201229488 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種流體中之微粒子檢測裝置及檢測方法，斗寺 別關於一種含有超臨界狀態或液相之高壓二氧化碳的微粒子之檢 測裝置及檢測方法。 【先前技術】 已知有各種檢測存在於流體中之微粒子的方法。例如，直接 鏡檢法，係將以過濾膜過濾被測定水時在過濾膜上捕捉到的微粒 子，使用光學顯微鏡或掃瞄型電子顯微鏡加以檢測(非專利文獻 1)。直接鏡檢法，因被測定流體之壓力直接作用在過濾膜 ，膜=容器(猶膜支持H)，故若被測定流體為高_超過過遽膜 或過濾膜支持器之耐壓極限。因此難以將高壓流 2、 m ’ =文獻丨揭露將高壓流體直接施行直技 此等盘：流體，動的配管設有2處之分支配管， 承受高支持器之兩側相連接。因^^慮膜自兩面 承受到大if力壓力她，·止過_錢_支持器 粒計有细雷射光之散射崎粒子之微 之光透過性2)=測〒體通過被稱作流動室(flow 設置於包夹軸t ^ ^ 。於錢室之—綱照射雷射光，201229488 6. TECHNOLOGICAL FIELD The present invention relates to a microparticle detecting device and a detecting method in a fluid, and a detecting device and a detecting device for a microparticle containing a high-pressure carbon dioxide in a supercritical state or a liquid phase. method. [Prior Art] Various methods for detecting microparticles present in a fluid are known. For example, in the direct microscopic examination, the microparticles captured on the filtration membrane when the water to be measured is filtered by a filtration membrane are detected by an optical microscope or a scanning electron microscope (Non-Patent Document 1). Direct microscopic examination, because the pressure of the fluid to be measured directly acts on the filter membrane, membrane = container (the membrane supports H), so if the fluid to be measured is high _ exceeds the pressure limit of the membrane or filter membrane holder. Therefore, it is difficult to apply high-pressure flow 2, m ’ = literature to expose the high-pressure fluid directly to the straight line. These disks: fluid, moving piping is provided with two branch pipes, which are connected to the sides of the high support. Because ^^ considers the film from the two sides to withstand the pressure of the big if force, · stop _ money _ support granules with fine laser light scattering slag particles of light light permeability 2) = measuring the body through the called flow Room (flow is set on the clamping axis t ^ ^. In the room of the money room - the laser light,
粒子(乾式PC法)，二气。可於流動室導入氣溶膠狀態之微 法可於線上評價，交^、^入έ有微粒子之液體(濕式PC法）。PC 或藍t等之特殊^_室係使用石英 、與PC法類似的 難收升。 法)的方法(專利文獻3 / σ亦知悉有稱為凝結粒子計數法(CPC 周圍使乙醇蒸氣或水卜方法以微粒子為核，於微粒子之 動室，以凝結粒子二成長。將凝結成長之氣溶膠導入流 益’貝又氣溶膠之個數。關於流動室之对壓 4 201229488 室 性能與pc法仍存在同樣的課題。與PC法相 5:為提升流動室之耐壓性能，揭露以曲面構成流路剖二 [習知技術文獻] [專利文獻] 曰本特開2009-52981號公報 曰本特許第3530078號 曰本特開2000-180342號公報 曰本特開2007-57532號公報 曰本特開2008-224342號公報 專利文獻1 專利文獻2 專利文獻3 專利文獻4 專利文獻5 [非專利文獻] 子檢讀1 :日本工業規格__1995「超純水中之微粒 【發明内容】 [本發明所欲解決的問題] 理法i接ϊϊ法^使用專利文獻1之技術則可處理高壓之被處 ’母次測定時必須取下過渡膜，故直接鏡檢法不適 迅速計測。Pc法及cpc法，對流動室之耐 壓!·生此要未咼度可罪性，可適用之壓力亦有極限。 厭對，麟體賴而測定即可麟上述課題。將流體減 壓料f知之構件° _，由於此—構件隨著作動產 生金屬叔專之微粒子，無法實現高的測定精度。 本，明之目的在於提供一流體中微粒子檢測裝置及檢測方 /，可向精度並效率佳地檢測高壓流體所含之微粒子。 [解決問題之技術手段] I,人發明之一實施態樣，具有：流體供給部，將被測定流體 财之微粒子制裝置；縮小管，—端與流體供給 ft接，相對於流體供給部將流路縮小；以及微粒子檢測機構， /、流路縮小管之另一端連接，檢測自流路縮小管流入之微粒子。 5 201229488 —流路縮小管相對於流體供給部將流路縮小。因此，流路縮小 管可藉由縮小之效果將被測定流體減壓，並可藉流路縮小管内辟、 與被測定流體之摩擦損失將被測定流體緩緩地減壓。將減壓之二 體導入微粒子檢測機構，故難以產生構件之耐壓性問題，可將g 去以來應驗健越之檢峨構直接使用。且，流仏縮小管並 j可動部，此外可緩緩地將壓力減少，故並無伴隨作動而產生 金，粉等之微粒子的疑慮，即便是微量之微粒子亦能夠以高精度 測疋。由於可介由流路縮小管將自流體供給部供給之被 連續地導入微粒子檢測機構，故可有效率的測定。 — —依本發明之另—實施態樣，流體中之微粒子檢測方法具有： 精由流體供給部供給制定越之步驟；藉由麟供給之被測定 ^體通過相對於流體供給部將流路縮小之流路縮小管，將被測定 流體減壓之步驟；以及檢測經減壓之被測定流體所含的微粒子之 步驟。 [本發明之效果] 如同以上#明’依本發明，能夠提供―種流體♦之微粒子檢 測裝置及檢測方法，可高精度並效率佳地檢測高壓越所含之微 【實施方式】 [實施本發明之最佳形態] =下^參考附圖對本發明之流體中微粒子檢測裝置及測定方 法，貝施形態加以說明。制於本發明之流體的壓力及種類雖無 本發明特射朗於高壓之超臨界、液體或氣體的二氧 匕石，所S，，粒子的測定。因此，以下的說明係以超臨界、液體 或氣體的一氧化碳為對象來進行。 本測，裝气可與既存之二氧化碳製造設備或供給設備連接以 ^ 。此处，先就二氧化碳製造設備或供給設備之概要加以說明。 ^ 1，作為-例之二氧化碳供給設備i的概略構成圖。c〇2缸 同2貯藏液體二氧化碳。將c〇2缸筒2所貯藏之液體二氧化碳以 6 201229488 金屬氣體過濾器3a過濾，導入凝結器4。二氧化碳以凝結器4凝 結’被送至C〇2槽5°C〇2槽5之二氧化碳先以預冷卻器6過冷卻， 成為液體之二氧化碳。以預冷卻器6進行之過冷卻，係為了防止 氣體^^一氧化碳在後段的循環果7產生。二氧化碳以循環栗7升 壓，以金屬氣體過濾器8過濾，成為乾淨的高壓之液體二氧化碳， 通過閥12d，被送往未圖示之使用點。使未使用的高壓之液體二氧 化碳於保壓閥9之出口側膨漲，更以蒸發器10轉換為氣相。此係 巧了提升後段之金屬氣體過濾器3b的除粒子效率。如此，二氧化 碳供給設備，使二氧化碳沿著循環迴圈循環，並因應必要於使用 點供給高壓之液體二氧化碳。關於超臨界狀態之二氧化碳的供給 設備，除了將液體二氧化碳加熱以使其升溫至臨界溫度以上^ 以外，可為同樣之構成。 微^子檢測裝置11，可設置於此一二氧化碳供給設備丨之線 上的任意位置。例示之採樣處P1〜P3分別為金屬氣體過濾器8之 出口部、C〇2槽5之底部及金屬氣體過濾器北之出口部。微粒子 檢測裝置11介由閥12a〜12c與二氧化碳供給設備！相連接。微 ，子檢測裝置11檢測自各採樣處P1〜P3流入的二氧化碳所含之 微粒子。採樣處P1〜P3巾的二氧化碳之壓力雖無關，依本發 明，可取出特別為壓力1MPa以上之高壓二氧化碳。 圖2A，顯示微粒子檢測裝置u之概略構成圖。微粒子檢測 裝’具備例如以具有既定内徑之配管構成的供給被測定流體 之&體供給部13、作域壓機構之流路縮小管14、以及微粒子檢 測機構15。圖中之虛線示意二氧化碳的流動。 流體供給部13之-端’介由μ 12a〜12c與二氧化碳供 備1連接，另一端則與流路縮小管14連接。超臨界、液體 之高壓二氧化碳通财體供麟13賴地供給予 =。流體供給部13，圖2A中雖以配管顯*，但依闊i2a〜仏(測 疋點)之狀況’可選擇鋼管等之配管或高壓管、接頭等。亦可去除 ΐ 所示之流體供給部13 ’將閥12a〜12c與流路縮小管14直 接連接，制12a〜12e作為越供給部_。絲況，亦可介由 201229488 化碳供給設備1之循環迴圈(母管)與流路縮小管14 體供給部作用。採用任-.可。此外，亦對於流體供給部13將流路縮小即 之高;二，給;藉由調整保壓闕將-定流量 管路另f—端14a與流體供給部13連接，流路縮小 微粒子檢測‘ 15 測機構15連接。流路縮小管14與 閥等連接，連接並無特別限定，可介由配管、接頭、 微粒子檢測機為來/要之^路^、管14與 出之分支管構介由_二氧化奴—部分往大氣排 果，擦Si: 由，^ 縮小效果與摩擦損失：被測ί流減 容易度)與加叫性峨之表面處理的 給碳之供 化碳之勤賴降低，碰=遽賴麵錢將縫二氧 剖面之ί以圓形 徑的比為10以上、500_0以下。g 4之例使配官長對内 流路縮小管Μ的情況對=之^==己管構成 靡。以下。因此，自設置空間之二之看更：：：= 8 201229488 情形。此一情形，可以彎曲為螺旋狀、或捆捲為圓形(參考圖2B) 等適宜之方法使其變形，將設置空間縮小。 流路縮小管14之兩端14a、14b附近，設有將流路縮小管14 加熱之加熱器(力π熱機構)l6a、16b。加熱器16a、16b之設置位置 並不限定於此，可設於流路縮小管14之入口附近或出口附近之兩 ^任一處，或设於其他位置。加熱器16a、l6b之種類亦無特別限 例如，可為捲繞流路縮小管14之線圈狀的加熱器、帶狀加熱 器(，狀的加熱器)等。然而如圖2B所示，使用束為圓形的流路縮 小管24之情況，入口側與出口側為未捆捲狀態，宜至少在未捆捲 之部分設置加熱器16a、16b。此外，亦可以加熱器將捆捲之流路 縮小管全體加熱。 設置與加熱器16a、16b鄰接而測定二氧化碳溫度的溫度計 。加熱1116a、16b及溫度計17a、17b _整越之溫度 ^控，裝置is相連接。作為溫度計可使用例如熱電偶。 f度計,17a、17b之溫度計測部可位於流路縮小管14之内部，但 為防止微粒子的產生，宜設於流路縮小管14之外面。控制裝置Μ ^應溫度計17a、l7b之計測結果，控制加熱器恤、脱的發孰 ^。具體而言’控繼置18將流動於流路縮小f 14之内部的二 :化碳維持為蚊溫度，以使二氧化碳自流路縮小管丨4以完全之 粒子之檢測不造成大影響程度的極少量固相或 液相之乳相，流入微粒子檢測機構15。 杆-縮小管14之内部將二氧化碳減麵移動時，可視為施 给變化。圖3示意二氧化碳之p-h線圖。橫 i示壓力’虛線表示等溫線^右側表示溫 人流路縮小管14時，二氧化碳之狀態自Particles (dry PC method), two gases. The micro-method that can introduce the aerosol state in the flow chamber can be evaluated on-line, and the liquid with fine particles (wet PC method) can be transferred. The special ^_ room of PC or blue t is quartz, which is similar to the PC method. The method of the method (Patent Document 3 / σ also knows that there is a method called coagulation particle counting (the method of making ethanol vapor or water in the vicinity of CPC is made of microparticles as a core, and in the moving chamber of the microparticles, the coagulated particles are grown. The number of aerosols introduced into the flow of 'Yibei' and the number of aerosols. The pressure on the flow chamber 4 201229488 Room performance and the PC method still have the same problem. Compared with the PC method 5: to improve the pressure resistance of the flow chamber, expose the surface 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 [ 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 JP-A-2008-224342 Patent Document 1 Patent Document 2 Patent Document 3 Patent Document 4 Patent Document 5 [Non-Patent Document] Sub-examination 1 : Japanese Industrial Specifications __1995 "Particles in Ultrapure Water [Invention Content] [This The problem to be solved by the invention] The method of the method of the invention is to use the technique of the patent document 1 to handle the high pressure. The transition film must be removed during the mother-to-child measurement, so the direct microscopic method is not suitable for rapid measurement. Pc method and cpc Law, on the flow room Withstand pressure! · It is guilty to be guilty of this, and there is a limit to the pressure that can be applied. It is ridiculous, and it can be measured by the lining of the body. The fluid decompression material knows the component ° _, because of this - The member can produce high-precision precision with the micro-special particles of the metal. The purpose of the present invention is to provide a micro-particle detecting device and a detecting unit in a fluid, which can accurately and efficiently detect the micro-particles contained in the high-pressure fluid. [Technical means for solving the problem] I, in one embodiment of the invention, has a fluid supply unit, a microparticle device for measuring a fluid, and a reduction tube, the end is connected to the fluid supply ft, and the fluid supply portion is The flow path is narrowed; and the other end of the flow path narrowing pipe is connected to the fine particle detecting means, and the small amount of the flow path narrowing pipe is detected. 5 201229488 - The flow path narrowing pipe narrows the flow path with respect to the fluid supply part. The reduction tube can reduce the pressure of the fluid to be measured by the effect of reduction, and can reduce the pressure of the tube and the friction loss of the fluid to be measured by the flow path, and gradually reduce the pressure of the fluid to be measured. Since the decompressed two-body is introduced into the microparticle detection mechanism, it is difficult to cause the problem of the pressure resistance of the member, and the inspection can be directly used after the g-test has been performed. Moreover, the flow-reduction tube and the movable portion can be slowed down. Since the pressure is reduced by the ground, there is no doubt that the particles such as gold and powder can be generated by the action, and even a small amount of fine particles can be measured with high precision. Since the flow path narrowing pipe can be supplied from the fluid supply unit The microparticle detection mechanism is continuously introduced, so that the measurement can be efficiently performed. According to another embodiment of the present invention, the microparticle detection method in the fluid has the following steps: the step of supplying the fluid supply unit by the fluid supply unit; The step of reducing the flow path by reducing the flow path with respect to the fluid supply unit, decompressing the fluid to be measured, and detecting the fine particles contained in the fluid to be measured under reduced pressure. [Effects of the Invention] As described above, according to the present invention, it is possible to provide a fine particle detecting device and a detecting method for a seed fluid ♦, and it is possible to accurately and efficiently detect the high voltage contained therein. [Embodiment] [Implementation] BEST MODE FOR CARRYING OUT THE INVENTION The lower portion of the fluid detecting device and the measuring method of the present invention will be described with reference to the accompanying drawings. The pressure and type of the fluid to be used in the present invention are not measured by the super-critical, liquid or gaseous dioxite, S, and particles of the present invention. Therefore, the following description is directed to carbon monoxide which is supercritical, liquid or gas. In this test, the gas can be connected to the existing carbon dioxide manufacturing equipment or supply equipment. Here, an outline of a carbon dioxide manufacturing facility or a supply facility will be described first. ^ 1, a schematic configuration diagram of the carbon dioxide supply device i as an example. C〇2 cylinder The same as 2 storage liquid carbon dioxide. The liquid carbon dioxide stored in the c〇2 cylinder 2 is filtered by the 6 201229488 metal gas filter 3a, and introduced into the condenser 4. The carbon dioxide is condensed by the condenser 4, and the carbon dioxide which is sent to the C 〇 2 tank 5 ° C 〇 2 tank 5 is first supercooled by the pre-cooler 6 to become liquid carbon dioxide. The supercooling by the precooler 6 is to prevent the generation of the gas 5 in the subsequent cycle. The carbon dioxide is filtered at a pressure of 7 liters of the pump, and is filtered by a metal gas filter 8 to become a clean high-pressure liquid carbon dioxide, which is sent to a point of use not shown through the valve 12d. The unused high-pressure liquid carbon dioxide is swollen on the outlet side of the pressure-retaining valve 9, and is further converted into a gas phase by the evaporator 10. This is a method of improving the particle removal efficiency of the metal gas filter 3b in the rear stage. Thus, the carbon dioxide is supplied to the apparatus to circulate carbon dioxide along the circulation loop and supply high-pressure liquid carbon dioxide at the point of use as necessary. The supply device for carbon dioxide in a supercritical state may have the same configuration except that the liquid carbon dioxide is heated to raise the temperature to a critical temperature or higher. The micro-detection device 11 can be disposed at any position on the line of the carbon dioxide supply device. The sampled portions P1 to P3 are exemplified by the outlet portion of the metal gas filter 8, the bottom of the C 〇 2 tank 5, and the outlet portion of the metal gas filter north. The microparticle detecting device 11 is connected to the carbon dioxide supply device via the valves 12a to 12c! Connected. The micro-detection device 11 detects the microparticles contained in the carbon dioxide flowing from the respective sampling points P1 to P3. The pressure of carbon dioxide in the sampling place P1 to P3 is irrelevant. According to the present invention, high-pressure carbon dioxide having a pressure of 1 MPa or more can be taken out. Fig. 2A shows a schematic configuration diagram of the fine particle detecting device u. The microparticle detecting device includes, for example, a "body supply unit 13 for supplying a fluid to be measured, a flow path reducing tube 14 serving as a field pressure mechanism, and a fine particle detecting unit 15 which are constituted by a pipe having a predetermined inner diameter. The dotted line in the figure indicates the flow of carbon dioxide. The end of the fluid supply portion 13 is connected to the carbon dioxide supply 1 via the μs 12a to 12c, and the other end is connected to the flow path reduction tube 14. Supercritical, liquid high-pressure carbon dioxide through the financial body for the Linyi 13 to give =. In the fluid supply unit 13, the piping is shown in Fig. 2A, but the piping of the steel pipe or the like, the high pressure pipe, the joint, or the like can be selected depending on the condition of the width i2a to 仏 (measurement point). It is also possible to remove the fluid supply portion 13' shown by ΐ and connect the valves 12a to 12c directly to the flow path reducing tube 14 to produce 12a to 12e as the supply portion _. The wire condition can also be applied to the circulation loop (female pipe) of the 201229488 carbon supply device 1 and the flow supply reduction pipe 14 body supply portion. Use any -. Further, the fluid supply unit 13 also reduces the flow path to a high level. Second, by adjusting the pressure maintaining 阙, the constant flow rate line is connected to the fluid supply unit 13 and the flow path is reduced by the microparticle detection. 15 The measuring mechanism 15 is connected. The flow path narrowing pipe 14 is connected to a valve or the like, and the connection is not particularly limited, and the pipe, the joint, the microparticle detecting machine can be used as the main pipe, the pipe 14 and the branch pipe are separated from the slave pipe. Partially draining the fruit to the atmosphere, rubbing Si: by, ^ reduction effect and friction loss: the ease of measurement is reduced, and the surface treatment of the carbonization of the carbon is reduced by the hard work of carbon supply. In the case of the face money, the ratio of the circular diameter of the dioxin profile is 10 or more and 500_0 or less. In the case of g 4, the situation in which the official is reduced to the internal flow path is 对 = =============== the following. Therefore, from the second place of the setting space:::= 8 201229488 situation. In this case, it is possible to bend it into a spiral shape or to wind it into a circular shape (refer to FIG. 2B) to deform it, and to reduce the installation space. In the vicinity of both ends 14a and 14b of the flow path reducing pipe 14, heaters (force π heat means) 16a and 16b for heating the flow path reducing pipe 14 are provided. The installation positions of the heaters 16a and 16b are not limited thereto, and may be provided at either of the vicinity of the inlet of the flow path reduction pipe 14 or the vicinity of the outlet, or at another position. The type of the heaters 16a and 16b is not particularly limited. For example, it may be a coil-shaped heater that winds the flow path reducing pipe 14, a ribbon heater, or the like. However, as shown in Fig. 2B, in the case where the flow path narrowing tube 24 having a circular shape is used, the inlet side and the outlet side are in an unwound state, and it is preferable to provide the heaters 16a, 16b at least in the unwound portion. Further, the heater may heat the entire narrowing pipe of the winding. A thermometer that measures the carbon dioxide temperature adjacent to the heaters 16a and 16b is provided. Heating 1116a, 16b and thermometers 17a, 17b _ the temperature of the whole control, the device is connected. As the thermometer, for example, a thermocouple can be used. The thermometer measuring portion of the f-meters 17a and 17b may be located inside the flow path reducing tube 14, but it is preferably provided outside the flow path reducing tube 14 in order to prevent the generation of fine particles. The control device Μ ^ should be controlled by the thermometers 17a, l7b to control the heater shirt and the hairpin. Specifically, the control relay 18 maintains the flow of the carbon dioxide in the interior of the flow path to be reduced to the mosquito temperature, so that the carbon dioxide is reduced from the flow path by the tube 4 so that the detection of the complete particles does not cause a large degree of influence. A small amount of the solid phase or the liquid phase of the liquid phase flows into the fine particle detecting mechanism 15. When the inside of the rod-reduction tube 14 moves the carbon dioxide reduction surface, it can be regarded as a change in application. Figure 3 illustrates the p-h diagram of carbon dioxide. The horizontal direction shows the pressure 'the dotted line indicates the isotherm ^ the right side indicates the temperature of the warm flow path reduction tube 14, the state of the carbon dioxide from
化碳供魏縮小管14流出。因將氣相之:氧 法檢測^ΐ ]機構15，故如戰述依乾式PC法或CPC 其次，考慮捨較小的狀態，亦即供給較A點低溫之二氧化碳 201229488 的情況(c點）。低溫之二氧化碳等捨變化，則依減壓條件，有成為 氣固混合狀態之可能性(D，，點）。氣固混合狀態係指，二氧化碳的^ 況下，於氣相中產生固相的乾冰之狀態。因固相在減壓進行下仍 持續存在，故二氧化碳若以氣固混合狀態流出流路縮小管14並流 入，粒子檢測機構15，則二氧化碳之固相與原本應檢測之微粒^ 變得無法區別。此處’使加熱器l6a、l6b作動，重新使二氧化碳 之度上升(E點）。此一結果，使二氧化碳的焓增加，即便減壓仍 防止其成為氟固混合狀態(B’點）。此外，使用乾式pc法或cpc進 行微粒子之檢測的情況，宜使二氧化碳完全地汽化。此處，藉著 以加熱器16a、16b將二氧化碳加熱，亦可避免氣液混合狀態曰 點）。 ^ 产加熱器16a、16b之目的為，將二氧化碳加熱以使二氧化碳在 氣相之狀態下檢測微粒子。此外，加熱器16a、16b之目的為，將 導入至=測器之二氧化碳的溫度保持一定。因此，加熱器i6"i6b 不必非得設於流路縮小管14’亦可設於微粒子檢測機構15之入口 然則，因流路縮小管14為配管且構造簡單，故加熱器之設 此外即便一氣化碳之固相或液相暫時產生，於導入微粒子 =機,15之時點消失即可。亦即二氧化碳即便暫時成為d，點或 ^點之狀態，只要最終成為E，點或E”之狀態即可。然則，因狀態 變化需要若干程度之_，故盡可能於流路縮小管14、之上游側二 熱者，在避免氣固混合狀態或氣液混合狀態上較為適宜。自此一 觀點七看，宜將加熱器16a設於流路縮小管14之入口 14a附近。 ”ίΐί期加熱，亦可於不產生氣固混合狀態或氣液混合狀態 ^问^區域施行等焓變化(D—Ε—Β，）。另一方面，為了將二氧化 ΪΪϋ氣相導入微粒子檢測機構15，亦宜將加熱器16b設於 "IL g 14之出口 14b附近，進一步亦可於入口 14a附近與出 之兩方位置分別設置加熱器16a、16b。如此可因^目 的適^決疋加熱器l6a、l6b之設置位置。 右使流路縮小管14之内徑增大則縮小效果減少，減壓之程度 10 201229488 ，小。同樣地若使流路縮小管14之配管長度減短，則減壓之程度 變小。可合併進行流路縮小管14之配管長與流路面積(内抵)的調 整、以及加熱器16a、16b的流路縮小管14之溫度控制。即便在 使流，縮小管14之流路面積與長度適當化的情況，為避免氣固混 合狀態或氣液混合狀態更宜施行流路縮小管14之溫度控制。 、使用流路縮小管14之減壓方法因不須如習知之減壓閥般的機 械性作動之部分，在原理上不會有伴隨作動產生金屬粉等之微粒 子。因此，得以以高精度檢測二氧化碳所含之微粒子.。作為其他 減壓方法雖亦考慮使用過濾器，但因過濾器在長時間之使用中重 ，微粒子的附著、剝離，難以精密測定。與此相對使用流路縮小 管14之減壓方法，幾乎沒有就微粒子檢測機構15而言成為汙染 源(或對照微粒子數上升之原因）的金屬粉等之微粒子的產生，可^ 精度地測定。且，調整流路縮小管14之流路面積(内徑)及全長， 進一步施行加熱器16a、16b之溫度控制，故難以受到採樣處ρι 〜P3之溫賴力餅的影響，舊可钱崎度佳地施行微粒 檢測。 ， 流路縮小管14之其他優點為，因配管長度長故熱傳面積 =。因此加減圍設定之自由度高，亦得以確保可溫度控制之範 ^大，故可細緻地進行溫度控制。因具有廣大熱傳面積，依 核境溫度’即便不必須設置加熱||仍可將二氧化碳轉 ^度範圍。減壓閥與過濾器，因減壓係集中於實際上之一點 行，故難以細緻地進行溫度控制。此外，流、^ 可靠性高，維修之必要性亦小，於成本面亦為有/構化早而 微粒子檢測麵15，檢測自流路縮小；f 14 臨液體或氣^二氧化碳，藉流路縮小管M減壓後成為氣相， 一氧化碳原本所έ之微粒子存在於氣相中。將此一含有 J相的二氧化碳導人微粒子檢顺構”，檢測氣械二氧化^ 3之微粒子。此一微粒子檢測法，可使用乾式pc法或cp =乾式PC法之微粒子檢測機構15，具有於微粒子照射射 光之機構、以及制來自雜子之雷射光的散射光之機構。乾式 201229488 pc法，係以半導體雷射所產生之雷射光照射氣相中之微粒子，檢 測來自微粒子之直接的散射光。 圖2顯示依據CPC法之微粒子檢測機構15 ^微粒子檢測機構 15具有凝，室20 ’該凝結室20具備乙醇等之蒸氣的供給口 2〇a。 於成為乙醇等之過飽和氛圍的凝結室2〇導入微粒子，以此一微粒 子為核使乙醇專之蒸氣凝結成長。凝結室2〇之下游側為以雷射光 可穿透之材料所製作的流動室21。流動室21之側方，配置：半導 體雷射22 ’於蒸氣之凝結成長的微粒子照射雷射光；以及光電轉 換器23/檢測來自蒸氣之凝結成長的微粒子之雷射光的散射光。 微粒子係為蒸氣附著而凝結成長之氣溶膠(液滴），於此一液滴照射 雷射光。使液滴之粒徑大至光散射法可測定之程度，藉光散射法 計測微粒子之個數(濃度）。因此CPC法，與乾式pc法相較可檢測 至更小粒徑之微粒子為止。另一方面，因乾式PC法係於微粒子照 射直接雷射光，故可求出微粒子之粒徑分布。 、·此外，因在流路縮小管14被減壓之流體的流速增加，有對微 粒'^檢測機構15造成不必要之負荷的情況。因此，亦可如實施例 所示，於微粒子檢測機構15之下游側設置泵以將適當流速•流量 的被測定流體導入微粒子檢測機構15，並於微粒子檢測機構15 之上游側设置大氣開放機構，將未導入至微粒子檢測機構15之流 體排氣。果可設於微粒子檢測機構15與大氣開放機構之間，但因 自栗產生之微粒子有被導入微粒子檢測機構15之可能性，故宜設 置於微粒子檢測機構15之下游側。 【實施例】 於圖4顯示實施例的流程圖。高壓流體，係使用以株式會社 Pl^ERON JAPAN社製金屬氣體過濾器(過濾精度〇〇〇3μιη)過濾 之高壓二氧化碳。高壓二氧化碳，通過内徑4.35mm之流體供給 部’連續地供給至作為減壓機構之流路縮小管。高壓二氧化破 之流體供給部設有分支管19，將一部分的二氧化碳通過保壓閥2〇 而排氣。保壓閥20之設定壓力為9MPa，將一定流量(3g/min)之高 壓二氧化碳供給予流路縮小管14。流路縮小管14，管徑為 12 201229488 Φ200μιη、管長為30m，以SUS316製作。流路縮小管14捆捲為 Φ 48cm之圓形，兩端為未捆捲狀態。 … 於流路縮小管14之入口附近與出口附近的2處設置加熱器 16a、16b ’控制溫度使流路縮小管14外面的溫度分別成為6(rc'^ =°C。具體而言，準備寬度4cm、長度3m之帶狀加熱器作為加^ 器16a，自流路縮小管14之始端起沿著流路縮小管14之未捆捲. 分安裝，更將餘下的部分安裝於流路縮小管14之束起部分。同^ 地，準備寬度4cm、長度3m之帶狀加熱器作為加熱器脱，自位 於流路縮小管14下游側之排氣管分支部27 _近起沿著流 小管14之未捆捲部分安裝，更將餘下的部分安裝於流路縮小管14 之束起部分中、與未捆捲部分連接之部分。圖4， 加熱器16a、16b之範圍。 π I衣 將於流路縮小管14賴之二氧化碳巾所含的微粒子數 度），以使用cpc法之微粒子檢測裝置15(TSI社製cpc377 測。微粒子檢測裝置15之下游侧設有泵28，於減壓之二氧化碳°中 抽吸一定流量(lL/min)的份而導入微粒子檢測裝置 排氣管分支部27放$至大氣。 自 比㈣1 株#轉城賴之好關^作為減 構，比較例2使用減壓閥(TESC0M社製)作為減壓機構。比較例= 於，較例1之流量限制器的後段，與實施例同樣地，設置設 熱器之流路縮小管14〇2GGmiii、3Gm)。比較例i、3 器，為可去除粒徑2μιη以上之微粒子的過渡器。 閥，外周部設有寬度4Cm、長度3cm之帶狀加轨器，^ 偶的溫度控制為職。控制使流量限制11其^部溫度 圖5Α〜5C顯示實施例及各比較例巾，計 子數制之結果， 例Ιΐΐ ^ ^示比f例3之測定結果，圖5c顯示實施 机貝疋尨果，板軸為經過時間、縱軸為檢測到的粒子 lcc之檢测粒子數）。圖5B、5C之縱抽為相同比例，但圖&之 13 201229488 轴的比例與圖5B、5C相比為放大ιοοο倍。 考慮比較例2減壓閥之作動所致使的金屬粉等之微粒子的產 生，以微粒子之濃度低的流體為測定對象之情況下，難以獲得實 用if測疋精度。比較例2檢測粒子數雖較比較例1少，但仍檢測 到遠較後述之實施例為多之微粒子。考慮比較例丨中，受到重複 在過濾器附著、剝離的微粒子之影響。進一步地推論觀察因比較 例1、2溫度控制不充分，二氧化碳部分變為固相或液相流入測定 ^置。考慮比較例3由於在比較例丨之過濾器後段設置實施例的 設有加，器之流路縮小管14，二氧化碳完全地成為氣相。比較例 3可說是將重複在過濾器附著、剝離的微粒子之影響的份抽出之例 子。比較例1〜3，被測定對象原本所含之微粒子以外的微粒子對 測定結果造成影響，檢測粒子數高，計測値不安定。 /另一方面，實施例中檢測粒子數較各比較例變得更少，幾乎 未受到被測定對象原本所含之微粒子以外的微粒子之影響，獲得 安定之計測値。 a ^ ^其次，圖6顯示本實施例中，計測高壓二氧化碳供給裝置其 採樣處Ρ2、Ρ3 ’ Η之粒徑超過i〇nm的微粒子數(濃度)之結果。 採樣處P1〜P3為如同圖丨所示之位置。雖確認變更採樣處時有過 渡性的微粒子數增加之現象，但獲得幾乎與採樣處符合之微粒子 數。 〇進一步，圖7A顯示於同一採樣處中，計測施行閥29的開閉 操作時之粒徑超過l〇nm的微粒子數(濃度)之結果。此一閥29，為 了觀察到閥之開閉操作的影響，為以圖7B所示之結構設置。將設 有閥之線25與未設有閥之線26並排地構成，供給二氧化碳並施 行閥29之開閉動作，測定微粒子數。施行閥之開閉動作後微粒子 數暫時性地增加，其後再度回復為穩定的狀態。 如此’確認可連續地監測施行採樣處之變更或閥之開閉操作 時的微小微粒子數(濃度)之變化。 201229488 【圖式簡單說明】 圖1係二氧化碳供給設備的概略構成圖。 圖2A係本發明之微粒子檢測裝置的概略構成圖。 圖2B係流路縮小管的部分放大圖。 圖3係二氧化碳之p-h線圖的示意圖。 圖4係實施例的流程圖。 圖5A係顯示比較例卜2之微粒子數的檢測結果之圖表。 圖5B係顯示比較例3之微粒子數的檢測結果之圖表。 圖5C係顯示實施例之微粒子數的檢測結果之圖表。 圖6係改變採樣處情況之檢測結果的變動之圖表。 圖7A係施行閥之開閉動作時之檢測結果的變動之圖表。 圖7B係顯示一實施例之線構成的概略圖。 【主要元件符號說明】 1二氧化碳供給設備 2 C〇2缸筒 3a、3b金屬氣體過濾器 4凝結器 5 C02 槽 6預冷卻器 7循環泵 8金屬氣體過濾器 9保壓閥 10蒸發器 11微粒子檢測装置 12a、12b、12c、12d、29 閥 13流體供給部 14、24流路縮小管 14a流路縮小管之一端 14b流路縮小管之另一端 15 201229488 15微粒子檢測機構 16a、16b加熱器(加熱機構) 17a、17b 溫度計 18控制裝置 19分支管 20凝結室 20a供給口 21流動室 22半導體雷射 23光電轉換器 25、26 線 27排氣管分支部 28泵 P1〜P3 採樣處 16The carbon is supplied to the Wei to reduce the flow of the tube 14. Because the gas phase: oxygen method detects the mechanism 15 , the second step is to consider the state of the smaller PC, or the lower temperature of the carbon dioxide 201229488 (point c). . When the carbon dioxide is changed at a low temperature, depending on the decompression conditions, there is a possibility of being in a gas-solid state (D, point). The gas-solid mixed state refers to the state of dry ice which produces a solid phase in the gas phase under the condition of carbon dioxide. Since the solid phase continues to exist under reduced pressure, if the carbon dioxide flows out of the flow path reducing tube 14 in a gas-solid mixed state and flows into the particle detecting mechanism 15, the solid phase of carbon dioxide and the originally detected particle ^ become indistinguishable. . Here, the heaters l6a and 16b are actuated to increase the degree of carbon dioxide (point E). As a result, the enthalpy of carbon dioxide is increased, and even if it is depressurized, it is prevented from becoming a fluorine-solid mixed state (point B). Further, in the case where the dry PC method or cpc is used for the detection of fine particles, it is preferred to completely vaporize the carbon dioxide. Here, by heating the carbon dioxide with the heaters 16a, 16b, the gas-liquid mixing state can also be avoided. The purpose of producing the heaters 16a, 16b is to heat the carbon dioxide so that the carbon dioxide detects the fine particles in the gas phase. Further, the purpose of the heaters 16a, 16b is to keep the temperature of the carbon dioxide introduced into the detector constant. Therefore, the heaters i6"i6b need not necessarily be provided in the flow path reducing pipe 14' or may be provided in the inlet of the fine particle detecting means 15, and the flow path reducing pipe 14 is a pipe and has a simple structure, so that the heater is provided even if it is vaporized. The solid phase or liquid phase of carbon is temporarily generated, and it can be removed at the point of introduction of the microparticles = machine. In other words, even if carbon dioxide temporarily becomes a state of d, point or ^ point, it may be a state of E, point or E". However, since the state changes to a certain extent, the tube 14 is reduced as much as possible in the flow path. It is preferable to avoid the gas-solid mixing state or the gas-liquid mixing state on the upstream side of the two heats. From this point of view, it is preferable to set the heater 16a near the inlet 14a of the flow path reducing pipe 14. "" It is also possible to perform the enthalpy change (D-Ε-Β,) without generating a gas-solid mixing state or a gas-liquid mixing state. On the other hand, in order to introduce the ruthenium dioxide gas phase into the fine particle detecting means 15, it is preferable to provide the heater 16b in the vicinity of the outlet 14b of the "IL g 14", and it is also possible to separately set the vicinity of the inlet 14a and the outlet. Heaters 16a, 16b. In this way, the setting positions of the heaters l6a and 16b can be determined. When the inner diameter of the flow path reducing tube 14 is increased to the right, the reduction effect is reduced, and the degree of decompression is 10 201229488, which is small. Similarly, if the length of the pipe of the flow path reducing pipe 14 is shortened, the degree of pressure reduction becomes small. The adjustment of the pipe length and the flow path area (internal offset) of the flow path reduction pipe 14 and the temperature control of the flow path reduction pipe 14 of the heaters 16a and 16b can be combined. Even in the case where the flow path and the flow path area and length of the reduction pipe 14 are made appropriate, it is preferable to perform the temperature control of the flow path reduction pipe 14 in order to avoid the gas-solid mixing state or the gas-liquid mixing state. The decompression method using the flow path reduction tube 14 does not require a mechanical action such as a conventional pressure reducing valve, and in principle, there is no microparticle generated by the action of metal powder or the like. Therefore, it is possible to detect the fine particles contained in the carbon dioxide with high precision. Although the filter is also considered as another decompression method, it is difficult to accurately measure the adhesion and peeling of the fine particles due to the use of the filter for a long period of time. In contrast, the method of decompressing the flow path reducing tube 14 is used, and the generation of fine particles such as metal powder, which is a source of contamination (or a cause of an increase in the number of particles in the control), is hardly measured. Further, the flow path area (inner diameter) and the total length of the flow path reducing tube 14 are adjusted, and the temperature control of the heaters 16a and 16b is further performed, so that it is difficult to be affected by the temperature of the sampling place ρι to P3. Perform particle detection with a good degree. The other advantage of the flow path reduction tube 14 is that the heat transfer area = due to the long length of the pipe. Therefore, the degree of freedom in addition and subtraction setting is high, and the temperature control can be ensured to be large, so that temperature control can be performed in detail. Due to the large heat transfer area, depending on the nuclear temperature, the carbon dioxide can be converted to a range of degrees even if it is not necessary to set the heating||. Since the pressure reducing valve and the filter are concentrated in one point of actual decompression, it is difficult to perform temperature control in detail. In addition, the flow and reliability are high, and the necessity of maintenance is also small. On the cost side, there is also a structure/structure early and the particle detection surface 15 is detected. The self-flow path is reduced; f 14 is liquid or gas-carbon dioxide, and is narrowed by the flow path. After the tube M is depressurized, it becomes a gas phase, and the microparticles originally oxidized by the carbon monoxide are present in the gas phase. The carbon dioxide-conducting microparticles containing the J phase are subjected to the detection of the microparticles of the gas-crystal dioxide. The microparticle detection method can be performed by using the dry PC method or the cp = dry PC method. A mechanism for irradiating light to the fine particles and a mechanism for scattering light from the laser light of the hybrid. The dry 201229488 pc method irradiates the fine particles in the gas phase with laser light generated by the semiconductor laser to detect direct scattering from the fine particles. Fig. 2 shows a microparticle detection mechanism 15 according to the CPC method. The microparticle detection mechanism 15 has a condensation chamber, and the condensation chamber 20 has a supply port 2〇a for vapor such as ethanol. The condensation chamber is a supersaturated atmosphere such as ethanol. 2〇Introducing the microparticles, and using the microparticles as the core, the ethanol-specific vapor is condensed and grown. The downstream side of the condensation chamber 2 is a flow chamber 21 made of a material transparent to laser light. The side of the flow chamber 21 is arranged. : semiconductor laser 22 'radiation of particles condensed by vapor condensation; and photoelectric converter 23 / laser for detecting particles growing from vapor condensation Light-scattering light. Micro-particles are aerosols (droplets) that are condensed by vapor adhesion, and the droplets illuminate the laser light. The particle size of the droplets is as large as the light scattering method can be measured by light scattering method. The number (concentration) of the fine particles is measured. Therefore, the CPC method can detect fine particles having a smaller particle diameter than the dry PC method. On the other hand, since the dry PC method is used to irradiate direct laser light to the fine particles, the fine particles can be obtained. In addition, the flow rate of the fluid decompressed in the flow path reducing tube 14 increases, which may cause an unnecessary load on the particle detecting mechanism 15. Therefore, as shown in the embodiment, A pump is provided on the downstream side of the fine particle detecting means 15 to introduce a fluid to be measured having an appropriate flow rate and flow rate into the fine particle detecting means 15, and an atmospheric opening means is provided on the upstream side of the fine particle detecting means 15, and is not introduced into the fine particle detecting means 15. The fluid is exhausted. The fruit may be disposed between the microparticle detecting mechanism 15 and the atmosphere opening mechanism, but the microparticles generated from the chestnut may be introduced into the microparticle detecting mechanism 15 The flow chart of the embodiment is shown in Fig. 4. The high-pressure fluid is a metal gas filter manufactured by Pl^ERON JAPAN Co., Ltd. (filtering accuracy 〇〇〇3μιη). High-pressure carbon dioxide filtered. High-pressure carbon dioxide is continuously supplied to a flow path reducing pipe as a pressure reducing mechanism through a fluid supply unit '4.35 mm in diameter. The high-pressure dioxide-dissolved fluid supply unit is provided with a branch pipe 19 to partially carbon dioxide. The pressure is set to 2 MPa through the pressure-retaining valve. The set pressure of the pressure-retaining valve 20 is 9 MPa, and a high-pressure carbon dioxide of a constant flow rate (3 g/min) is supplied to the flow path reduction tube 14. The flow path reduction tube 14 has a diameter of 12 201229488 Φ200μιη, tube length 30m, made of SUS316. The flow path narrowing tube 14 is wound into a circular shape of Φ 48 cm, and both ends are unwound. The heaters 16a and 16b are provided in the vicinity of the inlet of the flow path reduction pipe 14 and the vicinity of the outlet. The temperature is controlled so that the temperature outside the flow path reduction pipe 14 becomes 6 (rc'^ = °C. Specifically, preparation is made. A strip heater having a width of 4 cm and a length of 3 m is used as the adder 16a, and is unwound from the beginning of the flow path reducing tube 14 along the flow path reducing tube 14. The mounting is carried out, and the remaining portion is attached to the flow path reducing tube. A bundled heater having a width of 4 cm and a length of 3 m is prepared as a heater, and the exhaust pipe branch portion 27 from the downstream side of the flow path reduction pipe 14 is moved along the flow tube 14 The unwound portion is mounted, and the remaining portion is mounted in the bundled portion of the flow path reduction tube 14 and connected to the unwound portion. Fig. 4, the range of the heaters 16a, 16b. The number of microparticles contained in the carbon dioxide towel by the flow path reducing tube 14 is measured by the microparticle detecting device 15 of the cpc method (cpc377 manufactured by TSI Corporation). The downstream side of the microparticle detecting device 15 is provided with a pump 28 for decompressing carbon dioxide. Introduce a fraction of a certain flow rate (lL/min) into the microparticle test The device exhaust pipe branching portion 27 is placed in the atmosphere to the atmosphere. Since the ratio is (4), the pressure is reduced, and the pressure reducing valve (manufactured by TESC0M) is used as the pressure reducing mechanism in Comparative Example 2. Comparative Example = In the latter stage of the flow rate limiter of the first example, the flow path reduction pipes 14〇2GGmiii and 3Gm) of the heater are provided in the same manner as in the embodiment. In Comparative Examples i and 3, a transition device capable of removing fine particles having a particle diameter of 2 μm or more was used. The valve is provided with a strip-shaped rail feeder having a width of 4 cm and a length of 3 cm in the outer peripheral portion, and the temperature control of the couple is employed. Controlling the flow rate limit 11 The temperature of the part is shown in Fig. 5 to 5C. The results of the example and the comparative example are shown, the results of the number of counts are shown, the results of the measurement are shown in Fig. 5, and the results are shown in Fig. 5c. The plate axis is the elapsed time, and the vertical axis is the number of detected particles of the detected particles lcc). The longitudinal drawing of Figs. 5B and 5C is the same ratio, but the ratio of the axis of Fig. & 13 201229488 is magnified by ιοοο compared with Figs. 5B and 5C. When the generation of fine particles of metal powder or the like by the operation of the pressure reducing valve of Comparative Example 2 is considered, and the fluid having a low concentration of fine particles is used as the measurement target, it is difficult to obtain the actual if-measurement accuracy. In Comparative Example 2, although the number of detected particles was smaller than that of Comparative Example 1, it was detected that there were many more fine particles than the examples described later. Considering the comparative example, it is affected by the fine particles which are repeatedly attached to the filter and peeled off. Further, it is inferred that the temperature control of Comparative Examples 1 and 2 is insufficient, and the carbon dioxide portion becomes a solid phase or a liquid phase inflow measurement. Considering Comparative Example 3, since the flow path narrowing pipe 14 of the embodiment was provided in the latter stage of the filter of the comparative example, the carbon dioxide completely became the gas phase. Comparative Example 3 can be said to be an example in which a portion affected by the fine particles attached to and removed from the filter is extracted. In Comparative Examples 1 to 3, the fine particles other than the fine particles originally contained in the object to be measured affected the measurement result, and the number of detected particles was high, and the measurement was unstable. On the other hand, in the examples, the number of detected particles was smaller than that of the comparative examples, and the measurement was not performed by the fine particles other than the fine particles originally contained in the object to be measured. a ^ ^ Next, Fig. 6 shows the result of measuring the number (concentration) of the fine particles of the high-pressure carbon dioxide supply device at which the particle diameter of the 高压2, Ρ3' Η exceeds i〇nm in the present embodiment. The sampling locations P1 to P3 are as shown in the figure. Although it was confirmed that the number of particles having transitional properties was increased when the sampling site was changed, the number of particles almost coincident with the sampling portion was obtained. Further, Fig. 7A shows the result of measuring the number (concentration) of fine particles having a particle diameter exceeding l 〇 nm in the opening and closing operation of the application valve 29 in the same sampling position. This valve 29 is provided in the structure shown in Fig. 7B in order to observe the influence of the opening and closing operation of the valve. The valve line 25 is formed in parallel with the line 26 where the valve is not provided, carbon dioxide is supplied, and the opening and closing operation of the valve 29 is performed, and the number of fine particles is measured. After the opening and closing operation of the valve, the number of fine particles temporarily increases, and thereafter returns to a stable state. Thus, it is confirmed that the change in the number of fine particles (concentration) at the time of performing the change of the sampling position or the opening and closing operation of the valve can be continuously monitored. 201229488 [Simplified description of the drawings] Fig. 1 is a schematic configuration diagram of a carbon dioxide supply device. Fig. 2A is a schematic configuration diagram of a fine particle detecting device of the present invention. Fig. 2B is a partially enlarged view of the flow path reduction tube. Figure 3 is a schematic illustration of the p-h diagram of carbon dioxide. Figure 4 is a flow chart of an embodiment. Fig. 5A is a graph showing the results of detection of the number of fine particles of Comparative Example 2. Fig. 5B is a graph showing the results of detection of the number of fine particles of Comparative Example 3. Fig. 5C is a graph showing the results of detection of the number of fine particles in the examples. Fig. 6 is a graph showing changes in the detection result of the situation at the sampling place. Fig. 7A is a graph showing changes in detection results when the valve is opened and closed. Fig. 7B is a schematic view showing the configuration of a line of an embodiment. [Main component symbol description] 1 Carbon dioxide supply device 2 C〇2 cylinder 3a, 3b metal gas filter 4 condenser 5 C02 tank 6 precooler 7 circulation pump 8 metal gas filter 9 pressure maintaining valve 10 evaporator 11 fine particles Detection device 12a, 12b, 12c, 12d, 29 valve 13 fluid supply portion 14, 24 flow path reduction tube 14a flow path reduction tube one end 14b flow path reduction tube other end 15 201229488 15 particle detection mechanism 16a, 16b heater ( Heating mechanism) 17a, 17b Thermometer 18 Control device 19 Branch pipe 20 Condensation chamber 20a Supply port 21 Flow chamber 22 Semiconductor laser 23 Photoelectric converter 25, 26 Line 27 Exhaust pipe branch 28 Pump P1 to P3 Sampling place 16