201137338 六、發明說明： 【發明所屬之技術領域】 本創作係關於一種測量薄膜滲透係數之裝置，尤指可進行氣 體分離及純化之薄膜，利用該裝置動態氣體壓力的供給且薄膜在 變壓環境中，藉由自動監測氣體壓力與氣體通過薄膜流通量之變 化，可在短時間内連續測得薄膜兩侧壓差與氣體滲透分離之關 係’進而連續且精確地測得薄膜的渗透係數，且該渗透係數可包 含廣泛之壓力範圍。 【先前技術】 按，近年來由於化石燃料過度開發與使用，加上生態環境的 破壞’尋找替代性能源以及潔淨能源已成為相關當局主要的議 題。現今替代能源及潔淨能源之開發中，氫能為目前最具前瞻性 的指標之一，再加上近年來燃料電池技術的逐漸成熟及其應用的 蓬勃發展，氫氣分離與純化的技術日益重要。 又’氫氣在工業上一直扮演著重要的角色。舉例而言，氫氣 向來為氨氣製造、煉油廠内脫氫與加氫反應、半導體製程、石油 化工過程、冶金過程之主要原料。除此之外，純氫在火箭及太空 梭的應用，亦為一不可或缺的推進燃料。近年來，由於燃料電池 及氫内燃機的發展，加上氫能經濟極具前瞻性，若未來氫能技術 曰益成熟，預期氫氣的需求量將大量增加。 目則氫氣產生的來源多以碳氫化合物（如化石燃料及生質物） 及水為原料，藉由蒸氣重組、水氣轉移、部分氧化、自熱重組、 氣化及裂解等熱化學程序獲得。一般而言，化學反應進行後，產 氣中通常伴隨CO與C〇2的產生，CO將造成低溫燃二電池（如質 子交換膜燃料電池，PEMFC).的毒化，而使其效能降低；c〇2為 溫室氣體之一，若大量進行產氫反應所產生之c〇2也將對環^造 成影響。因此，若將反應產生之氫氣進行純化與分離，對於設備一201137338 VI. Description of the invention: [Technical field to which the invention pertains] This creation relates to a device for measuring the permeability coefficient of a film, especially a film which can be subjected to gas separation and purification, using the dynamic gas pressure supply of the device and the film in a pressure-variing environment By automatically monitoring the gas pressure and the change of the gas flow through the film, the relationship between the pressure difference between the two sides of the film and the gas permeation separation can be continuously measured in a short time, and the permeability coefficient of the film can be continuously and accurately measured, and The permeability coefficient can include a wide range of pressures. [Prior Art] According to the excessive development and use of fossil fuels in recent years, coupled with the destruction of the ecological environment, the search for alternative energy sources and clean energy has become a major issue for relevant authorities. Hydrogen energy is one of the most forward-looking indicators in the development of alternative energy and clean energy. Coupled with the maturity of fuel cell technology and the booming application in recent years, hydrogen separation and purification technologies are increasingly important. Also, hydrogen has always played an important role in the industry. For example, hydrogen has been a major raw material for ammonia gas production, dehydrogenation and hydrogenation reactions in refineries, semiconductor processes, petrochemical processes, and metallurgical processes. In addition, the application of pure hydrogen in rockets and space shuttles is also an indispensable fuel for propulsion. In recent years, due to the development of fuel cells and hydrogen internal combustion engines, and the hydrogen energy economy is very forward-looking, if the future of hydrogen energy technology is mature, it is expected that the demand for hydrogen will increase significantly. Hydrogen is produced from hydrocarbons (such as fossil fuels and biomass) and water, and is obtained by thermal chemical processes such as steam recombination, water vapor transfer, partial oxidation, autothermal reforming, gasification and cracking. In general, after the chemical reaction is carried out, the gas is usually accompanied by the production of CO and C〇2, and CO will cause poisoning of the low-temperature fuel cell (such as proton exchange membrane fuel cell, PEMFC), and its efficiency is lowered; 〇2 is one of the greenhouse gases. If a large amount of hydrogen production reaction occurs, c〇2 will also affect the ring. Therefore, if the hydrogen produced by the reaction is purified and separated, for equipment one
1 S 201137338 及環境皆具有益處。 傳統上，可利用變壓吸附法（pressure swing absorption )或低 溫精顧法（cryogenic distillation )進行氫氣的分離純化。除了變壓 吸附法與低溫精餾法外，近年來，利用薄膜分離技術純化氫氣已 成為許多學者研究的主題。相較於其他分離技術，由於薄膜分離 對於氫氣的分離有很高的選擇性，且對於滲透過後的氫氣純度也 可以高達99%以上，加之所需空間不大，因此未來若低溫燃料電 池普使用，且大量應用於汽車，薄膜分離及純化氫氣之技術將廣 泛運用於生活上。 關於薄膜分離及純化氫氣方面，一般而言材料可分為兩大 類，一種為無機薄膜，另一種為有機薄膜。過去研究及測試已知， 無機薄膜比有機薄膜更能忍受嚴苛的操作條件，當中鈀與其合金 薄膜更是主要被研究之無機金屬薄膜。無機薄膜為固體薄膜的一 種，由無機材料，如金屬、金屬氧化物、陶竞、多孔玻璃、沸石、 無機高分子材料等製成的半透膜。相較於有機薄膜，無機薄膜具 有下列之優點： 1. 化學穩定性好：能耐酸、耐鹼、耐有機溶劑。 2. 機械強度大：擔載無機薄膜可承受幾十大氣壓的外壓，並可反 向沖洗。 3. 抗微生物能力強：不與微生物產生作用，可以應用於生物工程 及醫學科學領域。 4. 耐高溫：一般均可在400°C以下操作，最高溫度可達800°C。 5. 孔徑分佈窄：分離效率較高。 薄膜分離氫氣技術是藉由一種能吸附氫氣的薄膜，在薄膜兩 端製造壓力差，而將所氣體中之氫氣滲透到薄膜之另一端，以達 到將氫氣與其他氣體分離，並純化氫氣之效果。目前最廣泛使用 於氫氣分離與純化的金屬薄膜是鈀薄膜，此種材料特性在於可以 201137338 大量吸附氫氣，對於氫氣有極高選擇性，且對於氫氣的滲透通量 亦高。 為評估薄膜對於特定氣體的分離與純化效果，薄膜的滲透係 數（permeance )是一重要指標。渗透係數的物理意義為薄膜單位 面積、單位時間及單位壓力差分離氣體的能力，其最常用的單位 為mol ηΤ2 s_1 Pa_n，其中η為壓力指數。滲透係數的測量為在薄 膜兩端製造壓力差，而後被分離與純化的氣體將通過薄膜，並測 定被分離氣體的質量流率，藉以求得薄膜之滲透係數。傳統上， 薄膜兩端為固定壓力差，且僅挑數個壓力差進行薄膜之滲透係數 測量，因此較為費時、壓力範圍受限、且分析數據較少，因此可 能造成測得之薄膜滲透係數精確度不足。 【發明内容】 有鑑於上述問題，發明人乃研究出一種「精確測量薄膜滲透 係數之裝置與方法（An apparatus and method of precisely measuring permeance of a membrane )」，有別於過去傳統設定固定壓力差的方 式測量薄膜滲透係數，本設計裝置與方法乃透過動態壓力差變 化，觀察被分離及純化氣體之暫態滲透現象，藉由壓力感測器及 電子式流量計，自動測量及記錄即時系統壓力與氣體滲透量，以 精確測得薄膜之滲透係數。此外，相較於傳統的測量方法，本裝 置與方法可在短時間内，一次測量即可進行不同壓力差之氣體滲 透，因此可顯著縮短測量時間。 為達成上述目的之技術内容，係提供一種「精確測量薄膜滲 透係數之裝置」，其包含一進料單元、一加熱單元、一渗透單元、 一出口及監測單元，其中進料單元係進行裝置清洗及滲透氣體之 供應，加熱單元係提供薄膜的定溫環境，滲透單元則為一同心環 狀結構之不鏽鋼鋼管，内包含有一薄膜管，出口及監測單元則進 行薄膜管兩側壓力及氣體流量之自動測量及記錄，藉由上述各單 201137338 元之串接及整合’並在特定操作程序之方法下，可在甚短的時間 内進行薄膜滲透係數之測量，所得之滲透係數不但包含範圍廣泛 之壓力差，且所得之薄膜滲透係數與壓力差關係為 精確測得薄膜之滲透係數。 連仏因而 【實施方式】 本發明裝置方法請參閱如圖1所示之氣體滲透測量裝置作為 ，選的實施例結構，其可觀察薄膜兩端在壓力差變化環境下，氫 亂通過薄膜管之動態滲透現象，並可在短時間内精確測得薄膜之 滲透係數’該薄膜滲透測量裝置（丨）包括： 、 進料單元（10)，具有一氣體儲存鋼瓶（11)、一氮氣清洗 鋼瓶（12)、一虱氣清洗鋼瓶（13)、一塵力感測器（14)、一壓力 訊號傳輸線（15)、訊號記錄器（16)、三通閥件一（17)及三通 閥件二（18)，氣體儲存鋼瓶（11)乃儲存測量薄膜滲透係數所需 之滲透氣體，氮氣清洗鋼瓶（12)及氫氣清洗鋼瓶（13)則儲存 清洗系統所需之氮氣及氫氣，壓力感測器（14)進行系統壓力之 測量，藉由壓力訊號傳輸線（15)可將壓力訊號傳輸至訊號記錄 器（16)以顯示並紀錄系統壓力，其中訊號記錄器（16)可為電 腦，三通閥件一（17)及三通閥件二（18)係作為氣體流通之控 制； 一加熱單元（20)，具有加熱器（21)、熱感應器（22)、溫度 控制器（23)、功率輸出調整器（24)及電源開關（25)，溫度控 制器（23)可設定加熱器（21)之溫度，並由熱感應器（22)所 測知之即時溫度訊號回授予功率輸出調整器（24)進行系統加熱， 以使滲透裝置達到所需溫度，電源開關（25)則可控制加熱單元 (20)電源之開啟與關閉； 一渗透單元（30)，具有薄膜管（31)、尾氣端導管（32)、滲 透端導管（33)及背壓冑（34)，薄膜管（31)纟多孔性不鏽鋼管 (35)、密閉性不鏽鋼管（36)及薄膜（37)所組成，其中多孔性 201137338 不鏽鋼管（35)表㈣上薄臈（37)，薄膜可為把薄膜、1 S 201137338 and the environment are all beneficial. Traditionally, hydrogen separation and purification can be carried out by pressure swing absorption or cryogenic distillation. In addition to the pressure swing adsorption method and the cryogenic rectification method, in recent years, the purification of hydrogen by membrane separation technology has been the subject of many scholars. Compared with other separation techniques, membrane separation has high selectivity for hydrogen separation, and the purity of hydrogen after permeation can be as high as 99% or more, and the required space is not large, so if the low-temperature fuel cell is used in the future And a large number of technologies used in automobiles, membrane separation and purification of hydrogen will be widely used in life. In terms of membrane separation and purification of hydrogen, materials can generally be classified into two broad categories, one being an inorganic thin film and the other being an organic thin film. It has been known in the past that inorganic thin films are more tolerant of harsh operating conditions than organic thin films, and that palladium and its alloy thin films are the main inorganic metal films to be studied. The inorganic thin film is a semipermeable membrane made of an inorganic material such as a metal, a metal oxide, a ceramic, a porous glass, a zeolite, an inorganic polymer material or the like. Compared with organic thin films, inorganic thin films have the following advantages: 1. Good chemical stability: acid, alkali and organic solvents. 2. High mechanical strength: The supporting inorganic film can withstand external pressure of several tens of atmospheric pressure and can be washed back. 3. Strong anti-microbial ability: It does not interact with microorganisms and can be applied in bioengineering and medical science. 4. High temperature resistance: Generally, it can be operated below 400 °C, and the maximum temperature can reach 800 °C. 5. Narrow pore size distribution: high separation efficiency. The membrane separation hydrogen technology uses a membrane capable of adsorbing hydrogen to create a pressure difference across the membrane, and permeates the hydrogen in the gas to the other end of the membrane to separate the hydrogen from other gases and purify the hydrogen. . At present, the most widely used metal film for hydrogen separation and purification is palladium film. This material is characterized in that it can adsorb hydrogen in a large amount in 201137338, has extremely high selectivity to hydrogen, and has high permeation flux for hydrogen. In order to evaluate the separation and purification of a film for a specific gas, the permeance of the film is an important indicator. The physical meaning of the permeability coefficient is the ability of the membrane to separate the gas per unit area, unit time and unit pressure difference. The most common unit is mol η Τ 2 s_1 Pa_n, where η is the pressure index. The permeability coefficient is measured by creating a pressure difference across the membrane, and then the separated and purified gas will pass through the membrane and determine the mass flow rate of the separated gas to determine the permeability coefficient of the membrane. Traditionally, the film has a fixed pressure difference at both ends, and only a few pressure differences are taken to measure the permeability coefficient of the film, so it is time consuming, the pressure range is limited, and the analysis data is small, so the measured membrane permeability coefficient may be accurate. Insufficient. SUMMARY OF THE INVENTION In view of the above problems, the inventors have developed an "An apparatus and method of precise measurement of permeance of a membrane", which is different from the conventional setting of a fixed pressure difference. By measuring the membrane permeability coefficient, the design device and method observe the transient permeation phenomenon of the separated and purified gas through the dynamic pressure difference change, and automatically measure and record the instantaneous system pressure by the pressure sensor and the electronic flowmeter. The amount of gas permeation to accurately measure the permeability coefficient of the film. In addition, compared with the traditional measurement method, the device and the method can perform gas permeation with different pressure differences in one measurement in a short time, thereby significantly shortening the measurement time. In order to achieve the above technical content, a device for accurately measuring the permeability of a thin film is provided, which comprises a feeding unit, a heating unit, a permeating unit, an outlet and a monitoring unit, wherein the feeding unit performs device cleaning. And the supply of permeating gas, the heating unit provides a constant temperature environment of the film, the permeation unit is a concentric annular structure of stainless steel pipe, which comprises a film tube, and the outlet and monitoring unit performs pressure and gas flow on both sides of the film tube. Automatic measurement and recording, through the serial connection and integration of the above single 201137338 yuan and the measurement of the membrane permeability coefficient in a very short time under the specific operating procedure, the resulting permeability coefficient not only covers a wide range of The pressure difference is obtained, and the relationship between the obtained membrane permeability coefficient and the pressure difference is an accurate measurement of the permeability coefficient of the film.实施 仏 仏 【 【 【 【 【 【 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体 气体Dynamic permeation phenomenon, and the permeability coefficient of the film can be accurately measured in a short time. The film permeation measuring device (丨) includes: a feeding unit (10) having a gas storage cylinder (11) and a nitrogen cleaning cylinder ( 12), a helium cleaning cylinder (13), a dust sensor (14), a pressure signal transmission line (15), a signal recorder (16), a three-way valve member (17) and a three-way valve member Second (18), gas storage cylinder (11) is used to store the permeate gas required to measure the membrane permeability coefficient, nitrogen purge cylinder (12) and hydrogen cleaning cylinder (13) to store the nitrogen and hydrogen required for the cleaning system, pressure sensing The device (14) measures the system pressure, and the pressure signal transmission line (15) can transmit the pressure signal to the signal recorder (16) to display and record the system pressure, wherein the signal recorder (16) can be a computer, a three-way Valve One (17) and three-way valve member two (18) are used as gas flow control; a heating unit (20) with heater (21), thermal sensor (22), temperature controller (23), power output The regulator (24) and the power switch (25), the temperature controller (23) can set the temperature of the heater (21), and the instantaneous temperature signal detected by the thermal sensor (22) is returned to the power output adjuster (24) The system is heated to bring the osmotic device to the desired temperature, the power switch (25) controls the opening and closing of the heating unit (20); a permeation unit (30) has a thin film tube (31) and an exhaust end conduit (32), a permeate end conduit (33) and a back pressure crucible (34), a thin film tube (31), a porous stainless steel tube (35), a hermetic stainless steel tube (36) and a film (37), wherein the porosity 201137338 stainless steel tube (35) table (four) upper thin enamel (37), the film can be a film,
刀離傻虱氣之輸送，尾氣端導管（32) 皮壓閥（34)則進行滲透單元（3〇)内壓 純化，滲透端導管（33 進行殘餘氣體之輸送， 力之控制；The knife is transported from the stupid air, the exhaust end pipe (32), the skin pressure valve (34) is subjected to internal pressure purification by the permeation unit (3〇), and the permeate end pipe (33 is used for the delivery of residual gas, and the force is controlled;
出口（43)氣體流量’所測得流量以電子訊號方式藉由訊號傳輸 線（45 )傳送至流量顯示器（46 )以顯示出氣體流量，而後再由 訊號傳輸線（45)傳送電子訊號至訊號記錄器（16)以記錄氣體 流量。 氣端出口（43)氣體流量， 出口（43)氣體流量，所浪 "本發明方法技術内容，請配合參考看圖2所*，首先開啟氮 氣清洗鋼瓶（12)，並調整三通閥件一（17)及三通閥件二〇8)， 使^氣沿管路經由三通閥件一（17)及三通閥件二〇8)，進入滲 • 透單元（30)以清洗整個薄膜滲透測量裝置（1)，此時若將背壓 閥（34)關閉，可進行系統密閉性測試。經由上述步驟清洗薄膜 滲透測量裝置（1)後，將加熱單元的電源開關開啟， 調整溫度控制器（23)及功率輸出調整器（24)至所設定之溫度。 田加熱單元（20)之溫度達設定值後，開啟氫氣清洗鋼瓶（13)， 調整三通閥件一（17)及三通閥件二（18)，使氫氣沿管路經由三 通閥件一（17)及三通閥件二（18)進入滲透單元（3〇)以清洗 整個薄膜滲透測量裝置（〇,並調整背壓閥（34)，藉由壓力感測 器（14)及訊號記錄器（16)觀察並控制系統壓力。在上述系統 清洗同時，將待滲透氣體填充至氣體儲存鋼瓶（，使其達設定 之壓力。一旦滲透端出口（ 44 )之氫氣流量達穩定狀態，關閉三【s 201137338 通閥件二（18) ’調整三通閥件一（17) ’使待滲透氣體自氣體儲 存鋼瓶（11)流出，經沿管路經由三通閥件一（丨7)進入滲透單 疋（30)。當待滲透氣體進入薄膜管（31)後，由於薄膜（37)兩 側的壓力差，待滲透氣體中的氫氣將被薄膜（37)吸收，並穿越 薄膜（37)，由高壓端滲透至低壓端，並流經滲透端導管（33)及 電子式流量計二（42 )’經由滲透端出口（ 44 )排至外界。隨著氫 氣的分離，氣體儲存鋼瓶（1〗）的壓力將逐漸下降，此時由壓力 感測器（14)及訊號記錄器（16)連續紀錄氣體儲存鋼瓶（11) 内的壓力，並由電子式流量計二（42)及訊號記錄器（16)連續 φ 紀錄氫氣滲透過薄膜的瞬間流量，壓力及流量測量連續進行，直 到氫氣滲透過薄臈的流量為零。 本發明可藉由以下實施例被進一步瞭解，該實施例僅做為說 明之用，而非用於限制本發明範圍。 實施例 在實施例中乃以本創作之精確測量薄膜滲透係數裝置，藉由 汉定軋體儲存鋼瓶之初始壓力，然後釋放氣體儲存鋼瓶之氣體， I 且關閉背壓閥，進行氫氣穿越薄膜動態滲透之觀察及薄膜滲透係 數之精確測量。在測量系統方面，氣體儲存鋼瓶之内部體積為2 25 公升’並儲存純氫’加熱單元及薄膜管内之薄膜為鈀薄膜 (palladium，Pd)，厚度為20μιη ’薄膜管溫度設定為35〇〇c，本處 進行三組薄膜滲透係數之測量，氣體儲存鋼瓶内氫氣初始壓力差 分別為 3atm、5atm、8atm。 配合參看圖3,其為在本發明測量裝置運轉及上述條件操作 下’氣體儲存鋼瓶之氫氣滲透過把薄膜之流量隨時間分佈圖。由 圖3可看出，隨著滲透時間的增加，氫氣穿越把薄膜的流量隨之 減少。當氣體儲存鋼瓶内氫氣初始壓力差越大，氣氣初始滲透流 201137338 里也，，，但流量隨時間衰退也較快；反之，氫氣初始壓力差越 小，氫氣初始滲透量也較減小，但流量隨時間衰退較慢。整體而 言，當滲透時間達80分鐘後’氫氣滲透過鈀薄膜之流量即趨近於 零。此說明在本發日綠置制下，確實可以觀察到動態的氣氣渗 透現象。圖4所示則為氣體儲存鋼瓶内氫氣壓力與滲透時間關係 圖，圖中可看出，隨著滲透時間的增加，鋼瓶内氫氣壓力也隨之 下降，其下降趨勢類似於圖3^但值得注意的是，當圖3中氫氣滲 透流量趨近於零時，鈀薄膜兩側壓力差並不為零，此說明鈮薄膜 兩侧存在一最小壓力差或閾值，當壓力差等於或小於該閾值時， φ 就不可能發生氫氣滲透現象。 依據以上閾值之觀察，把薄膜渗透係數（κ)可表示為：The measured flow rate of the outlet (43) gas flow is transmitted by electronic signal to the flow display (46) via the signal transmission line (45) to display the gas flow, and then the electronic signal is transmitted from the signal transmission line (45) to the signal recorder. (16) to record the gas flow rate. Gas outlet (43) gas flow, outlet (43) gas flow, wave" The technical content of the method of the present invention, please refer to the reference to Figure 2, first open the nitrogen cleaning cylinder (12), and adjust the three-way valve One (17) and three-way valve member 2〇8), the gas is passed along the pipeline through the three-way valve member (17) and the three-way valve member 2〇8), and enters the permeation unit (30) to clean the whole The membrane permeation measuring device (1), at this time, if the back pressure valve (34) is closed, the system tightness test can be performed. After cleaning the membrane permeation measuring device (1) through the above steps, the power switch of the heating unit is turned on, and the temperature controller (23) and the power output regulator (24) are adjusted to the set temperature. After the temperature of the field heating unit (20) reaches the set value, the hydrogen cleaning cylinder (13) is turned on, and the three-way valve member (17) and the three-way valve member two (18) are adjusted to make the hydrogen gas along the pipeline through the three-way valve member. One (17) and three-way valve member two (18) enters the permeation unit (3〇) to clean the entire membrane permeation measuring device (〇, and adjust the back pressure valve (34), with the pressure sensor (14) and the signal The recorder (16) observes and controls the system pressure. At the same time as the above system cleaning, the gas to be permeated is filled into the gas storage cylinder (to reach the set pressure. Once the hydrogen flow rate at the permeate end outlet (44) reaches a steady state, the gas is closed.三【s 201137338 Valves 2 (18) 'Adjust the three-way valve one (17) 'Let the gas to be permeated from the gas storage cylinder (11), enter through the pipeline through the three-way valve one (丨7) Permeating a single crucible (30). When the gas to be permeated enters the thin film tube (31), due to the pressure difference between the two sides of the membrane (37), the hydrogen in the gas to be permeated will be absorbed by the membrane (37) and traverse the membrane (37). , penetrates from the high pressure end to the low pressure end, and flows through the permeate end conduit (33) and electrons The flow meter two (42)' is discharged to the outside through the permeate outlet (44). As the hydrogen is separated, the pressure of the gas storage cylinder (1) is gradually decreased, and the pressure sensor (14) and the signal are recorded at this time. The device (16) continuously records the pressure in the gas storage cylinder (11), and continuously records the instantaneous flow rate of hydrogen permeating through the membrane by the electronic flowmeter two (42) and the signal recorder (16), and the pressure and flow measurement are continuously performed. The flow rate of the present invention is not limited by the following examples, and is not intended to limit the scope of the invention. According to the precise measurement of the membrane permeability coefficient device of the present invention, the initial pressure of the cylinder is stored by the Handing rolling body, and then the gas of the gas storage cylinder is released, and the back pressure valve is closed, and the dynamic permeation of the hydrogen permeating film and the membrane permeability coefficient are performed. Accurate measurement. In the measurement system, the internal volume of the gas storage cylinder is 2 25 liters 'and the pure hydrogen is stored'. The film in the heating unit and the film tube is a palladium film. (palladium, Pd), thickness 20μιη 'The temperature of the film tube is set to 35〇〇c. The permeability coefficient of the three groups of films is measured here. The initial pressure difference of hydrogen in the gas storage cylinder is 3atm, 5atm and 8atm respectively. 3. It is a distribution diagram of the flow rate of the film in the gas storage cylinder under the operation of the measuring device of the present invention and the above-mentioned conditions. As can be seen from Fig. 3, as the permeation time increases, the hydrogen traverses the film. The flow rate is reduced. When the initial pressure difference of hydrogen in the gas storage cylinder is larger, the initial gas permeation flow is also in 201137338, but the flow rate decays faster with time; on the contrary, the smaller the initial pressure difference of hydrogen, the initial hydrogen permeation. The amount is also reduced, but the flow decays slowly over time. Overall, the flow rate of hydrogen permeating through the palladium film approached zero when the permeation time reached 80 minutes. This description shows that dynamic gas permeation can be observed under the green setting on this date. Figure 4 shows the relationship between hydrogen pressure and permeation time in a gas storage cylinder. It can be seen that as the permeation time increases, the hydrogen pressure in the cylinder also decreases, and the downward trend is similar to Figure 3^ but worth Note that when the hydrogen permeate flow rate in Figure 3 approaches zero, the pressure difference across the palladium membrane is not zero, indicating that there is a minimum pressure difference or threshold across the membrane, when the pressure difference is equal to or less than the threshold. At the time, φ is unlikely to cause hydrogen permeation. According to the above threshold observation, the membrane permeability coefficient (κ) can be expressed as:
v - . m/A 上式中m、A、Pa、pb及n分別是氫氣滲透過鈀薄膜之流量、鈀薄 膜面積、滲透端氫氣分壓、滲透端氫氣最終分壓及氫氣壓力指數 等。，5所示為鈀薄膜在35〇。(：溫度環境下，氫氣滲透過薄膜通 量（m/A)與壓力差與於不同壓力指數（η)之關係圖。 整體而言，不論η值為何，滲透通量與壓力差之間皆呈現高度正 • 相關，即兩者之間表現出尚度線性。若進一步將上述曲線進行線 性迴歸分析，圖6所示為壓力指數（η)與R2關係圖，其中壓力 才S數範圍介於0.1到1.0之間。整體而言’ R2值皆大於〇 99，而針 對三種初始壓力差，最佳R2值的壓力指數落於〇 5至〇 7之間。 圖7所示為350°C下，三種不同初始壓力差、壓力指數、R2值與 薄膜滲透係數關係圖。 ~ 綜上所述，本發明「精確測量薄膜滲透係數之裝置與方法」， 藉由自行設計與架設之動態氫氣滲透裝置，可在短時間内觀察氫 氣滲透過鈀薄膜之動態現象，也可連續測得薄膜兩側壓力差與氫 氣滲透過薄膜通量之關係，進而精確測得薄膜之滲透係數。相較^ 201137338 於過去裝置與方法，本裝置與方法且 測量薄膜滲透係數之優點，亦即，^ 時、連續及精確 術田相夕古由^^^ 本發明方法係利用自然法則技 術〜之4創作，符合發明專利要件，Μ法俱文提出申請。 【圖式簡單說明】 圖1為本發明精確測量薄膜滲透係數之裝置。 圖2為實施本發明精確測量薄膜滲透係數之方法流程圖。 圖3為氫氣滲透流量與滲透時間關係圖。 圖4為氣體儲存鋼瓶内氫氣壓力與滲透時間關係圖。 圖5為不同壓力指數下薄膜渗透通量與壓力差之關係圖。 圖6為R2與壓力指數關係圖。 圖7為三種不同初始壓力差、壓力指數、r2值與薄膜滲透係數關 係圖。 【主要元件符號說明】 (1)薄膜滲透測量裝置 (10)進料單元 (11)氣體儲存鋼瓶 (12)氮氣清洗鋼瓶 (13)氫氣清洗鋼瓶 (14)壓力感測器 (15)壓力訊號傳輸線 (16)訊號記錄器 (17)三通閥件一 (20 )加熱單元 (18)三通閥件二 (21)加熱器 (22)熱感應器 (23)溫度控制器 (25)電源開關 (30)滲透單元 (24)功率輸出調整器 (31)薄膜管 (32)尾氣端導管 (33)滲透端導管 (34)背壓閥 (35)多孔性不鏽鋼管 (37)薄膜 (36 )密閉性不鏽鋼管 201137338 (40 )出口及監測單元 (41)電子式流量計一 (43)尾氣端出口 (45)訊號傳輸線 (42)電子式流量計二 (44 )滲透端出口 (46)流量顯示器v - . m/A In the above formula, m, A, Pa, pb and n are the flow rate of hydrogen permeating through the palladium film, the area of the palladium membrane, the partial pressure of hydrogen at the permeate end, the final partial pressure of hydrogen at the permeate end, and the hydrogen pressure index. 5 shows a palladium film at 35 Å. (In the temperature environment, the hydrogen permeation through the membrane flux (m / A) and the pressure difference and the different pressure index (η). Overall, regardless of the η value, between the permeate flux and the pressure difference It is highly positive and correlated, that is, it shows a linearity between the two. If the above curve is further linearly analyzed, Figure 6 shows the pressure index (η) and R2, where the pressure S range is between Between 0.1 and 1.0. Overall, the R2 values are greater than 〇99, and for the three initial pressure differences, the pressure index for the best R2 value falls between 〇5 and 〇7. Figure 7 shows the temperature at 350 °C. , three different initial pressure difference, pressure index, R2 value and film permeability coefficient relationship. ~ In summary, the present invention "device and method for accurately measuring the film permeability coefficient", by self-designed and erected dynamic hydrogen permeation device The dynamic phenomenon of hydrogen permeation through the palladium film can be observed in a short time, and the relationship between the pressure difference between the two sides of the film and the flux of hydrogen permeating through the film can be continuously measured, thereby accurately measuring the permeability coefficient of the film. Compared with ^201137338 Over Apparatus and method, the apparatus and method, and measuring the advantages of the membrane permeability coefficient, that is, the time, the continuous and the precise operation of the field. The method of the invention is created by using the natural law technique ～4, in accordance with the invention patent BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1 is a schematic diagram of a method for accurately measuring the permeability coefficient of a film according to the present invention. Fig. 2 is a flow chart of a method for accurately measuring the permeability coefficient of a film according to the present invention. Fig. 4 is a graph showing the relationship between the hydrogen pressure and the permeation time in a gas storage cylinder. Fig. 5 is a graph showing the relationship between the permeation flux and pressure difference of the membrane under different pressure indices. Fig. 6 is a graph showing the relationship between R2 and pressure index. 7 is the relationship between three different initial pressure difference, pressure index, r2 value and membrane permeability coefficient. [Main component symbol description] (1) Membrane permeation measuring device (10) Feeding unit (11) Gas storage cylinder (12) Nitrogen cleaning Cylinder (13) hydrogen cleaning cylinder (14) pressure sensor (15) pressure signal transmission line (16) signal recorder (17) three-way valve one (20) heating unit (18) three-way valve two (21) Heater (22) Thermal sensor (23) Temperature controller (25) Power switch (30) Permeation unit (24) Power output regulator (31) Thin film tube (32) Exhaust end conduit (33) Permeate end Catheter (34) Back Pressure Valve (35) Porous Stainless Steel Tube (37) Film (36) Airtight Stainless Steel Tube 201137338 (40) Outlet and Monitoring Unit (41) Electronic Flow Meter 1 (43) Exhaust End Exit (45) Signal transmission line (42) electronic flow meter two (44) permeate end outlet (46) flow display