539644 A7 B7 _ --------—______ 五、發明說明（1 ) 發明背景 1. 發明領域 本發明係關於一種純化氮氣之裝置和方法，且尤其是 關於使用可硝化氮純化合金之吸氣劑以吸收並去除雜胃i 使用Pd/Al2〇3以氧化甲烷成二氧化碳和水之改良裝置和方 法。 2. 技術背景之說明 氮氣是常用之氣體。在電子業、化工業、鋼鐵及船業 等工業領域中，氮氣之使用與日倶增。在傳統氮氣製造方 法中’使用壓縮機將空氣壓縮，而後將壓縮空氣重覆地絕 熱膨脹’直到壓縮空氣轉變成液態氣體，然後在高壓狀態 下自液態氣體中分離出氮氣，藉此得到高純度液態氮。液 態氮以液態或氣態方式裝塡在容器中而後被賣出。氮氣是 代表性之鈍氣且廣泛用於金屬與半導體製造方法中之加熱 製程。尤其是，氮氣也用於電子工業中之精密機械方法。 在此例中，必須在完成處理之前，使用高純度氮氣。在工 業領域中，液態氮被蒸發，且爲了大量使用以導管供應之 。此時’能快速且完全地移除包含在蒸發氮氣中之雜質， 例如氧氣，一氧化碳，二氧化碳，氫氣，碳氫化合物，水 等是非常重要的。在上述雜質中，碳氫化合物必須能被快 速地移除，因爲其會嚴重影響半導體之製造產率。 在工業上，使用各種不同的氮氣純化裝置以藉由移除 3方 < 氣氣中之雑質而徹底純化氮氣。 傳統氣體純化裝置使用氧化物催化劑，如錬，鉻等之 4 私紙張尺度中國國@準（CNS)A4規格（21〇 x 297公釐) " ' (請先閱讀背面之注意事項再填寫本頁)539644 A7 B7 _ ------------______ V. Description of the invention (1) Background of the invention 1. Field of the invention The present invention relates to a device and method for purifying nitrogen, and more particularly to a device for purifying alloys using nitrifiable nitrogen. Getter to absorb and remove miscellaneous stomach i An improved device and method using Pd / Al203 to oxidize methane to carbon dioxide and water. 2. Description of technical background Nitrogen is a commonly used gas. In the electronics, chemical, steel and shipbuilding industries, the use of nitrogen is increasing. In the traditional nitrogen manufacturing method, 'compress the air using a compressor, and then adiabaticly expand the compressed air repeatedly' until the compressed air is converted into a liquid gas, and then the nitrogen is separated from the liquid gas under high pressure, thereby obtaining high purity Liquid nitrogen. Liquid nitrogen is packaged in containers in liquid or gaseous form and sold. Nitrogen is a typical inert gas and is widely used in heating processes in metal and semiconductor manufacturing methods. In particular, nitrogen is also used in precision mechanical methods in the electronics industry. In this example, high purity nitrogen must be used before the process is completed. In the industrial sector, liquid nitrogen is evaporated and is supplied in large quantities by conduit. At this time, it is very important to be able to quickly and completely remove impurities contained in the evaporated nitrogen, such as oxygen, carbon monoxide, carbon dioxide, hydrogen, hydrocarbons, water, and the like. Among the above impurities, hydrocarbons must be able to be removed quickly because it may seriously affect the manufacturing yield of semiconductors. In the industry, various nitrogen purifying devices are used to purify nitrogen thoroughly by removing tritium in the gas. Traditional gas purification devices use oxide catalysts, such as osmium, chromium, etc., 4 Chinese paper standards @ 中国 （准 （CNS) A4） （21〇x 297mm） " '(Please read the precautions on the back before filling in this page)
I n n n n n n^OJf n I ί ϋ I n i I 線p· 539644 A7 B7_ 五、發明說明（7 ) 金屬氧化物以氧化一氧化碳’碳氫化合物，氫氣等，藉此 獲得二氧化碳與水，然後使用分子篩與活性碳來吸收與移 除雜質。 此外，在氣體純化裝置中，使用Ti-Mn族（其爲氫氣 吸收形式之合金），T-Fe族’稀土元素族-Ni族。在此例 中，會減少純化效率。 在USP 4,206,887中，揭示Fe-Zi*吸氣劑合金且由15-30重量％Fe與70-85重量％Zr所形成，其能選擇性吸收雜 質而不需要吸收氮氣。 發明摘述 因此，本發明之目的爲提供一種純化氮氣之裝置和方 法，其能藉由處理吸氣劑合金而增強氮氣純化效率。 本發明之另一目的爲提供一種純化氮氣之裝置和方法 ，其能移除，例如甲烷，一氧化碳，二氧化碳等雜質。 本發明之另一目的爲提供一種吸氣劑合金之處理方法 ，其與傳統合金吸氣劑相較下，具有改良的純化效率。 爲了達成上述目的，提供一種氮氣純化方法，其中由 Zi-V-Fe，Zr-Fe，Zr作爲主要成分所形成之吸氣劑合金在 與外界空氣連接之狀態下或在高真空狀態下與氮氣反應並 被塡入純化塔之較低部位（在雙純化塔之例中爲較低塔） ，而Pd/Al203催化劑被塡入溫度爲200-450°C之純化塔之 較高部位（在雙純化塔中爲較高塔），然後含在氮氣流（ 其將於200-450°C之溫度下被純化）中之甲烷成份會被氧 化，藉此從硝化吸氣劑中移除雜質，例如水，二氧化碳， 5 表紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁)I nnnnnn ^ OJf n I ϋ ni I ni I line p · 539644 A7 B7_ V. Description of the invention (7) Metal oxides oxidize carbon monoxide 'hydrocarbons, hydrogen, etc. to obtain carbon dioxide and water, and then use molecular sieve and activity Carbon to absorb and remove impurities. Further, in the gas purification device, a Ti-Mn group (which is an alloy in the form of hydrogen absorption), a T-Fe group, a rare earth element group, and a Ni group are used. In this example, purification efficiency is reduced. In USP 4,206,887, a Fe-Zi * getter alloy is disclosed and formed of 15-30% by weight of Fe and 70-85% by weight of Zr, which can selectively absorb impurities without absorbing nitrogen. SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a device and a method for purifying nitrogen, which can enhance the purification efficiency of nitrogen by treating a getter alloy. Another object of the present invention is to provide a device and method for purifying nitrogen, which can remove impurities such as methane, carbon monoxide, carbon dioxide and the like. Another object of the present invention is to provide a method for treating a getter alloy, which has an improved purification efficiency compared with a conventional alloy getter. In order to achieve the above object, a method for purifying nitrogen is provided, in which a getter alloy formed of Zi-V-Fe, Zr-Fe, Zr as a main component is connected with external air or under high vacuum with nitrogen The reaction is pushed into the lower part of the purification tower (lower tower in the case of the double purification tower), while the Pd / Al203 catalyst is pushed into the higher part of the purification tower at the temperature of 200-450 ° C (in the double purification tower) The higher column in the purification column) and then the methane component contained in the nitrogen stream (which will be purified at a temperature of 200-450 ° C) will be oxidized to remove impurities from the nitrated getter, such as Water, carbon dioxide, 5 paper sizes are applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)
539644 A7 ___ B7 _ 五、發明說明（\ ) 一氧化碳與氧氣。 爲了達成上述目的，提供一種氮氣純化裝置，其中由 Zr-V-Fe ’ Zr-Fe，Ζι*作爲主要成分所形成之吸氣劑合金在 與外界空氣連接之狀態下或在高真空狀態下與氮氣反應並 被塡入純化塔之較低部位，而Pd/Al203催化劑被塡入溫度 爲200-450°C之純化塔之較高部位，以藉此安裝成一純化 塔或另外形成兩個塔，而Pd/Al203被塡入較高塔，且吸氣 劑合金被塡入與較高塔連接之較低塔中。 圖式簡單說明 本發明藉由參考所附之圖式且經由說明而變得更加明 瞭，但本發明並不被所附之圖式所限定。 圖1氮氣在使用根據本發明氮氣純化裝置處理之前， 分析氮氣之氣相色層分離圖；及 圖2爲氣相色層分離圖，氮氣在使用根據本發明氮氣 純化裝置處理之後氮氣的分析。 較鱼具體實施例之詳細說明 本發明將參考所附之圖式以說明之。 一種由Zr-V-Fe，Zr-Fe，Zr作爲主要成分所形成之用 於氮氣純化的吸氣劑被插入一室溫容器中。該容器包括內 壁’其直接與氮氣接觸並由經良好拋光之金屬所形成，該 金屬具有用於將氣體吸收減到最小並預防因腐蝕而生成粉 末之繁密表面。習知有不銹鋼，咍司特鎳合金（hastelloy )’因科諾依合金（incoloy)與蒙淫耳合金可作爲前述金 屬材料。在本發明中，內壁之材料並不局限於此。可採用 6 谷紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) ---I--丨—訂--------- 539644 A7 ____B7 —___ 五、發明說明（V ) 具有相同性質之特殊材料。 接著，容器被加熱到200-450°C，並維持溫度，然後 將純氮氣（99.9999%以上）供給到容器內。在絕對壓力 0.卜1〇托耳下進行氮氣之注入。反應是在容器爲密封之狀 態下進行或在高真空狀態下進行。當氮氣被吸收時’合金 被硝化，而合金顏色會變成金色。當反應完成時’留在氮 氣反應容器內之氣體被抽出以藉此被移除。 被前述方法硝化之吸氣劑可被塡入純化塔之較低部位 (在雙純化塔之例中爲較低塔），而Pd/Al203催化劑被塡 入純化塔之較高部位（在雙純化塔中爲較高塔），然後含 在氮氣流（其將於200-450°C之溫度下被純化）中之甲烷 成份會被氧化。 此時，催化劑之數量是以含在氮氣流中之甲烷數量爲 基準。相對於吸氣劑合金，將使用0.001-10重量％。在甲 烷量很大之例中，氧氣可以如甲烷相同數量來提供。甲烷 會被氧化並生成二氧化碳與水。含有雜質之經氧化二氧化 碳及水與一氧化碳和氧氣被安裝於較低部位的吸氣劑所吸 收並移除。 在使用傳統硝化吸氣劑之例中，不可能從氮氣流中去 移除甲烷與碳氫化合物成份。在本發明中，有可能藉由連 接Pd/Al2〇3於較高部位並連接經硝化吸氣劑於溫度範圍在 200-450°C之內的較低部位以移除，例如甲烷、水、氧氣、 一'氧化碳、二氧化碳等雑質。 實施例1 7 衣紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) ---I I---訂.--------▲ 539644 A7 _______Β7_ 五、發明說明（< ) 在實施例1中，使用由22-25重量％?6與75-78重量 %Zr所形成並由義大利米蘭市之SAES getters S.P.A.所製 造之吸氣劑。400克之具有直徑3mm且高度4mm之小粒 子外型之圓柱形狀的Zr-Fe吸氣劑被插入一可與1公升玻 璃體積及壓力測量轉化器交替之微壓容器中。使用真空栗 將空氣抽至25毫托耳’接著移除真空泵之閥，然後檢測壓 力變化與用於在約1300托耳絕對壓力下添加氮氣所需之時 間的函數，再檢測氮氣吸收。反應完全之後，進行空氣安 定反應。吸氣劑被安裝於純化塔之較低部位，而Pd/Al2〇3 催化劑則塡入較高部位。在溫度400 °C時，進行含 235.5ppm —氧化碳，195.9ppm二氧化碳及218.8ppm甲院 之雜質的氮氣純化方法。含雜質之氮氣係於25°C之溫度， 6kg/cm2之壓力（錶壓)及0.17L/min之流率下流入純化器中 。氮氣通過具有溫度爲40(TC之吸氣劑層且在41 kg/cm2(錶 壓）的壓力下被抽空。在氣體吹入後，過40分鐘後，檢測 不同氣體雜質之位能。圖1與圖2說明在進行純化之後的 數據。 分析條件如下。 分析器(GC) : HP-5890系列II 偵測器：FID(甲烷化器）539644 A7 ___ B7 _ 5. Description of the invention (\) Carbon monoxide and oxygen. In order to achieve the above object, a nitrogen purifying device is provided, in which a getter alloy formed of Zr-V-Fe'Zr-Fe, Zil * as a main component is connected with external air or in a high vacuum state with Nitrogen reacts and is pumped into the lower part of the purification tower, and the Pd / Al203 catalyst is pumped into the higher part of the purification tower at a temperature of 200-450 ° C, thereby installing into a purification tower or forming two additional towers, And Pd / Al203 is entrained into the higher column, and the getter alloy is entrained into the lower column connected to the higher column. Brief Description of the Drawings The present invention is made clearer by referring to the attached drawings and through description, but the present invention is not limited by the attached drawings. Figure 1 shows the gas phase chromatographic separation of nitrogen before treatment with a nitrogen purification device according to the present invention; and Figure 2 shows the gas chromatographic separation diagram of nitrogen after treatment with the nitrogen purification device according to the present invention. Detailed description of the specific embodiment of the fish The present invention will be described with reference to the accompanying drawings. A getter for nitrogen purification, consisting of Zr-V-Fe, Zr-Fe, and Zr as main components, was inserted into a room temperature container. The container includes an inner wall ' which is in direct contact with nitrogen and is formed from a well polished metal having a dense surface for minimizing gas absorption and preventing the formation of powder due to corrosion. It is known that stainless steel, Hastelloy ' Incoloy and Moncole can be used as the aforementioned metal materials. In the present invention, the material of the inner wall is not limited to this. Can use 6-grain paper standard for China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) --- I-- 丨 --Order ------ --- 539644 A7 ____B7 —___ 5. Description of the invention (V) Special materials with the same properties. Next, the container is heated to 200-450 ° C, and the temperature is maintained, and then pure nitrogen (more than 99.9999%) is supplied into the container. Nitrogen injection was performed at an absolute pressure of 0.10 Torr. The reaction is carried out in a state in which the container is sealed or under a high vacuum. When nitrogen is absorbed, the alloy is nitrated and the alloy color becomes golden. When the reaction is complete, the gas remaining in the nitrogen reaction vessel is pumped out to be removed therefrom. The getter which has been nitrated by the aforementioned method can be poured into the lower part of the purification column (lower column in the case of the double purification column), while the Pd / Al203 catalyst is poured into the higher part of the purification column (in the double purification column) The tower is higher) and then the methane component contained in a nitrogen stream (which will be purified at a temperature of 200-450 ° C) will be oxidized. At this time, the amount of catalyst is based on the amount of methane contained in the nitrogen stream. Relative to the getter alloy, 0.001-10% by weight will be used. In the case of a large amount of methane, oxygen can be provided in the same amount as methane. Methane is oxidized and generates carbon dioxide and water. Oxidized carbon dioxide and water, carbon monoxide and oxygen containing impurities are absorbed and removed by a getter installed at a lower position. In the case of conventional nitrifying getters, it is not possible to remove methane and hydrocarbon components from the nitrogen stream. In the present invention, it is possible to remove Pd / Al203 by connecting it to a higher position and connecting a nitrated getter to a lower position within a temperature range of 200-450 ° C, such as methane, water, Oxygen, carbon monoxide, carbon dioxide, etc. Example 1 7 The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) --- I I --- order. ---- ▲ 539644 A7 _______ Β7_ 5. Description of the invention (<) In Example 1, the use of SAES getters SPA formed from 22-25% by weight? 6 and 75-78% by weight Zr and formed by Milan, Italy Made of getter. 400 g of a cylindrical shape Zr-Fe getter having a small particle shape of 3 mm in diameter and 4 mm in height was inserted into a micro-pressure container that can be alternated with a 1 liter glass volume and pressure measuring converter. The vacuum pump was used to draw air to 25 mTorr 'followed by removing the valve of the vacuum pump, and then measuring the pressure change as a function of the time required to add nitrogen at an absolute pressure of about 1300 Torr, and then detecting the nitrogen absorption. After the reaction was completed, an air-stabilized reaction was performed. The getter is installed in the lower part of the purification tower, while the Pd / Al203 catalyst is inserted into the higher part. At a temperature of 400 ° C, a nitrogen purification method containing 235.5 ppm of carbon oxide, 195.9 ppm of carbon dioxide, and 218.8 ppm of impurities in the A hospital was performed. The nitrogen gas containing impurities flows into the purifier at a temperature of 25 ° C, a pressure (gauge pressure) of 6 kg / cm2 and a flow rate of 0.17 L / min. Nitrogen was evacuated through a getter layer with a temperature of 40 ° C and a pressure of 41 kg / cm2 (gauge pressure). After the gas was blown in, the potential energy of different gas impurities was detected after 40 minutes. Figure 1 Figure 2 illustrates the data after purification. The analysis conditions are as follows. Analyzer (GC): HP-5890 Series II Detector: FID (Methanator)
純化塔：Porapak QPurification tower: Porapak Q
烤箱溫度：維持35t 偵測溫度：250°C 注射口 A溫度：50°C 8 木紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) --------訂---------線一 539644 A7 ______ ___ B7___ 五、發明說明（G ) 注射口 B溫度：375t： 載體：He 20mL/min 在本發明中，吸氣劑合金具有極佳純化效率。有可能 完全移除一氧化碳氣體，二氧化碳氣體及甲烷氣體。 當本發明可以不脫離本發明之精神或基本特徵之數種 形式被舉例時，應瞭解前述具體實施例並不被任何前述說 明之細節限制，除非在其他方面特有指明，但仍應被廣泛 地解釋於所附申請專利範圍的精神與範疇內，因此所有改 變與修飾應屬於申請專利範圍之集合與限制內，或該等集 合與限制之相等物因此被意圖包括在所附申請專利範圍中 (請先閱讀背面之注意事項再填寫本頁) 9 —訂---------線* 表紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）Oven temperature: Maintain 35t. Detection temperature: 250 ° C. Injection port A temperature: 50 ° C. 8 Paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm). (Please read the precautions on the back before filling. (This page) -------- Order --------- line one 539644 A7 ______ ___ B7___ V. Description of the invention (G) Injection port B temperature: 375t: Carrier: He 20mL / min In the invention, the getter alloy has excellent purification efficiency. It is possible to completely remove carbon monoxide gas, carbon dioxide gas and methane gas. When the present invention can be exemplified in several forms without departing from the spirit or essential characteristics of the present invention, it should be understood that the foregoing specific embodiments are not limited by the details of any of the foregoing descriptions, and should be broadly defined unless otherwise specifically indicated otherwise. The explanation is within the spirit and scope of the scope of the attached patent application, so all changes and modifications should fall within the collection and limitation of the scope of the patent application, or equivalents of such collections and limitations are therefore intended to be included in the scope of the attached application patent ( Please read the notes on the back before filling in this page) 9 —Order --------- line * The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)