment is Widely used to analyze the total organic carbon content of water samples. The total organic carbon analysis equipment usually oxidizes the organic matter in the water sample, and the total organic carbon concentration in the water sample is measured by a Non-Dispersion Infrared Analyzer (NDIR).
要將水樣中的有機物氧化的方法至少包含有以下三種：高溫燃燒法、UV過硫酸鹽法與二階段式高級氧化法。針對高溫燃燒法，一般是讓水樣中的有機物於高溫爐壁上氧化，然如此會導致高溫爐壁上殘留物質，而衍生清洗困難等被人所詬病的問題。針對UV過硫酸鹽法，一般是藉由UV光活化過硫酸鹽以產生氫氧自由基，而對水樣中的有機物進行氧化，然，當水樣中氯離子(Cl-)濃度超過0.5%時，氫氧自由基的產生就會受到抑制，且當水樣的濁度較高時，UV光可能會受到阻擋，使得過硫酸鹽的活化不足，如此導致水樣中的有機物無法完全氧化，使得水樣中總有機碳含量的分析失準。針對二階段式高級氧化法，一般是透過鹼藥劑(NaOH)的加入而將水樣中的有機物氧化成二氧化碳，然後藉由二氧化碳的量測數據，而分析水樣中的總有機碳含量，然鹼藥劑中原本就會溶解二氧化碳，故鹼藥劑的使用會有非屬於有機物氧化的二氧化碳，而干擾水樣中總有機碳含量的分析。The method for oxidizing the organic matter in the water sample includes at least the following three types: a high temperature combustion method, a UV persulfate method, and a two-stage advanced oxidation method. For the high-temperature combustion method, the organic matter in the water sample is generally oxidized on the wall of the high-temperature furnace, which may cause residual substances on the wall of the high-temperature furnace, and the problems such as difficulty in derivation and cleaning are criticized. For the UV persulfate method, the persulfate is generally activated by UV light to generate hydroxyl radicals, and the organic matter in the water sample is oxidized. However, when the concentration of chloride ions (Cl-) in the water sample exceeds 0.5% At the time, the production of hydroxyl radicals is inhibited, and when the turbidity of the water sample is high, the UV light may be blocked, so that the activation of the persulfate is insufficient, so that the organic matter in the water sample cannot be completely oxidized. The analysis of the total organic carbon content in the water sample is inaccurate. For the two-stage advanced oxidation method, the organic matter in the water sample is generally oxidized to carbon dioxide by the addition of an alkali agent (NaOH), and then the total organic carbon content in the water sample is analyzed by the measurement data of carbon dioxide. Alkali agents will dissolve carbon dioxide, so the use of alkali chemicals will be carbon dioxide that is not oxidized by organic matter, and interfere with the analysis of the total organic carbon content in the water sample.
有鑑於上述，如何解決上述的種種問題，使水樣中的有機物能夠順利完成氧化，而提升分析水樣中總有機碳含量的準確性，即為本案發明主要的技術思想。In view of the above, how to solve the above problems, the organic matter in the water sample can be successfully oxidized, and the accuracy of analyzing the total organic carbon content in the water sample is the main technical idea of the invention.
鑒於上述先前技術之種種問題，本發明係提供一種水樣總有機碳含量的分析設備，係使用非分散式紅外線分析儀分析水樣的揮發性有機碳含量，係包括：設備本體、水樣導入模組、氧氣提供模組與UV光提供模組。設備本體的內部具有溶液空間。水樣導入模組係連通溶液空間，俾將水樣導入溶液空間中。氧氣提供模組係連通溶液空間，俾對水樣提供氧氣而釋出水樣中的揮發性有機物。UV光提供模組係接收水樣釋出的揮發性有機物，俾對揮發性有機物提供UV光，而透過UV光的光照讓揮發性有機物反應生成二氧化碳，而供非分散式紅外線分析儀分析該水樣中的揮發性有機碳含量。In view of the above problems of the prior art, the present invention provides an analysis device for total organic carbon content of water samples, which is a non-dispersive infrared analyzer for analyzing volatile organic carbon content of water samples, including: equipment body, water sample introduction Module, oxygen supply module and UV light supply module. The inside of the device body has a solution space. The water sample introduction module communicates with the solution space, and the water sample is introduced into the solution space. The oxygen supply module is connected to the solution space, and the oxygen is supplied to the water sample to release volatile organic compounds in the water sample. The UV light supply module receives the volatile organic matter released from the water sample, and the UV light is supplied to the volatile organic substance, and the volatile organic substance reacts to generate carbon dioxide by the illumination of the UV light, and the water is analyzed by the non-dispersive infrared analyzer. The content of volatile organic carbon in the sample.
另外，本發明還提供一種水樣總有機碳含量的分析設備，係使用非分散式紅外線分析儀分析水樣的非揮發性有機碳含量，係包括：設備本體、水樣導入模組、藥劑提供模組、氧氣提供模組以及UV光提供模組。設備本體的內部具有一溶液空間。水樣導入模組係連通溶液空間，俾將水樣導入溶液空間中。藥劑提供模組係連通溶液空間，並對水樣提供包含催化劑的藥劑而形成第一溶液，其中，催化劑係包含過渡金屬離子。氧氣提供模組係對第一溶液提供氧氣而形成第二溶液。UV光提供模組係接收第二溶液，俾對第二溶液提供UV光，而透過UV光的光照與催化劑的催化，讓氧氣與水樣反應生成氫氧自由基，而透過氫氧自由基氧化第二溶液中水樣的非揮發性有機物以生成二氧化碳，而供非分散式紅外線分析儀分析水樣中的非揮發性有機碳含量。In addition, the present invention also provides an analysis device for the total organic carbon content of a water sample, which is a non-dispersive infrared analyzer for analyzing the non-volatile organic carbon content of the water sample, comprising: a device body, a water sample introduction module, and a drug supply. Module, oxygen supply module and UV light supply module. The inside of the device body has a solution space. The water sample introduction module communicates with the solution space, and the water sample is introduced into the solution space. The agent supply module is connected to the solution space, and provides a first solution to the water sample by providing a catalyst containing a catalyst, wherein the catalyst system comprises transition metal ions. The oxygen supply module provides oxygen to the first solution to form a second solution. The UV light supply module receives the second solution, and the UV light is supplied to the second solution, and the UV light is catalyzed by the catalyst to react the oxygen with the water sample to form hydroxyl radicals, and is oxidized by the hydroxyl radical. The water-like non-volatile organic matter in the second solution is used to generate carbon dioxide, and the non-dispersive infrared analyzer is used to analyze the non-volatile organic carbon content in the water sample.
可選擇性地，在本發明的分析設備中，UV光提供模組係對第二溶液提供波長介於100至200nm之間與200至280nm之間的UV光，讓氧氣與水樣反應生成氫氧自由基。Alternatively, in the analysis device of the present invention, the UV light providing module provides UV light having a wavelength between 100 and 200 nm and between 200 and 280 nm for the second solution, allowing oxygen to react with the water to form hydrogen. Oxygen free radicals.
可選擇性地，在本發明的分析設備中，氧氣提供模組還對第二溶液提供氧氣，迫使二氧化碳朝非分散式紅外線分析儀流動，藉以分析水樣中的非揮發性有機碳含量。Alternatively, in the analytical device of the present invention, the oxygen supply module also supplies oxygen to the second solution, forcing the carbon dioxide to flow toward the non-dispersive infrared analyzer to analyze the non-volatile organic carbon content of the water sample.
可選擇性地，在本發明的分析設備中，藥劑提供模組所提供的藥劑還包含酸劑，以令水樣的PH值小於1，使水樣中的無機碳酸化而生成二氧化碳，並由氧氣提供模組所提供的氧氣排除二氧化碳，藉以排除水樣中的無機碳。Optionally, in the analyzing device of the present invention, the agent provided by the agent providing module further comprises an acid agent, so that the pH of the water sample is less than 1, so that the inorganic carbonization in the water sample generates carbon dioxide, and The oxygen supply module provides oxygen to remove carbon dioxide, thereby eliminating inorganic carbon from the water sample.
可選擇性地，在本發明的分析設備中，還包括純水提供模組，純水提供模組係連通溶液空間，以對溶液空間提供純水，而對溶液空間的水樣進行稀釋，以調整溶液空間水樣的濃度至適當值。Optionally, in the analysis device of the present invention, a pure water supply module is further included, and the pure water supply module is connected to the solution space to provide pure water to the solution space, and the water sample in the solution space is diluted to Adjust the concentration of the solution space water sample to an appropriate value.
可選擇性地，在本發明的分析設備中，設備本體還包括底部排液模組、過量排液模組、定量排液模組與溶液定量儲存模組。底部排液模組係連通溶液空間的底部，俾自溶液空間的底部，排出溶液空間中的溶液。過量排液模組係連通溶液空間，俾排出溶液空間中過量的溶液。定量排液模組係連通溶液空間，俾排出溶液空間中部分的溶液。溶液定量儲存模組係連通溶液空間，俾將溶液空間中定量的溶液儲存。Optionally, in the analyzing device of the present invention, the device body further includes a bottom draining module, an excess draining module, a quantitative draining module, and a solution quantitative storage module. The bottom drain module is connected to the bottom of the solution space, and is taken from the bottom of the solution space to discharge the solution in the solution space. The excess liquid discharge module is connected to the solution space, and the excess solution in the solution space is discharged. The quantitative draining module is connected to the solution space, and the solution is partially discharged from the solution space. The solution quantitative storage module communicates with the solution space, and stores the quantitative solution in the solution space.
再者，本發明還提供一種水樣總有機碳含量的分析方法，係包括以下步驟：(i)提供一水樣；(ii)提供一藥劑，以製備包含該水樣及該藥劑之第一溶液，其中，該藥劑係包含催化劑，而該催化劑係包含過渡金屬離子；(iii)在步驟(ii)期間或之後的任何時間，在該第一溶液中加入氧氣以形成第二溶液；以及(iv)在步驟(iii)期間或之後的任何時間，對該第二溶液提供UV光，而使該第二溶液反應生成氫氧自由基，而透過該氫氧自由基氧化該第二溶液中水樣的非揮發性有機物而生成二氧化碳，藉以分析該水樣中的總有機碳含量。Furthermore, the present invention also provides a method for analyzing the total organic carbon content of a water sample, comprising the steps of: (i) providing a water sample; (ii) providing a medicament for preparing the water sample and the first medicament; a solution, wherein the agent comprises a catalyst, and the catalyst comprises a transition metal ion; (iii) at any time during or after step (ii), adding oxygen to the first solution to form a second solution; Iv) providing UV light to the second solution during or after step (iii), and reacting the second solution to form hydroxyl radicals, and oxidizing the water in the second solution through the hydroxyl radicals The non-volatile organic matter produces carbon dioxide to analyze the total organic carbon content of the water sample.
可選擇性地，在本發明的分析方法中，在步驟(i)期間或步驟(ii)期間之前的任何時間，在該水樣中加入酸劑，以令該水樣的PH值小於1，使該水樣中的無機碳酸化而生成二氧化碳，藉以排除該水樣中的無機碳。Alternatively, in the analysis method of the present invention, an acid agent is added to the water sample at any time before the step (i) or before the step (ii) to make the pH of the water sample less than 1, The inorganic carbon in the water sample is carbonated to form carbon dioxide, thereby eliminating inorganic carbon in the water sample.
可選擇性地，在本發明的分析方法中，在步驟(iv)期間或之後的任何時間，在該第二溶液中加入氧氣，迫使由該水樣的非揮發性有機物氧化所生成二氧化碳離開該第二溶液，藉以分析該水樣中的非揮發性有機碳含量。Alternatively, in the analysis method of the present invention, oxygen is added to the second solution at any time during or after the step (iv) to force the carbon dioxide generated by the oxidation of the non-volatile organic substance of the water sample to leave the The second solution is used to analyze the non-volatile organic carbon content of the water sample.
另外，本發明還提供一種水樣總有機碳含量的分析方法，係包括以下步驟：(i)提供一水樣；以及(ii)在該水樣中加入氧氣以釋出該水樣中的揮發性有機物，而後對該揮發性有機物提供UV光，而讓該揮發性有機物反應生成二氧化碳，藉以分析該水樣中的揮發性有機碳含量。In addition, the present invention also provides a method for analyzing the total organic carbon content of a water sample, comprising the steps of: (i) providing a water sample; and (ii) adding oxygen to the water sample to release the volatiles in the water sample. The organic matter is then supplied with UV light to the volatile organic compound, and the volatile organic compound is reacted to form carbon dioxide, thereby analyzing the volatile organic carbon content in the water sample.
相較於先前技術，本發明的水樣總有機碳含量分析設備及其分析方法，係透過UV光的光照與催化劑的催化，讓氧氣與水樣反應生成臭氧進而生成氫氧自由基，而後藉由氫氧自由基氧化水樣中的有機物，使得水樣中的有機物能夠順利完成氧化，藉以分析水樣中總有機碳的含量，可解決先前技術中，採用高溫燃燒法氧化有機物的高溫爐壁清洗困難等問題，採用UV過硫酸鹽法氧化有機物的受到氯離子抑制等問題，採用二階段式高級氧化法氧化有機物的鹼藥劑干擾等問題。Compared with the prior art, the water sample total organic carbon content analysis device and the analysis method thereof of the present invention pass the irradiation of UV light and the catalysis of the catalyst, and allow oxygen to react with the water sample to generate ozone to generate hydroxyl radicals, and then borrow The organic matter in the water sample is oxidized by the hydroxyl radical, so that the organic matter in the water sample can be successfully oxidized, thereby analyzing the total organic carbon content in the water sample, and the high temperature furnace wall which oxidizes the organic substance by the high temperature combustion method in the prior art can be solved. Problems such as difficulty in cleaning, problems such as suppression of chloride ions by oxidizing organic substances by the UV persulfate method, and problems such as interference of alkali chemicals by oxidizing organic substances by a two-stage advanced oxidation method.
以下內容將搭配圖式，藉由特定的具體實施例說明本發明之技術內容，熟悉此技術之人士可由本說明書所揭示之內容輕易地了解本發明之其他優點與功效。本發明亦可藉由其他不同的具體實施例加以施行或應用。本說明書中的各項細節亦可基於不同觀點與應用，在不背離本發明之精神下，進行各種修飾與變更。尤其是，於圖式中各個元件的比例關係及相對位置僅具示範性用途，並非代表本發明實施的實際狀況。The other aspects of the present invention will be readily understood by those skilled in the art from this disclosure. The invention may also be embodied or applied by other different embodiments. The details of the present invention can be variously modified and changed without departing from the spirit and scope of the invention. In particular, the relative relationship and relative positions of the various elements in the drawings are for illustrative purposes only and are not representative of actual implementation of the invention.
本發明係提供一種水樣總有機碳含量分析設備及其分析方法，可以透過UV光的光照讓水樣中的揮發性有機物氧化，藉以分析水樣中的揮發性有機碳含量，還可以透過UV光的光照與催化劑的催化，讓氧氣與水樣反應生成氫氧自由基(OH．)，而透過氫氧自由基氧化水樣中的非揮發性有機物，藉以準確分析水樣中總有機碳(Total Organic Carbon，簡稱TOC)的含量。針對本發明的技術思想，以下係參照本發明圖式中圖1至圖6揭示的內容進行例示說明：The invention provides a water sample total organic carbon content analysis device and an analysis method thereof, which can oxidize volatile organic compounds in a water sample by ultraviolet light illumination, thereby analyzing volatile organic carbon content in the water sample, and can also pass UV The illumination of light and the catalysis of the catalyst allow oxygen to react with the water sample to form hydroxyl radicals (OH.), and the non-volatile organic compounds in the water sample are oxidized by the hydroxyl radicals to accurately analyze the total organic carbon in the water sample ( Total Organic Carbon (TOC). For the technical idea of the present invention, the following is exemplified with reference to the contents disclosed in FIGS. 1 to 6 of the drawings of the present invention:
本發明的水樣總有機碳含量的分析設備1，係使用非分散式紅外線分析儀2來分析水樣中的總有機碳含量。本發明的水樣總有機碳含量的分析設備1係具有設備本體11、水樣導入模組12、藥劑提供模組13、反應管路模組14、待氧化液提供模組15、UV光提供模組16、氧氣提供模組17、揮發性有機物提供模組18以及純水提供模組19。The analysis apparatus 1 for the total organic carbon content of the water sample of the present invention uses a non-dispersive infrared analyzer 2 to analyze the total organic carbon content in the water sample. The analysis device 1 for water sample total organic carbon content of the invention has a device body 11, a water sample introduction module 12, a drug supply module 13, a reaction pipeline module 14, a solution to be oxidized liquid supply 15, and a UV light supply. The module 16, the oxygen supply module 17, the volatile organic material supply module 18, and the pure water supply module 19 are provided.
設備本體11的內部具有用於容納液體的溶液空間111。水樣導入模組12係具有管路而連通溶液空間111，俾將水樣導入溶液空間111中以進行總有機碳含量的分析。另外，本發明的設備本體11還可設置底部排液模組112、過量排液模組113、定量排液模組114與溶液定量儲存模組115。底部排液模組112係具有管路連通溶液空間111的底部，俾自溶液空間111的底部，排出溶液空間111中的溶液，進而調整溶液空間111中溶液的容量。過量排液模組113係具有管路連通溶液空間111，俾在水樣總有機碳含量的分析過程中，排出溶液空間111中過量的溶液，以避免溶液空間111中的溶液過量，而影響分析設備1的正常運行。定量排液模組114係具有管路連通溶液空間111，俾排出溶液空間111中多餘的溶液，使溶液空間111中的溶液具有預定的容量，而使分析設備1的分析條件符合預期。溶液定量儲存模組115係具有管路連通溶液空間111，俾將溶液空間111中預定容量的水樣儲存，以定量本發明分析的水樣，而確保本發明水樣總有機碳含量的分析結果準確。The inside of the apparatus body 11 has a solution space 111 for containing a liquid. The water sample introduction module 12 has a pipeline to communicate with the solution space 111, and the water sample is introduced into the solution space 111 for analysis of the total organic carbon content. In addition, the device body 11 of the present invention may further be provided with a bottom drain module 112, an excess drain module 113, a quantitative drain module 114 and a solution quantitative storage module 115. The bottom drain module 112 has a bottom portion of the pipeline communication solution space 111, which is discharged from the bottom of the solution space 111, and discharges the solution in the solution space 111, thereby adjusting the capacity of the solution in the solution space 111. The excess drain module 113 has a pipeline communication solution space 111, and during the analysis of the total organic carbon content of the water sample, the excess solution in the solution space 111 is discharged to avoid excess solution in the solution space 111, and the influence analysis The normal operation of device 1. The quantitative drain module 114 has a line communication solution space 111, and the excess solution in the solution space 111 is discharged, so that the solution in the solution space 111 has a predetermined capacity, and the analysis conditions of the analysis device 1 are in line with expectations. The solution quantitative storage module 115 has a pipeline communication solution space 111, and stores a predetermined volume of water sample in the solution space 111 to quantify the water sample analyzed by the present invention, thereby ensuring the analysis result of the total organic carbon content of the water sample of the present invention. accurate.
再者，本發明的設備本體11可設置標準液導入模組116，標準液導入模組116係具有管路連通溶液空間111，俾將包含定量有機物的標準液導入溶液空間111中，以供分析標準液的總有機碳含量，並將分析結果作為本發明分析水樣總有機碳含量的參考。Furthermore, the apparatus body 11 of the present invention can be provided with a standard liquid introduction module 116 having a pipeline communication solution space 111, and a standard liquid containing a quantitative organic substance is introduced into the solution space 111 for analysis. The total organic carbon content of the standard solution is used as a reference for analyzing the total organic carbon content of the water sample of the present invention.
藥劑提供模組13係具有管路而連通溶液空間111。於本發明中，藥劑提供模組13可對水樣提供包含例如氫離子(H +)的酸劑，以令水樣的PH值小於1，使水樣的無機碳酸化而生成二氧化碳，並由氧氣提供模組17提供的氧氣排除二氧化碳，藉以排除水樣中的無機碳，於本發明的一實施例中，水樣的無機碳酸化而生成二氧化碳的化學反應式，如下：CO 3 2- (aq)+H +→CO 2 (g)。 The medicine supply module 13 has a line to communicate with the solution space 111. In the present invention, the drug supply module 13 can provide an acid agent containing, for example, hydrogen ions (H + ) to the water sample, so that the pH of the water sample is less than 1, and the inorganic water of the water sample is carbonized to generate carbon dioxide. The oxygen supply module 17 provides oxygen to remove carbon dioxide, thereby eliminating inorganic carbon in the water sample. In one embodiment of the invention, the chemical reaction of the water sample by inorganic carbonation to form carbon dioxide is as follows: CO 3 2- ( Aq) +H + →CO 2 (g) .
再者，藥劑提供模組13還可對水樣提供包含過渡金屬離子的催化劑而形成第一溶液。氧氣提供模組17係具有管路連通溶液空間111，俾對溶液空間111提供氧氣(O2)，以使溶液空間111中的水樣釋出揮發性有機物，還可對第一溶液提供氧氧而形成第二溶液。Furthermore, the drug supply module 13 can also provide a first sample solution by providing a catalyst containing transition metal ions to the water sample. The oxygen supply module 17 has a pipeline communication solution space 111, and the solution space 111 supplies oxygen (O2) to release the volatile organic matter in the water sample in the solution space 111, and also provides oxygen and oxygen to the first solution. A second solution is formed.
純水提供模組19係具有管路連通溶液空間111，可對溶液空間111提供純水，而對溶液空間111的水樣進行稀釋，以調整溶液空間111水樣的濃度至適當值，而提升本發明水樣總有機碳含量分析的準確性。The pure water supply module 19 has a pipeline communication solution space 111, which can supply pure water to the solution space 111, and dilute the water sample of the solution space 111 to adjust the concentration of the water in the solution space 111 to an appropriate value. The accuracy of the analysis of the total organic carbon content of the water sample of the invention.
反應管路模組14係具有管路而連通溶液空間111，可接收水樣所釋出的揮發性有機物，還可藉由待氧化溶液提供模組15接收溶液空間中的第二溶液。UV光提供模組16係設置於反應管路模組14中，俾可提供波長介於100至200nm之間與200至280nm之間的UV光，而可氧化水樣所釋出的揮發性有機物，還可讓第二溶液中的催化劑、氧氣與水樣反應生成臭氧（O 3）進而生成氫氧自由基（OH．），以透過氫氧自由基氧化第二溶液中水樣的非揮發性有機物而生成二氧化碳，於本發明的一實施例中，臭氧與水樣反應生成氫氧自由基(OH．)的化學反應式，如後：O 3+H 2O→2OH．+O 2；第二溶液中水樣的有機物氧化的化學反應式，如後：CxHy (aq)+(O 3+OH．)→CO 3 2- (aq)。 The reaction line module 14 has a pipeline to communicate with the solution space 111, and can receive the volatile organic matter released by the water sample, and can receive the second solution in the solution space by providing the module 15 to be oxidized. The UV light providing module 16 is disposed in the reaction line module 14 to provide UV light with a wavelength between 100 and 200 nm and between 200 and 280 nm, and the volatile organic compounds released by the oxidizable water sample The catalyst, oxygen and the water sample in the second solution are further reacted to form ozone (O 3 ) to form a hydroxyl radical (OH.) to oxidize the non-volatile water sample in the second solution through the hydroxyl radical. The organic matter generates carbon dioxide. In an embodiment of the invention, the ozone reacts with the water sample to form a chemical reaction formula of a hydroxyl radical (OH.), such as: O 3 + H 2 O→ 2 OH. +O 2 ; the chemical reaction formula of oxidation of the water-like organic matter in the second solution, such as: CxHy (aq) + (O 3 + OH.) → CO 3 2- (aq) .
應說明的是，本發明催化劑所添加的過渡金屬離子可以促進氫氧自由基的生成，進而提升氫氧自由基在第二溶液中的濃度，而確保水樣中的非揮發性有機物可以氧化生成二氧化碳。因此，本發明不需要加入額外的鹼藥劑，故可大幅降低藥劑的製備難度，也不會有額外的二氧化碳干擾，如此，可以縮短水樣中總有機碳含量的分析時間。再者，本發明也不需要經由過硫酸鹽產生氫氧自由基氧化有機物，故可解決氯離子干擾的問題，且有機物濃度超過偵測範圍時，偵測值也不會降低。It should be noted that the transition metal ion added by the catalyst of the invention can promote the formation of hydroxyl radicals, thereby increasing the concentration of hydroxyl radicals in the second solution, and ensuring that non-volatile organic compounds in the water sample can be oxidized. carbon dioxide. Therefore, the present invention does not require the addition of an additional alkali agent, so that the preparation of the agent can be greatly reduced, and there is no additional carbon dioxide interference, so that the analysis time of the total organic carbon content in the water sample can be shortened. Furthermore, the present invention also does not require the production of oxyhydrogen radicals to oxidize organic substances via persulfate, so that the problem of chloride ion interference can be solved, and the detection value does not decrease when the organic substance concentration exceeds the detection range.
應說明的是，本發明的氧氣提供模組17所提供的氧氣，還可迫使溶液空間111中水樣非揮發性有機物氧化後的二氧化碳流向非分散式紅外線分析儀2，以提供非分散式紅外線分析儀2分析水樣中的總有機碳含量。較佳地，如圖1所示，本發明的分析設備1還針對流向非分散式紅外線分析儀2的流體，提供有氣液分離模組3與冷卻模組4，以藉由氣液分離模組3阻隔液體流向非分散式紅外線分析儀2，還藉由冷卻模組4冷卻流向非分散式紅外線分析儀2的氣體的溫度，俾令非分散式紅外線分析儀2能有效對流體的成分進行分析。It should be noted that the oxygen supplied by the oxygen supply module 17 of the present invention can also force the carbon dioxide oxidized by the non-volatile organic matter in the solution space 111 to flow to the non-dispersive infrared analyzer 2 to provide non-dispersive infrared rays. Analyzer 2 analyzes the total organic carbon content of the water sample. Preferably, as shown in FIG. 1, the analyzing device 1 of the present invention further provides a gas-liquid separation module 3 and a cooling module 4 for the fluid flowing to the non-dispersive infrared analyzer 2, by means of gas-liquid separation mode. The group 3 barrier liquid flows to the non-dispersive infrared analyzer 2, and the temperature of the gas flowing to the non-dispersive infrared analyzer 2 is also cooled by the cooling module 4, so that the non-dispersive infrared analyzer 2 can effectively perform the fluid composition. analysis.
關於冷卻模組4，應說明的是，冷卻模組4係可吸收外界冷卻氣流而提供冷卻功能，甚至還可以對UV光提供模組16提供冷卻氣流，而避免UV光提供模組16高溫而毀壞，俾增加UV光提供模組16的使用壽命。Regarding the cooling module 4, it should be noted that the cooling module 4 can absorb the external cooling airflow to provide a cooling function, and can even provide a cooling airflow to the UV light providing module 16, while avoiding the high temperature of the UV light providing module 16. Destroy, 俾 increase the UV light to provide the life of the module 16.
針對本發明水樣總有機碳含量的分析方法，如圖6所示，於步驟S11的執行過程中，提供水樣。於步驟S12的執行過程中，製備包含水樣及藥劑之第一溶液，如圖3所示，溶液定量儲存模組115係具有管路連通溶液空間111，俾將溶液空間111中預定容量的第一溶液儲存，以定量本發明分析的第一溶液。較佳地，第一溶液所包含的藥劑係包含催化劑，而催化劑係包含過渡金屬離子。For the analysis method of the total organic carbon content of the water sample of the present invention, as shown in Fig. 6, during the execution of step S11, a water sample is provided. During the execution of step S12, a first solution containing a water sample and a medicament is prepared. As shown in FIG. 3, the solution quantitative storage module 115 has a pipeline communication solution space 111, and a predetermined capacity in the solution space 111. A solution is stored to quantify the first solution analyzed in the present invention. Preferably, the first solution comprises a chemical comprising a catalyst and the catalyst comprises a transition metal ion.
另外，由於所提供的水樣可能包含無機碳，於步驟S11的執行期間或步驟S12期間之前的任何時間，如圖2所示，藥劑還可具有包含例如氫離子(H +)的酸劑，以令水樣的PH值小於1，使水樣中的無機碳酸化而生成二氧化碳，藉以排除水樣中的無機碳，而避免水樣中的無機碳影響水樣總有機碳含量的分析。惟，水樣中無機碳的排除方式不以上述內容為限。 In addition, since the provided water sample may contain inorganic carbon, the agent may further have an acid agent containing, for example, hydrogen ions (H + ), as shown in FIG. 2 during the execution of step S11 or at any time before step S12. In order to make the water sample PH value less than 1, the inorganic carbonization in the water sample produces carbon dioxide, thereby eliminating the inorganic carbon in the water sample, and avoiding the inorganic carbon in the water sample affecting the analysis of the total organic carbon content of the water sample. However, the method of removing inorganic carbon in water samples is not limited to the above.
接著，於步驟S12的執行期間或之後的任何時間執行步驟S13，在第一溶液中加入氧氣以形成第二溶液。而後，於步驟S13期間或之後的任何時間執行步驟S14，如圖4所示，令待氧化溶液提供模組15，將第二溶液提供給UV光提供模組16，讓UV光提供模組16對第二溶液提供UV光，而使第二溶液反應生成氫氧自由基(OH．)，而透過氫氧自由基氧化第二溶液中水樣的非揮發性有機物以生成二氧化碳，藉以分析水樣中的非揮發性有機碳含量，一般而言，水樣中的揮發性有機碳含量會遠小於非揮發性有機碳含量，因而水樣中的非揮發性有機碳含量的分析結果，可用來判斷水樣總有機碳含量。Next, step S13 is performed at any time during or after the execution of step S12, and oxygen is added to the first solution to form a second solution. Then, step S14 is performed at any time during or after step S13. As shown in FIG. 4, the solution to be oxidized is supplied to the module 15, and the second solution is supplied to the UV light providing module 16, and the UV light providing module 16 is provided. Providing UV light to the second solution, and reacting the second solution to generate hydroxyl radicals (OH.), and oxidizing the non-volatile organic matter in the second solution through the hydroxyl radical to generate carbon dioxide, thereby analyzing the water sample In the non-volatile organic carbon content, in general, the volatile organic carbon content in the water sample is much smaller than the non-volatile organic carbon content, so the analysis result of the non-volatile organic carbon content in the water sample can be used to judge Total organic carbon content of water samples.
於本發明中，在步驟S14的期間或之後的任何時間，如圖5所示，可令氧氣提供模組17對第二溶液提供氧氣，而迫使第二溶液中氧化而生成的二氧化碳流出溶液空間111，依據經由氣液分離模組3與冷卻模組4而進入非分離式紅外線分析儀2，以對水樣中的非揮發性有機碳含量進行分析。In the present invention, at any time during or after step S14, as shown in FIG. 5, the oxygen supply module 17 can be made to supply oxygen to the second solution, and the carbon dioxide generated by oxidation in the second solution is forced out of the solution space. 111, according to the non-separating infrared analyzer 2 via the gas-liquid separation module 3 and the cooling module 4, to analyze the non-volatile organic carbon content in the water sample.
另外，本發明水樣總有機碳含量的分析方法，由於所分析的水樣可能包含揮發性有機碳，在進行非揮發性有機碳含量分析之前，還包含有分析水樣中揮發性有機碳含量的步驟。如圖7所示，於步驟S21的執行過程中，提供水樣，由於所提供的水樣可能包含揮發性有機碳，於步驟S22的執行過程中，如圖1所示，在水樣中加入氧氣以釋出水樣中的揮發性有機物，而後，於步驟S23的執行過程中，透過揮發性有機物提供模組18，將水樣中所釋出的揮發性有機物提供給UV光提供模組16，使UV光提供模組16對揮發性有機物提供UV光，而讓揮發性有機物氧化而生成二氧化碳，藉以分析水樣中的揮發性有機碳含量。In addition, the method for analyzing the total organic carbon content of the water sample of the present invention may include volatile organic carbon in the analyzed water sample, and the volatile organic carbon content in the analyzed water sample may be included before the analysis of the non-volatile organic carbon content. A step of. As shown in FIG. 7, during the execution of step S21, a water sample is provided, and since the supplied water sample may contain volatile organic carbon, in the execution of step S22, as shown in FIG. 1, the water sample is added. The oxygen is released to release the volatile organic compounds in the water sample, and then, during the execution of step S23, the volatile organic compounds released from the water sample are supplied to the UV light supply module 16 through the volatile organic material supply module 18. The UV light providing module 16 provides UV light to the volatile organic compounds, and oxidizes the volatile organic compounds to generate carbon dioxide, thereby analyzing the volatile organic carbon content in the water sample.
綜上所述，本發明的水樣總有機碳含量分析設備及其分析方法，係透過氫氧自由基氧化水樣中的非揮發性有機物，故可解決高溫燃燒法中的高溫爐壁清洗困難問題，也可解決UV過硫酸鹽法中，氯離子抑制氫氧自由基產生的問題，亦可解決二階段式高級氧化法中，鹼藥劑中溶解二氧化碳而干擾水樣中非揮發性有機碳含量分析的問題，此外還可以透過UV光氧化水樣中的揮發性有機物，是以，本發明可針對水樣中的總有機碳含量進行分析。In summary, the water sample total organic carbon content analysis device and the analysis method thereof are characterized in that the non-volatile organic matter in the water sample is oxidized by the hydroxyl radical, so that the high temperature furnace wall cleaning difficulty in the high temperature combustion method can be solved. The problem can also solve the problem of chlorine ion inhibiting the generation of hydroxyl radical in the UV persulfate method, and also solve the problem of dissolving carbon dioxide in the alkali agent and interfering with the content of non-volatile organic carbon in the water sample in the two-stage advanced oxidation method. The problem of analysis, in addition, can also oxidize volatile organic compounds in the water sample by UV light, so that the present invention can be analyzed for the total organic carbon content in the water sample.
上述實施例僅例示性說明本發明之原理及功效，而非用於限制本發明。任何熟習此項技術之人士均可在不違背本發明之精神及範疇下，對上述實施例進行修飾與改變。因此，本發明之權利保護範圍，應如本發明申請專利範圍所列。The above embodiments are merely illustrative of the principles and effects of the invention and are not intended to limit the invention. Modifications and variations of the above-described embodiments can be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the invention should be as defined in the scope of the invention.
1‧‧‧水樣總有機碳含量的分析設備1‧‧‧Analysis equipment for total organic carbon content in water samples
11‧‧‧設備本體11‧‧‧Device body
111‧‧‧溶液空間111‧‧‧solution space
112‧‧‧底部排液模組112‧‧‧Bottom drain module
113‧‧‧過量排液模組113‧‧‧Excessive drain module
114‧‧‧定量排液模組114‧‧‧Quantitative drainage module
115‧‧‧溶液定量儲存模組115‧‧‧Solution Quantitative Storage Module
12‧‧‧水樣導入模組12‧‧‧Water sample introduction module
13‧‧‧藥劑提供模組13‧‧‧Pharmaceutical supply module
14‧‧‧反應管路模組14‧‧‧Reaction line module
15‧‧‧待氧化溶液提供模組15‧‧‧The module to be oxidized
16‧‧‧UV光提供模組16‧‧‧UV light supply module
17‧‧‧氧氣提供模組17‧‧‧Oxygen supply module
18‧‧‧揮發性有機物提供模組18‧‧‧Volatile Organic Compound Module
19‧‧‧純水提供模組19‧‧‧Pure water supply module
2‧‧‧非分散式紅外線分析儀2‧‧‧ Non-dispersive infrared analyzer
3‧‧‧氣液分離模組3‧‧‧ gas-liquid separation module
4‧‧‧冷卻模組4‧‧‧Cooling module
S11~S14‧‧‧步驟S11~S14‧‧‧Steps
S21~S23‧‧‧步驟S21~S23‧‧‧Steps
圖1，係本發明水樣總有機碳含量的分析設備之執行分析水樣中的揮發性有機碳含量的示意圖。Fig. 1 is a schematic view showing the analysis of the volatile organic carbon content in a water sample by an analysis apparatus for the total organic carbon content of the water sample of the present invention.
圖2，係本發明水樣總有機碳含量的分析設備之執行排除水樣中的無機碳的示意圖。Figure 2 is a schematic illustration of the performance of an analytical apparatus for the total organic carbon content of the water sample of the present invention to exclude inorganic carbon from the water sample.
圖3，係本發明水樣總有機碳含量的分析設備之執行分析水樣中的非揮發性有機碳含量的第一狀態示意圖。Figure 3 is a schematic view showing the first state of the analysis of the non-volatile organic carbon content in the water sample by the analysis apparatus for the total organic carbon content of the water sample of the present invention.
圖4，係本發明水樣總有機碳含量的分析設備之執行分析水樣中的非揮發性有機碳含量的第二狀態示意圖。Figure 4 is a schematic view showing the second state of the analysis of the non-volatile organic carbon content in the water sample by the analysis apparatus for the total organic carbon content of the water sample of the present invention.
圖5，係本發明水樣總有機碳含量的分析設備之執行分析水樣中的非揮發性有機碳含量的第三狀態示意圖。Figure 5 is a schematic view showing the third state of the analysis of the non-volatile organic carbon content in the water sample by the analysis apparatus for the total organic carbon content of the water sample of the present invention.
圖6，係本發明水樣總有機碳含量的分析方法的第一流程示意圖。Fig. 6 is a schematic view showing the first flow of the method for analyzing the total organic carbon content of the water sample of the present invention.
圖7，係本發明水樣總有機碳含量的分析方法的第二流程示意圖。Figure 7 is a schematic view showing the second flow of the analysis method for the total organic carbon content of the water sample of the present invention.
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| CN101907558A (en) * | 2010-03-31 | 2010-12-08 | 浙江环茂自控科技有限公司 | Total organic carbon online analyzer and method for analyzing total organic carbon |
| US20160018376A1 (en) * | 2014-05-23 | 2016-01-21 | Hach Company | Measurement of total organic carbon |
| TWM554167U (en) * | 2017-06-28 | 2018-01-11 | Anatek Enterprise Co Ltd | Total organic carbon analysis equipment for water specimen |
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| CN101907558A (en) * | 2010-03-31 | 2010-12-08 | 浙江环茂自控科技有限公司 | Total organic carbon online analyzer and method for analyzing total organic carbon |
| US20160018376A1 (en) * | 2014-05-23 | 2016-01-21 | Hach Company | Measurement of total organic carbon |
| TWM554167U (en) * | 2017-06-28 | 2018-01-11 | Anatek Enterprise Co Ltd | Total organic carbon analysis equipment for water specimen |
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