1275786 面，再者，此洗淨水作爲試料水也包含於分析之標的物。 成爲分析含有採集氣體與附著氣體之整體氣體組成，其結 果，可預期特別提高於微量分析領域之分析精度。 排氣採集時，於設置排氣管等之狀態下，由於裝設能自 動洗淨管內的裝置，構造上採集管之裝置必須具有高便利 性，將採集管作成雙層構造。於外管與內管之中間，設爲 流入洗淨液之構造。於採集管管線，設置注入洗淨水之細 孔。利用排氣抽氣幫浦進行抽取，能夠回收至吸收瓶內。 進一步可以作成藉由以幫浦將洗淨水灌入排氣採集管之構 造。於本發明進一步藉由設計注入洗淨水之細孔部分的位 置等、水量及洗淨時間等條件，便可以進行採集。 【實施方式】 以下，茲將根據圖示之實施例，具體說明本發明，第1 圖係有關本發明之自動測定裝置的槪念圖。另外，第2圖 係排氣採集管部分之放大圖。於煙道1內，氣體採集管2 之前端與排氣3相接觸，此部分爲單管。通常，此氣體採 集管之材質係使用耐排氣溫度之不銹鋼。另外，採集管之 管徑約爲5mm左右。 從裝設煙道之凸緣7附近起朝向煙道外部，採集管4、 5爲雙層構造。氣體採集管2連接排氣之吸收瓶1 2，再連 接抽氣幫浦14與氣體流量計1 5。之後，此圖省略了進一 步連接自動採集已吸收排氣成分之試料水的自動分析裝 置。 另外，雙層管構造部分4、5之內部，亦即，於內側管 與外側管之中間，係注入洗淨液之構造。洗淨液係利用洗 1275786 淨液幫浦1 1，從位於雙層管構造部分4、5之末端的洗淨液 注入口 9，注入洗淨液的構造。 針對氣體採集方法進行說明。首先，使排氣抽氣幫浦14 進行運轉。藉此，開始進行煙道排氣之抽取，排氣係通過 排氣採集管，進一步以氣體吸收瓶1 2吸收作爲分析對象之 成分，亦即，此情形爲吸收氨氣，經反應之後，排氣將再 被抽取，經由氣體流量計1 5而予以排放。 定量進行排氣採集之後，抽氣幫浦1 4仍維持運轉，將 洗淨液1 3注入採集管之雙層構造部分。 洗淨液通過內側管與外側管之間的雙層管構造部分4、 5，從其前端部之細孔6，洗淨液注入內側管，亦即，氣體 採集管2之內部。 由於進行抽氣幫浦14之運轉，已注入排氣採集管內部 之洗淨液將朝氣體吸收瓶方向而流向抽取方向，藉此，採 集管裏面將被洗淨，洗淨移送附著於管裏面之氨成分而貯 藏於吸收瓶。藉由進行此採集管裏面之洗淨，能夠有效且 確實地予以回收氨。 進一步說明於排氣採集管之雙層構造部分所發生的現 象，於雙層管之煙道側前端附近，由於與排氣相接觸，加 熱至200〜3 00°C，注入洗淨液之初期，洗淨液（此情形爲純 水）於此部分進行沸騰，已沸騰之水蒸氣，從細孔6朝排 氣抽取方向被抽取，於通過的路徑中’被冷卻成爲液體， 回收至吸收瓶。 再者，若繼續注入洗淨液，整個雙層管將被冷卻’接著 於液體狀態，從細孔6注入洗淨液。此洗淨液同樣被回收 1275786 吸收液 硼酸溶液5g/l 硼酸溶液5g/l 硼酸溶液5g/l 硼酸溶液5g/l 吸收液量 50 ml 50 ml 50 ml 50 ml 洗淨液量 約 150 ml Μ J \ M j \ \\ 約 100 ml 分析用試料溶液 量 250 ml 250 ml 250 ml 250 ml 分析前塵粒處理 膜濾器 分析法 離子層析法 【表2】 高濃度範圍之實驗結果 連續測試No. 連續測定方法 手動分析測定法 連續測定方法 本發明之方法 及加熱方法 JIS法 與手動分析法之比較 濃度A ppm 濃度B ppm A-B ppm 1 加熱方法1 109.0 122.0 -13.0 2 122.0 104.0 18.0 3 126.0 162.0 -36.0 4 109.0 92.0 17.0 5 115.0 136.0 -21.0 6 122.0 147.0 -25.0 7 121.0 131.0 -10.0 8 122.0 124.0 -2.0 9 本發明之方法 126.0 117.0 9.0 10 125.0 104.0 21.0 11 130.0 137.0 -7.0 12 132.0 115.0 17.0 13 132.0 121.0 11.01275786, in addition, this washing water is also included in the object of analysis as the sample water. As a result of analyzing the overall gas composition containing the collected gas and the attached gas, the results can be expected to be particularly improved in the analysis accuracy in the field of micro analysis. At the time of exhaust gas collection, in the state where an exhaust pipe or the like is provided, since the device for automatically cleaning the pipe is installed, the device for constructing the collecting pipe must have high convenience, and the collecting pipe is formed into a two-layer structure. Between the outer tube and the inner tube, a structure into which the cleaning liquid flows is set. In the collection pipe line, a fine hole for injecting the washing water is set. The exhaust pumping pump is used for extraction and can be recycled to the absorption bottle. Further, it can be constructed by pouring the washing water into the exhaust gas collecting pipe by the pump. Further, in the present invention, the collection can be carried out by designing conditions such as the position of the pore portion into which the washing water is injected, the amount of water, and the washing time. [Embodiment] Hereinafter, the present invention will be specifically described based on the embodiments shown in the drawings, and Fig. 1 is a conceptual view of an automatic measuring device according to the present invention. In addition, Fig. 2 is an enlarged view of a portion of the exhaust gas collection pipe. In the flue 1, the front end of the gas collecting pipe 2 is in contact with the exhaust gas 3, and this portion is a single pipe. Usually, the material of this gas collecting pipe is made of stainless steel which is resistant to exhaust gas. In addition, the diameter of the collecting pipe is about 5 mm. The collecting tubes 4 and 5 have a two-layer structure from the vicinity of the flange 7 on which the flue is installed toward the outside of the flue. The gas collection pipe 2 is connected to the absorption bottle 12 of the exhaust gas, and is connected to the pumping pump 14 and the gas flow meter 15. Thereafter, this figure omits an automatic analysis device for further connecting the sample water that automatically collects the absorbed exhaust gas components. Further, the inside of the double pipe structure portions 4, 5, that is, the structure in which the cleaning liquid is injected between the inner pipe and the outer pipe. The washing liquid is a structure in which the washing liquid is injected from the washing liquid inlet port 9 at the end of the double-tube structure portions 4 and 5 by washing 1275786. The gas collection method will be described. First, the exhaust pumping pump 14 is operated. Thereby, the extraction of the flue gas is started, and the exhaust gas passes through the exhaust gas collection pipe, and further absorbs the component to be analyzed as the gas absorption bottle 12, that is, in this case, the ammonia gas is absorbed, and after the reaction, the exhaust gas is discharged. The gas will be extracted again and discharged via a gas flow meter 15. After the exhaust gas collection is quantitatively performed, the pumping pump 14 is still maintained, and the cleaning liquid 13 is injected into the double-layer structure of the collecting pipe. The cleaning liquid passes through the double-tube structure portions 4, 5 between the inner tube and the outer tube, and the cleaning liquid is injected into the inner tube, that is, the inside of the gas collecting tube 2, from the fine hole 6 at the front end portion thereof. Due to the operation of the pumping pump 14, the cleaning liquid injected into the exhaust gas collection pipe will flow toward the gas absorption bottle and flow to the extraction direction, whereby the inside of the collection tube will be washed, washed and transferred to the inside of the tube. The ammonia component is stored in the absorption bottle. By performing the cleaning in the collection tube, ammonia can be recovered efficiently and surely. Further, the phenomenon occurring in the double-layer structure portion of the exhaust gas collection pipe is in the vicinity of the front end of the flue side of the double pipe, and is heated to 200 to 300 ° C in contact with the exhaust gas, and the initial stage of the injection liquid is injected. The washing liquid (in this case, pure water) is boiled in this part, and the boiled water vapor is extracted from the pores 6 toward the exhaust gas extraction direction, and is cooled to a liquid in the passing path, and is recovered to the absorption bottle. . Further, if the washing liquid is continuously injected, the entire double tube will be cooled' followed by a liquid state, and the washing liquid is injected from the fine holes 6. This cleaning solution is also recovered 1275786 Absorbent solution Boric acid solution 5g/l Boric acid solution 5g/l Boric acid solution 5g/l Boric acid solution 5g/l Absorbent volume 50 ml 50 ml 50 ml 50 ml Washing liquid volume about 150 ml Μ J \ M j \ \\ Approx. 100 ml Analytical sample solution volume 250 ml 250 ml 250 ml 250 ml Pre-analysis dust treatment membrane filter analysis ion chromatography [Table 2] High concentration range of experimental results Continuous test No. Continuous measurement Method Manual Analytical Method Continuous Measurement Method Method and Heating Method of the Invention Comparison of JIS Method and Manual Analysis Method Concentration A ppm Concentration B ppm AB ppm 1 Heating Method 1 109.0 122.0 -13.0 2 122.0 104.0 18.0 3 126.0 162.0 -36.0 4 109.0 92.0 17.0 5 115.0 136.0 -21.0 6 122.0 147.0 -25.0 7 121.0 131.0 -10.0 8 122.0 124.0 -2.0 9 Method 126.0 117.0 9.0 10 125.0 104.0 21.0 11 130.0 137.0 -7.0 12 132.0 115.0 17.0 13 132.0 121.0 11.0
-11- 1275786 14 130.0 99.0 31.0 15 138.0 137.0 1.0 16 135.0 117.0 18.0 17 132.0 121.0 11.0 18 140.0 121.0 19.0 19 加熱方法2 121.0 105.0 16.0 20 126.0 107.0 19.0 21 131.0 141.0 -10.0 22 125.0 136.0 -11.0-11- 1275786 14 130.0 99.0 31.0 15 138.0 137.0 1.0 16 135.0 117.0 18.0 17 132.0 121.0 11.0 18 140.0 121.0 19.0 19 Heating method 2 121.0 105.0 16.0 20 126.0 107.0 19.0 21 131.0 141.0 -10.0 22 125.0 136.0 -11.0
【表3】 低濃度範圍之實驗結果 連續測試No. 連續測定方法 手動分析測定法 連續測定方法 本發明之方法 及加熱方法 JIS法 與手動分析法之比較 濃度A ppm 濃度B ppm A-B ppm 1 加熱方法1 9.0 12.0 -3.0 2 8.0 11.0 -3.0 、 3 7.0 11.0 -4.0 4 8.0 10.0 -2.0 5 7.0 10.0 -3.0 6 8.0 10.0 -2.0 7 8.0 11.0 -3.0 8 9.0 11.0 -2.0 9 9.0 11.0 -2.0 10 9.0 10.0 ,-1.0 11 本發明之方法 16.0 15.0 1.0[Table 3] Experimental Results of Low Concentration Range Continuous Test No. Continuous Measurement Method Manual Analysis Measurement Method Continuous Measurement Method Comparison of Method and Heating Method of the Invention JIS Method and Manual Analysis Method Concentration A ppm Concentration B ppm AB ppm 1 Heating Method 1 9.0 12.0 -3.0 2 8.0 11.0 -3.0 , 3 7.0 11.0 -4.0 4 8.0 10.0 -2.0 5 7.0 10.0 -3.0 6 8.0 10.0 -2.0 7 8.0 11.0 -3.0 8 9.0 11.0 -2.0 9 9.0 11.0 -2.0 10 9.0 10.0 , -1.0 11 Method 16.0 15.0 1.0 of the invention
-12- 1275786 12 16.0 16.0 0.0 13 16.0 15.0 1.0 14 16.0 16.0 0.0 15 15.0 15.0 0.0 16 16.0 14.0 2.0 17 17.0 13.0 4.0 18 17.0 15.0 2.0 19 16.0 13.0 3.0 還有’加熱方法係將加熱程度設爲二等級。於表1顯示 個別的排氣採集條件。彙整此等測定條件而將實驗之結果 顯示於表2、第3圖與表3、第4圖。表2、第3圖係於較 高的NH3濃度範圍I30ppm左右等級的比較實驗，連續測試 No·係用以盡可能避免實驗之偏異而連續進行實驗的序 號。另外，連續測定方法與手動分析JIS方法係同時進行 測定的。表3、第4圖係於較低的NH3濃度範圍I5ppm左 右寺級的比較實驗。 各個資料之特徵，若觀察第3圖、第4圖便可以大致上 明瞭’爲了更易於了解，相對於連續測定方法，與作爲基 準的ns方法之測定値的差値，將之作成直方圖，分別爲 第5圖、第6圖。若根據第5圖，於高濃度範圍，相對於 ns方法’加熱方法丨顯示低値，推斷些許之nH3氣體未被 兀全補捉，但連續測定方法可以得到穩定之結果。 相對於JIS方法，加熱方法2顯示大致相同之値，認爲 相較於加熱方法丨已呈現溫度提高之效果。另外，相對於 JIS方法，本發明之方法顯示相當高之値，推斷已完全捕捉 1275786 NHS氣體。同樣地，若觀察第6圖之低濃度範圍，加熱方 法1明確顯示低値。另外，本發明之方法於高濃度範圍同 樣顯示高値。亦即，得知根據本發明之方法，從氣體 濃度高的範圍至低的範圍均爲極佳的方法。 【發明之效果】 如上所述，若根據本發明之排氣採集方法，能夠極精確 地分析排氣之氨氣成分濃度。相較於習知之方法，若根據 本發明之方法，如圖3〜6所示，爲極佳的方法，藉由將此方 法導入連續測定之自動分析裝置，成爲一種極佳的自動分 析裝置。 ㈤【圖式簡單說明】 第1圖係有關本發明實施例之排氣採集方法的槪念 圖。 第2圖係有關本發明實施例之第1圖上的排氣採集管部 分之放大圖。 第3圖係顯示有關本發明實施例之NH3氣體高濃度情形 之各種排氣採集方法之實驗結果的折線圖。 第4圖係顯示有關本發明實施例之nh3氣體低濃度情形 之各種排氣採集方法之實驗結果的折線圖。 第5圖係顯示有關本發明實施例之n η 3氣體高濃度情形 之各種排氣採集方法之比較實驗結果的頻率圖。 第ό圖係顯示有關本發明實施例之ν η 3氣體低濃度情形 之各種排氣採集方法之比較實驗結果的頻率圖。 元件符號說明： -14- 1275786 1…煙道 2···氣體採集管 3…排氣 4…內管 5…外管 6…細孔 7…凸緣 8…封套 9···洗淨液注入口 10…抽氣口 11…洗淨液幫浦 12…氣體吸收瓶 13…洗淨液 14…抽氣幫浦 15…氣體流量計-12- 1275786 12 16.0 16.0 0.0 13 16.0 15.0 1.0 14 16.0 16.0 0.0 15 15.0 15.0 0.0 16 16.0 14.0 2.0 17 17.0 13.0 4.0 18 17.0 15.0 2.0 19 16.0 13.0 3.0 There is also a heating method that sets the degree of heating to two levels. Table 1 shows the individual exhaust gas collection conditions. The results of the experiments are summarized in Table 2, Table 3, Table 3, and Figure 4. Tables 2 and 3 are comparative experiments in the high NH3 concentration range of about I30 ppm, and the continuous test No. is used to avoid the experimental deviation as much as possible and continuously carry out the experiment. Further, the continuous measurement method was simultaneously measured with the manual analysis JIS method. Tables 3 and 4 show comparative experiments at a lower NH3 concentration range of I5 ppm. When the characteristics of each data are observed, it can be roughly understood that, in order to make it easier to understand, the difference between the continuous measurement method and the measurement method of the ns method as a reference is made into a histogram. They are Figure 5 and Figure 6, respectively. According to Fig. 5, in the high concentration range, the heating method is lower than the ns method, and it is inferred that a small amount of nH3 gas is not fully captured, but the continuous measurement method can obtain a stable result. The heating method 2 showed substantially the same enthalpy as compared with the JIS method, and it was considered that the effect of temperature increase was exhibited in comparison with the heating method. In addition, the method of the present invention shows a relatively high enthalpy relative to the JIS method, inferring that 1275786 NHS gas has been completely captured. Similarly, if the low concentration range of Fig. 6 is observed, the heating method 1 clearly shows low enthalpy. In addition, the method of the present invention also exhibits high enthalpy in a high concentration range. That is, it is known that the method according to the present invention is an excellent method from a range in which the gas concentration is high to a low range. [Effect of the Invention] As described above, according to the exhaust gas collection method of the present invention, the ammonia gas component concentration of the exhaust gas can be analyzed extremely accurately. Compared with the conventional method, according to the method of the present invention, as shown in Figs. 3 to 6, it is an excellent method, and this method is introduced into an automatic analyzer which continuously measures, thereby becoming an excellent automatic analyzer. (5) [Simplified description of the drawings] Fig. 1 is a conceptual view of an exhaust gas collection method according to an embodiment of the present invention. Fig. 2 is an enlarged view of an exhaust gas collecting pipe portion in Fig. 1 relating to an embodiment of the present invention. Fig. 3 is a line graph showing experimental results of various exhaust gas collection methods in the case where the NH3 gas is highly concentrated in the embodiment of the present invention. Fig. 4 is a line graph showing experimental results of various exhaust gas collection methods for the low concentration of nh3 gas in the embodiment of the present invention. Fig. 5 is a frequency chart showing comparative experimental results of various exhaust gas collection methods in the case of the high concentration of n η 3 gas in the embodiment of the present invention. The figure is a frequency diagram showing comparative experimental results of various exhaust gas collection methods for the low concentration of ν η 3 gas in the embodiment of the present invention. Description of the component symbols: -14- 1275786 1...Fume 2···Gas collecting pipe 3...Exhaust 4...Inner pipe 5...Outer pipe 6...Pore hole 7...Flange 8...Envelope 9···Washing liquid Inlet 10...Exhaust port 11...washing liquid pump 12...gas absorption bottle 13...washing liquid 14...pumping pump 15...gas flow meter
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