1298391 九、發明說明： 【發明所屬之技術領域】 本發明係有關於一種分析裝置，特別有關於一種液流式氣 體採樣分析裝置，可即時現址分析環境中之氣體。 【先前技術】 一台即時分析裝置，包括兩項主要裝置：即時採樣裝置與 即時分析裝置，在氣體方面之分析亦是如此。許多場所如大量 使用酸性或鹼性氣體進行蝕刻之半導體廠房，其酸鹼濃度將會 I 影響到製程的品質；或是貯存大量揮發性液體，揮發後空氣中 濃度過高可能引起爆炸之化工廠，則需要一台即時分析氣體裝 置，可隨時監控有害氣體的濃度。雖然電子儀器日新月異，在 資料的運算和處理上已有長足之進步，但在最基本的採樣和分 析上，仍有些許不足。舉例來說，在氣體採樣上，如石東生等 人於US2004261622所揭示，係將孔洞金屬片塗抹載流液後，以 該金屬片收集氣體樣品，再將載流液萃取出來進行分析，缺點 在於採樣時需要有一定的氣體流速與無法即時分析採樣氣體， ^ 而需一萃取之前置作業。此外如Kurosawa Kiyoko於專利 JP2004233061所揭示，係將氣體與載流液直接接觸，當一定氣 體進入載流液後再將氣體抽出以分析載流液，亦無法即時進行 採樣氣體之分析。另外美國URG Air Sampling Instrumentation 所發展之周邊離子監測器URG 9000 serials則是針對氣體中微 粒成分之分析，其特徵在於具有一小型旋風器用以收集待測氣 體之大粒子，與氣體本身之成份較無關聯。由上述可知，目前 既有之採樣器在操作上均過於複雜，因此開發一簡單而有效率 之即時採樣氣體儀器，即是刻不容緩之議題。 0718-A21271 TWF(N2)；P10940016TW；hsuhuche 5 12983911298391 IX. Description of the Invention: [Technical Field] The present invention relates to an analysis device, and more particularly to a liquid flow gas sampling and analysis device capable of analyzing a gas in an environment in real time. [Prior Art] An instant analysis device consists of two main devices: an instant sampling device and an instant analysis device, as well as gas analysis. In many places, such as a large number of semiconductor plants that use acidic or alkaline gas for etching, the acid-base concentration will affect the quality of the process; or a large amount of volatile liquids will be stored, and the concentration of the air will be too high, which may cause an explosion. , an instant analysis gas device is needed to monitor the concentration of harmful gases at any time. Although electronic instruments are changing with each passing day, there has been considerable progress in the calculation and processing of data, but there are still some shortcomings in the most basic sampling and analysis. For example, in the gas sampling, as disclosed in US Pat. No. 2004-216622, the metal sheet is coated with a carrier liquid, and the gas sample is collected from the metal sheet, and then the carrier liquid is extracted for analysis. A certain gas flow rate is required for sampling and the sample gas cannot be analyzed immediately, and an extraction operation is required. In addition, as disclosed in the patent JP2004233061 by Kurosawa Kiyoko, the gas is directly contacted with the carrier liquid, and when a certain gas enters the carrier liquid and then the gas is extracted to analyze the carrier liquid, the analysis of the sample gas cannot be performed immediately. In addition, the peripheral ion monitor URG 9000 serials developed by URG Air Sampling Instrumentation in the United States is aimed at the analysis of particulate components in gas. It is characterized by a small cyclone for collecting large particles of the gas to be tested, which is less than the composition of the gas itself. Association. From the above, it can be seen that the existing sampler is too complicated in operation, so developing a simple and efficient instant sampling gas instrument is an urgent issue. 0718-A21271 TWF(N2); P10940016TW; hsuhuche 5 1298391
另一方面，現時污染氣體之監測多以離子移動光譜儀（ion mobility spectrometry，IMS)或 FT-IR 光譜儀（Fourier transform infrared)為主。這類工具的體積龐大且昂貴，以FT-IR光譜儀來 說，由於其臨場檢測（特別應用於空氣污染）常會受到溫度、濕度 等參數之影響，因此其濃度常有誤差。若是先採樣氣體後再進 行檢測，則會受到採樣的範圍、方式所影響，且無法即時監控 臨場之氣體成份而進一步即時做出因應措施以避免損害擴大。 另一習知儀器IMS除了難以臨場分析外，其操作上必需利用輻 射物質以離子化被分析的氣體，即意味著必需多一層安全上的 考慮。此外，IMS之原理係檢測帶電離子之荷質比，因此分子 量類似之氣體訊號極有可能重疊，這在判斷上將造成混淆，使 分析人無法確實分辨所要分析之物種。上述兩種儀器較偏向以 氣體分子之物理性質做分析，且無法即時的分析臨場氣體，加 上造價昂貴，體積龐大，操作上需長時間訓練之技術人員等不 利因素。因此現在亟需開發一即時分析氣體之裝置，並結合即 時現址採樣氣體之技術，以達成即時採樣分析氣體之目標。 【發明内容】 本發明提供一種液流式氣體採樣分析裝置，包括：氣體採 樣器，包含：至少一薄膜以區分出氣體通道與載流液艙，使通 過氣體通道之待分析氣體透過薄膜擴散至載流液艙；載流液供 給裝置，供應載流液至載流液艙，以吸收擴散至載流液艙之待 分析氣體；以及分析儀器，用以接收並分析來自載流液艙之載 流液。 此外，本發明提供一種液流式氣體採樣分析方法，包括： 提供如上述之液流式氣體採樣分析裝置於具有待分析氣體之環 0718-A21271TWF(N2)；P10940016TW；hsuhuche ό 修正頁％年）月砣日修正替換頁j 1298391 第94136538號 修正日期:97.3.28 境；將待分析氣體抽入氣體通道後，使待分析氣體透過薄膜擴 散至載流液艙；以載流液供給裝置供應載流液，使其吸收待測 氣體後，以分析儀接收並分析來自載流搶之載流液。 【實施方式】 本發明之較佳實施例請參考第1圖與第2圖，液流式氣體 採樣分析裝置主要包括一氣體採樣器105、載流液供給裝置 101、分析儀器115。氣體採樣器105之外殼如第1圖、第2圖 所示，係一圓柱體，但亦可為其他形狀如方柱體、或其他合適 形狀。氣體採樣器105内包含薄膜203以區分出氣體通道205 與載流液艙201，使通過氣體通道205之待分析氣體11透過薄 膜203擴散至載流液艙201。第2圖顯示載流液艙201與氣體通 道205最簡單之一種設置方式，其他可能之設置方式尚包括第4 圖之多層同心圓，以及第5圖之螺旋式。熟悉此技藝人士自可 依實際需要調整本發明之設置方式，包括有效增加載流液艙與 氣體通道之接觸面積之設置方式，且不受限於第4圖同心圓之 層數，或第5圖螺旋之層數。 本發明用以區分載流液艙201與氣體通道205之薄膜203, 其厚度介於〇.3-0.8公厘，其結構如第3圖所示，係一多孔薄膜 302夾設於兩支撐膜301與303間，且支撐膜301與303之組成、 孔徑、或厚度可相同或不同。支撐膜301、303之孔徑一般遠大 於多孔薄膜302之孔徑，對於載流液分子或待測氣體分子並無 阻隔效果，主要是做為支撐多孔薄膜302之用。多孔薄膜302 之孔徑介於0.01-1微米，可阻隔載流液艙201之載流液分子13 穿過，但可讓氣體通道205之待測氣體11穿過以擴散至載流液 艙201。多孔薄膜302之材質包括但不限定於矽化橡膠（silicone 7 1298391 Γ:)、/:氟乙烯(Tefl°n)、或聚丙烯(pp)。支撐膜之材質可 為PE，或其他具有支撐能力之材料。 、 109、^= 給裝置可更包括載流液循環泵浦125、控制閥 循％官線1G2、1G8、11G、112以使載流液循H以上。 入=體知“ 1G5之氣體通道勝流速約為㈣W公升/分鐘。 在一貫施财，由錢液供給裝置⑻如餘液槽經由管線⑽ 艙201 ’吸收待測氣體u後流經載流液出口 1〇6與管線、 =後j直接流入分析儀器115進行分析。在另一實施例中，載 流液搶2G1之載流液13在吸收待測氣體11後，流經載流液出 口 1，與管線108至控制閥1〇9。控制閥1〇9可使載流液u直 接經由管線114，流至分析儀器丨15 ;或者進行循環。 利用載流液循環泵浦125循環之載流液13流經管線11〇、 、102再次進入載流液入口 1〇4，於氣體採樣器1〇5内再一 次吸收待測氣體後、經載流液出σ 1G6、管線⑽後流入控制閥 =9。利用控制閥1〇9決定是否進行再-次之循環，或直接將載 机液輪入分析儀器115進行分析。亦可調整控制閥⑺9將部份 之载流液13進行分析，另一部份之載流液13進行再循環。上 述之循環步驟主要是應用在極低濃度之氣體分析時，在較高濃 f之氣體分析則可省略此循環裝置。分析氣體之最佳濃度範圍 介於〇·〇1_100 ppm，可包含但不限定於下列物質：酸如氫說酸 或鹽酸；鹼如NH3 ;或有機化合物。一般之載流液為水，或常 見無機溶液與有機溶劑，端視待測氣體之成份而定。當待測氣 體為酸性時，可利用鹼性之載流液加快吸收速度，同理當待測 氣體為鹼性時，可利用酸性之載流液加快吸收速度。 1298391 上述之氣體採樣器，其採樣效率決定於待測氣體之分子大 小、多孔薄膜孔徑大小、待測氣體與載流液之溶解常數(Henry’s law coefficient)，以及待測氣體與載流液之反應常數（比如酸性 氣體對鹼性載流液）。在不考慮薄膜材質特性下， Gromley_Kennedy之預估公式如下： c/c〇=0.819exp(-14.627A)+0.0976exp(-89.22A)+0.01896exp(-212Δ)， △=^DL/4Q，On the other hand, current monitoring of polluted gases is dominated by ion mobility spectrometry (IMS) or FT-IR spectrometer (Fourier transform infrared). These tools are bulky and expensive. FT-IR spectrometers are often subject to errors due to temperature, humidity and other parameters due to their presence detection (especially for air pollution). If the gas is first sampled and then tested, it will be affected by the scope and mode of sampling, and the gas composition of the site cannot be monitored immediately, and the corresponding measures can be further taken to avoid damage expansion. Another conventional instrument IMS, in addition to being difficult to perform on-site analysis, must operate with a radiating substance to ionize the gas being analyzed, meaning that an additional layer of safety considerations is necessary. In addition, the principle of IMS is to detect the charge-to-mass ratio of charged ions. Therefore, the gas signals with similar molecular quantities are likely to overlap, which will cause confusion in the judgment, so that the analyst can not accurately distinguish the species to be analyzed. The above two instruments are more inclined to analyze the physical properties of gas molecules, and it is impossible to analyze the on-site gas in real time, and the disadvantages such as expensive technicians, large volume, and technicians who need long-term training in operation are added. Therefore, there is an urgent need to develop a device for analyzing gas in real time, and combining the technology of sampling gas at the current site to achieve the goal of sampling and analyzing gas in real time. SUMMARY OF THE INVENTION The present invention provides a liquid flow gas sampling and analysis device, comprising: a gas sampler, comprising: at least one film to distinguish a gas channel from a carrier liquid tank, and diffusing a gas to be analyzed through the gas channel through the film to a carrier fluid tank; a carrier fluid supply device for supplying carrier fluid to the carrier fluid tank for absorbing the gas to be analyzed which is diffused into the carrier tank; and an analytical instrument for receiving and analyzing the load from the carrier tank Fluid. In addition, the present invention provides a liquid flow gas sampling analysis method comprising: providing a liquid flow gas sampling and analyzing device as described above in a ring having a gas to be analyzed 0718-A21271TWF(N2); P10940016TW; hsuhuche 修正 correction page % year) Revised replacement page j 1298391 No. 9473638 Revision date: 97.3.28 Environment; after the gas to be analyzed is drawn into the gas passage, the gas to be analyzed is diffused through the membrane to the carrier tank; the carrier fluid supply device is supplied After the fluid is allowed to absorb the gas to be tested, the analyzer receives and analyzes the carrier fluid from the carrier. [Embodiment] Referring to Figs. 1 and 2, a liquid flow gas sampling and analyzing device mainly includes a gas sampler 105, a carrier liquid supply device 101, and an analytical instrument 115. The outer casing of the gas sampler 105 is a cylinder as shown in Figs. 1 and 2, but may be other shapes such as a square cylinder or other suitable shape. A gas film 203 is included in the gas sampler 105 to distinguish the gas passage 205 from the carrier liquid tank 201, so that the gas 11 to be analyzed passing through the gas passage 205 is diffused through the membrane 203 to the carrier liquid tank 201. Fig. 2 shows the simplest arrangement of the carrier tank 201 and the gas passage 205. Other possible arrangements include the multi-layer concentric circles of Fig. 4 and the spiral of Fig. 5. Those skilled in the art can adjust the setting mode of the present invention according to actual needs, including effectively increasing the setting manner of the contact area between the carrier liquid tank and the gas passage, and is not limited to the number of layers of concentric circles in FIG. 4, or 5th. The number of layers of the graph spiral. The invention is used for distinguishing the film 203 of the carrier tank 201 and the gas passage 205, and has a thickness of 〇.3-0.8 mm. The structure is as shown in Fig. 3, and a porous film 302 is sandwiched between the two supports. Between the membranes 301 and 303, the composition, pore size, or thickness of the support membranes 301 and 303 may be the same or different. The pore diameters of the support films 301 and 303 are generally much larger than the pore diameter of the porous film 302, and have no barrier effect on the carrier liquid molecules or the gas molecules to be tested, and are mainly used for supporting the porous film 302. The aperture of the porous membrane 302 is between 0.01 and 1 micrometer to block the passage of the carrier fluid molecules 13 of the carrier tank 201, but allows the gas 11 to be tested of the gas passage 205 to pass through to diffuse into the carrier tank 201. The material of the porous film 302 includes, but is not limited to, a deuterated rubber (silicone 7 1298391 Γ:), /: fluoroethylene (Tefl°n), or polypropylene (pp). The material of the support film can be PE, or other materials with supporting ability. 109, ^= The device may further include a carrier fluid circulating pump 125, and the control valve follows the % official line 1G2, 1G8, 11G, 112 to make the carrier liquid flow above H. Into = body knows that "1G5 gas channel win flow rate is about (four) W liters / minute. In the consistent financial operation, the money supply device (8), such as the remaining liquid tank through the pipeline (10) tank 201 'absorbing the gas to be tested u flow through the carrier fluid The outlet 1〇6 and the pipeline, and the rear j directly flow into the analytical instrument 115 for analysis. In another embodiment, the carrier fluid grabs the 2G1 carrier fluid 13 after absorbing the gas to be tested 11 and flows through the carrier fluid outlet 1 And the line 108 to the control valve 1〇9. The control valve 1〇9 allows the carrier liquid u to flow directly to the analytical instrument 丨15 via the line 114; or to circulate. The current carrying liquid is used to circulate the current of 125 cycles. The liquid 13 flows through the pipelines 11〇, 102 and enters the carrier fluid inlet 1〇4 again. After the gas to be tested is again absorbed in the gas sampler 1〇5, the carrier fluid flows out of the σ 1G6 and the pipeline (10) and flows into the control valve. = 9. Use the control valve 1〇9 to determine whether to perform the re-cycle, or directly transfer the carrier fluid into the analytical instrument 115 for analysis. The control valve (7) 9 can also be adjusted to analyze part of the carrier fluid 13 and A portion of the carrier fluid 13 is recycled. The above cycle steps are mainly applied at very low temperatures. For gas analysis of concentration, the gas analysis can be omitted in the gas analysis with higher concentration. The optimum concentration range of the analytical gas is 〇·〇1_100 ppm, which may include but is not limited to the following substances: acid such as hydrogen Or hydrochloric acid; alkali such as NH3; or organic compound. The general carrier liquid is water, or common inorganic solution and organic solvent, depending on the composition of the gas to be tested. When the gas to be tested is acidic, alkaline can be used. The carrier fluid accelerates the absorption rate. Similarly, when the gas to be tested is alkaline, the acid carrier fluid can be used to accelerate the absorption rate. 1298391 The gas sampler described above has a sampling efficiency determined by the molecular size of the gas to be tested and the pore size of the porous membrane. Size, the reaction constant of the gas to be tested and the carrier liquid (Henry's law coefficient), and the reaction constant of the gas to be tested and the carrier liquid (such as acid gas to alkaline carrier liquid). Regardless of the material properties of the film, Gromley_Kennedy The estimated formula is as follows: c/c〇=0.819exp(-14.627A)+0.0976exp(-89.22A)+0.01896exp(-212Δ), △=^DL/4Q,
其中C是待測氣體離開氣體採樣器之濃度，Co是待測氣體 進入氣體採樣氣之濃度，D是氣體擴散常數，L是待測氣體於採 樣器内移動之距離，Q是待測液的流速。由於後兩項太小可忽 略不計，上述公式可僅估第一項而簡化為： c/c〇=0.819exp(-14.627A)。 為使本領域技藝人士更了解本發明之氣體採樣器，其部份 實施例列舉如下。值得注意的是，本發明之適用情況並不限於 下述實施例，而是以申請專利範圍為主。 58 ppm的NH3，流速約為每分鐘16.85毫升；載流液為4% 檸檬酸水溶液，其流速約為每分鐘0.2毫升，其中所使用的薄膜 為石夕膠（silicone rubber)材質，其厚度為0.5 mm，孔徑平均大小 為0.2μπι ;採樣的環境溫度為室溫，約為22.5°C，相對濕度約 為80%。於90分中的實驗之後，效率約為11·5% ±0.7% 採樣時間 (min) 液體濃度 (ppm) 水中總質量濃度 (ug) 空氣總質量濃度 (ug) 吸收效率 (%) 30 0.4468 0.7686 6.975694 11.018 60 0.4556 0.7862 6.975694 11.271 90 0.4928 0.8606 6.975694 12.337 0718-A21271TWF(N2)；P10940016TW；hsuhuche 9 1298391 在本發明之液流式氣體採樣分析裝置中，分析儀器包括於 93/12/30申請，案號為93141381之連續注入分析儀(Sequential Injection Analyzer，SIA)或其他合適之即時分析之儀器。當待測 氣體含有多種化學物質時，分析儀器可更包括一分流元件將載 流液分流至複數個連續注入分析儀，以同時偵測該待測氣體之 多種化學成份。 SIA並不像URG 9000 serials需要額外之旋風器做為特定 粒子之收集器。此外，SIA與FT_IR或IMS等儀器相較，SIA ® 係根據化學特性而非物理性質進行分析，因此具有較佳之辨識 功能。除上述優點，本發明之儀器較上述習知儀器造價低，體 積小，維護簡易，而且相當輕便。 雖然本發明已以數個較佳實施例揭露如上，然其並非用以 限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範 圍内，當可作任意之更動與潤飾，因此本發明之保護範圍當視 後附之申請專利範圍所界定者為準。Where C is the concentration of the gas to be tested leaving the gas sampler, Co is the concentration of the gas to be sampled into the gas sampled gas, D is the gas diffusion constant, L is the distance the gas to be tested moves within the sampler, and Q is the liquid to be tested. Flow rate. Since the latter two are too small to be neglected, the above formula can be simplified by considering only the first term: c/c〇=0.819exp(-14.627A). To make those skilled in the art more aware of the gas sampler of the present invention, some of the embodiments are listed below. It is to be noted that the application of the present invention is not limited to the following embodiments, but is mainly based on the scope of patent application. 58 ppm NH3, the flow rate is about 16.85 ml per minute; the carrier liquid is 4% aqueous citric acid solution, the flow rate is about 0.2 ml per minute, and the film used is made of silicone rubber, the thickness of which is 0.5 mm, the average pore size is 0.2 μm; the ambient temperature of the sample is room temperature, about 22.5 ° C, and the relative humidity is about 80%. After the experiment in 90 minutes, the efficiency is about 11·5% ±0.7%. Sampling time (min) Liquid concentration (ppm) Total mass concentration in water (ug) Total air mass concentration (ug) Absorption efficiency (%) 30 0.4468 0.7686 6.975694 11.018 60 0.4556 0.7862 6.975694 11.271 90 0.4928 0.8606 6.975694 12.337 0718-A21271TWF(N2); P10940016TW; hsuhuche 9 1298391 In the liquid flow gas sampling and analysis device of the present invention, the analytical instrument is included in the application on 93/12/30, the case number It is a continuous injection analyzer (SIA) of 93141381 or other suitable instruments for real-time analysis. When the gas to be tested contains a plurality of chemicals, the analytical instrument may further comprise a shunt element to shunt the carrier liquid to a plurality of continuous injection analyzers to simultaneously detect various chemical components of the gas to be tested. Unlike the URG 9000 serials, the SIA requires an additional cyclone as a collector for specific particles. In addition, SIA is better than the FT_IR or IMS instruments, and the SIA ® is based on chemical properties rather than physical properties, so it has better identification. In addition to the above advantages, the apparatus of the present invention is lower in cost, smaller in size, easier to maintain, and relatively lighter than the above-mentioned conventional apparatus. While the invention has been described above in terms of several preferred embodiments, it is not intended to limit the invention, and the invention may be modified and modified without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.
0718-A21271 TWF(N2)；P10940016TW；hsuhuche 10 12983.91 【圖式簡單說明】 第1圖係本發明較佳實施例之液流式氣體採樣分析裝置之 示意圖。 第2圖係本發明較佳實施例之氣體採樣器之剖面圖。 第3圖係本發明較佳實施例之薄膜剖面圖。 第4圖與第5圖係本發明其他較佳實施例之氣體採樣器 中，載流液艙、薄膜、與氣體通道之配置圖。 【主要元件符號說明】0718-A21271 TWF(N2); P10940016TW; hsuhuche 10 12983.91 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a liquid flow gas sampling and analyzing device according to a preferred embodiment of the present invention. Figure 2 is a cross-sectional view of a gas sampler in accordance with a preferred embodiment of the present invention. Figure 3 is a cross-sectional view of a film of a preferred embodiment of the present invention. 4 and 5 are configuration diagrams of a carrier liquid tank, a film, and a gas passage in a gas sampler according to another preferred embodiment of the present invention. [Main component symbol description]
11〜待測氣體； 13〜載流液， 101〜載流液供給裝置； 102、108、110、112、114〜管線； 104〜載流液入口； 105〜氣體採樣器； 106〜載流液出口； 10 9〜控制閥； 115〜分析儀器； / 120〜氣體泵浦； 12 5〜載流液循壞果浦， 201〜載流液艙； 203〜薄膜； 205〜氣體通道； 301、303〜支撐膜； 302〜多孔薄膜。 0718-A21271 TWF(N2) ；P 10940016TW；hsuhuche11~ gas to be tested; 13~ carrier liquid, 101~ carrier liquid supply device; 102, 108, 110, 112, 114~ pipeline; 104~ carrier liquid inlet; 105~ gas sampler; 106~ carrier fluid 10; control valve; 115~ analytical instrument; / 120~ gas pump; 12 5~ carrier liquid circulating bad fruit, 201~ carrier liquid tank; 203~ film; 205~ gas channel; 301, 303 ~ Support film; 302 ~ porous film. 0718-A21271 TWF(N2) ;P 10940016TW;hsuhuche