200909043 九、發明說明： 【發明所屬之技術領域】 本發明係有關於一種含氟化合物氣體之處理方法，特 別有關於一種含氟化合物氣體的吸附置換反應。 【先前技術】 近年來環保意識高漲，為了降低溫室效應，在半 導體製程中使用的含氟化合物必須經過處理才可排 放至大氣中，一般所使用的含氟化合物例如為全氟碳 化合物（perfluorocarbons，簡稱 PFCs)，其為包括 CF4、 C2F4、C2HF3、C2F6、 C3F6等含有多個氟原子之 石炭氫化合物的統稱，具有極高之化學穩定性。 現行的含氟化合物處理技術主要有高溫直接分 解法、高能離子分解法及觸媒分解法，其中以高溫直 接分解法及觸媒分解法最為成熟，而觸媒分解法更具 有操作溫度低、分解效率高且安全性高之優點。 觸媒分解法主要有循環水解反應及吸附置換反 應兩種方式，水解反應必須在含有水氣之情況下進行 反應，PFC經觸媒反應後會轉化成氫氟酸及二氧化 碳，故需加設一濕式洗滌器以去除氫氟酸；而吸附置 換反應則是利用化學吸附劑在高溫（400〜700°C )情況 下，使化學吸附劑吸附PFC化合物後進行氧和氟的 置換反應將PFC去除，反應後產生一氧化碳或二氧 化碳，不會產生酸性氣體。循環水解具有較高的處理 0954-A22114TWCIPF(N2)；P54960008TWC1 ；kefly 6 200909043 J及壽命，但設備較為複雜且不易維護；吸附置換的 J理量與吸附劑量相關’但相對壽命較短，若處理高 /辰度PFC則需經常更換化學吸附劑。 ° GUild ―心…公司在美國%利早期公開第 US200W號中描述__種使用Al2〇3為載體= 性成分為Zr〇2及C〇2〇3的水解型觸媒分解pFCs，盆 觸媒活性在90%以上。Sh〇WaDenk〇&司在美國專利 第US63_18號中描述—種使用Al2Q3及aip〇4為载 體，活性成分為Ce〇2、La2〇3及Cr〇3的水解型觸媒 分解PFCs，其觸媒活性接近]〇〇%之轉化率。值得注 意的是，在上述之反應條件中都需含有水汽，若進氣 組成中不含水汽，則去除效果將大打折扣，轉化率僅 為 7.5 % 。200909043 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a method for treating a fluorine-containing compound gas, and more particularly to an adsorption displacement reaction of a fluorine-containing compound gas. [Prior Art] In recent years, environmental awareness has increased. In order to reduce the greenhouse effect, fluorine-containing compounds used in semiconductor processes must be processed before being discharged into the atmosphere. Generally, fluorine-containing compounds such as perfluorocarbons (perfluorocarbons) are used. Referred to as PFCs), it is a general term for carbon hydrocarbons containing a plurality of fluorine atoms, such as CF4, C2F4, C2HF3, C2F6, C3F6, etc., and has extremely high chemical stability. The current fluorine-containing compound treatment technologies mainly include high-temperature direct decomposition method, high-energy ion decomposition method and catalytic decomposition method. Among them, the high-temperature direct decomposition method and the catalytic decomposition method are the most mature, and the catalyst decomposition method has lower operating temperature and decomposition. High efficiency and high security. Catalytic decomposition method mainly has two methods: cyclic hydrolysis reaction and adsorption displacement reaction. The hydrolysis reaction must be carried out under the condition of containing water gas. PFC will be converted into hydrofluoric acid and carbon dioxide after the catalyst reaction, so it is necessary to add one. The wet scrubber removes hydrofluoric acid; and the adsorption displacement reaction uses a chemical adsorbent to remove the PFC compound at a high temperature (400 to 700 ° C), and then removes the PFC compound to remove the PFC. After the reaction, carbon monoxide or carbon dioxide is produced, and no acid gas is generated. Cyclic hydrolysis has higher treatment 0954-A22114TWCIPF(N2); P54960008TWC1; kefly 6 200909043 J and life, but the equipment is more complicated and difficult to maintain; the amount of adsorption displacement is related to the adsorption dose' but the relative life is shorter, if it is treated High/length PFCs require frequent replacement of chemical adsorbents. ° GUild ―Heart...The company described in the United States% of the early publication US200W __ using Al2〇3 as the carrier = the hydrolysis component of the Zr〇2 and C〇2〇3 decomposition of pFCs, pottery catalyst The activity is above 90%. Sh〇WaDenk〇&<>> described in U.S. Patent No. US63-18, a hydrolysis-type catalytic decomposition PFCs using Al2Q3 and aip(R)4 as carriers and active ingredients Ce2, La2?3 and Cr?3, Catalyst activity is close to the conversion rate of 〇〇%. It is worth noting that water vapor is required in the above reaction conditions. If there is no water vapor in the intake composition, the removal effect will be greatly reduced, and the conversion rate is only 7.5 %.
Showa Denko KK公司在美國專利第6,63〇 421 B1號中描述一種吸附置換反應型吸附劑，其為含有 氧化鋁與鎂、鈣、锶或鋇之碳酸鹽的鹼土 物’可在不含水汽的條件下將氟化物轉化成氧化物： 將其去除，優點為設備簡易且反應後不產生氫氟酸， 但缺點是使用壽命短，吸附劑更換頻率高。 因此，業界亟需一種用於去除含氟化合物之吸附置 換反應型吸附劑，其可以在不含水汽的條件下將氟化 物轉化成穩定化合物而將其去除，同時具有較長之觸媒 哥命。 【發明内容】 0954-A22114TWC!PF(N2)；P54960008TWC1 ；kelly 7 200909043 本發明提供一種含氟化合物氣體之處理方法，將含有含 氟化合物之氣體接觸活性吸附劑，使含氟化合物被活性吸 附劑吸附並與活性吸附劑反應，其中活性吸附劑之組成包 括沸石及驗土金屬化合物，且其中彿石和驗土金屬化合物 之重量比為1:20至4:6。 ▲為了讓本發明之上述目的、特徵、及優點能更明顯易 f董，以下配合所附圖式，作詳細說明如下： 【實施方式】 本發明之目的在於開發一種可處理pFC之化學吸附 背J，而本發明之含氟化合物氣體的處理方法，係利用下 述之吸附反應型觸媒作為活性吸附劑進行吸附置換反應， 由於該活性吸附劑之比表面積大⑥丨⑻m2/g，其進氣條件 中不需含有水氣或水氣含量低於丨重量％，即可使得初始 轉化率達到99%以上，並具有相當長之壽命。 〇 本發明所提供之去除氣體中含氣化合物的活性吸附劑 及處理方法係將-含有含氣化合物的氣體於·〜綱 °C通過由彿石與鹼土金屬化合物所形成之活性吸附 劑，氣體中的氟化物將會被活性吸附劑吸附並與豆反 應’將氟化物轉化成穩定的化合物，例如將CF4、轉 化成CO或C〇2，反應後氟將被活性吸附劑吸附或盘 活性吸附劑反應生成穩定化合物。 /、 本發明之活性吸附劑的組成包括：滞石及驗土金屬化 合物，且沸石和鹼土金屬化合物之重量比約為12〇至 4:6’其中鹼土金屬化合物例如為鎮令銷或鋇之碳酸鹽， 0954-A22114TWCIPF(N2)；P54960008TWC1；kelly 200909043 彿石之比表面積大於400m2/g，沸石之成分可為叫和 A1203’且Sl〇2和Al2〇3之莫耳比為1〇:1至⑽卜 本發明之时韻射^與驗土金纽合物的比例需在 二：圍内里當彿石成分太低時，無法達到快速分解含氟 ίΐ物之效果；#驗土金屬化合物太低時，則會降低吸附 谷罝。-般而言，在上述活性吸_的組成中，沸石約為 4〜40重量百分比’鹼土金屬化合物約為9“〇重量百分比。 除了彿石與驗土金屬化合物之外，本發明之顆粒狀活 性吸附劑中還可額外選擇性地包括—黏合劑（mn㈣以幫 助成型’適當的黏合劑在活性吸附劑中的重量比為 0.5%〜9% ’此處所使㈣黏合劑並無特別限制，孰悉此技 藝人士可視需要任意選用適當之黏合劑。黏合劑可為有機 或無機化合物，且其中有機化合物例如為甲基纖維素、聚 乙稀醇(polyviny〗 alcohol)、聚碳酸賴脂（p〇iycarb_te) 或聚丙烯酸(polyaerylie add)，無機化合物例如為秒溶膠及 氧化鋁或其前驅物硝酸鋁、水鋁土（b〇ehmite)、擬薄水鋁土 (pseudoboehmite)或三氣化鋁，常用之黏合劑包括，但不限 於：矽酸鈉、氧化鋁、曱酸鈉、氫氧化鈉、曱基纖維素、 聚乙浠醇等。黏合劑一般約佔該吸附劑〇·4〜1 〇重量％， 較佳約為0.5〜3重量％。 本發明之處理方法可去除的含氟化合物包括全氟碳化 物（perfluorocarbons)、氫就碳化物（hydrofluorocarbons)、NF3 或SF6等，含氟化合物在進氣氣體中的濃度可為0.01〜5 莫耳％(mol%)，並且在進氣氣體中氧氣的濃度可為2〜20 0954-A22114TWCIPF(N2)；P54960008TWC1 ；Kel!y 9 200909043 莫耳％(mol%)。本發明 系統，將上述之顆粒大】、免理方法可利用傳統固定床反應 Μ毫升置入内徑2公二、為〇.3〜0·8公分的活性吸附劑取約 控制進料氣體進入^刀的不鏽鋼管中，利用電熱爐加熱並 之間，進氣氣體的空的入口溫度約在300〜峨 流量約為525 ml/分鐘，:約為437小時」，進料氣體總 本發明之纽料 附容⑽估測試。 體戋光電及活性吸附劑特別適用於處理半導 的氣體’此外，本發明之處理方法及 何亦並非僅限用於半導體或光電產業，反之，任 Π 3 4化。物成分之卫業廢氣均可利用本發明之活性 吸附劑及處理方法加以處理。同時，由於本發明之處理 係採用吸ρ付置換反應，因此不像水解反應會產生 虱亂酸’故不需加設濕式洗滌器以去除氫氟酸。 尸以下為本發明之活性吸附劑的製備與處理纟氣化合物 氣體之實施例，以及傳統的吸附反應型觸媒的製造方法與 處理含氟化合物氣體之比較例。 【實施例1】 活性吸附劑CaCC^/Y-Zeolite (重量比為70/30)的製備 取碳酸#5 (純度98.6%) 140克加γ型沸石6〇克， 其中Y型沸石之成分包括Si〇2和a12〇3，且Si02和 Al2〇3的莫耳比為30: 1，充分混合後加入54克lwt % 曱基纖維素及42克的水，以混練機將混合物充分擾 拌及混練約2 0分鐘’直至混練物呈現麵團狀，再以 0954-A22114TWCIPF(N2)；P54960008TWC1 ikelty 10 200909043 型機將其擠出成長條狀(直徑〇4公分）後， 二4:下乾燥4小時，再移至高溫爐中以城锻 " 立。將燒結後之白色產物粉碎過篩取0.3〜0.8 公分之柱狀物備用。 【實施例2】 活性吸附劑CaC〇3/ ZSM_5_Z_te (重量比為期〇) 的製備 取碳酸鈣（純度98.6%)157.5克加ZSM_5型沸石 67.5克，其中ZSM-5型沸石之成分包括和 AhO3，且Si〇2和八丨2〇3的莫耳比為5〇 :卜充分混 合後加入54克lwt %曱基纖維素及4〇克的水，以混 練機將混合物充分攪拌及混練約2〇分鐘，直至混練 物呈現麵團狀’再以擠出成型機將其擠出成長條狀 (直徑0.4公分）後，在〗i(TC下乾燥4小時，再移至 高溫爐中以55(TC煅燒4小時。將燒結後之白色產物 粉碎過篩取〇, 3〜0.8公分之柱狀物備用。 【實施例3】 活性吸附劑CaCCVY-Zeolite (重量比為^24)的製備 取碳酸鈣（純度98.6%) 130克加入γ型彿石4〇 克’其中Y型）弗石之成分包括Si〇2和AI2O3，且Si〇2 和Al2〇3的莫耳比為30 : 1 ’充分混合後加入黏結劑 (54克lwt %曱基纖維素及擬薄水鋁土（pseud〇 boehmite) 1 5克）和35克的水’以混練機將混合物充 分攪拌及混練約20分鐘’直至混練物呈現麵團狀， 0954-A22114TWCIPF(N2)；P54960008TWC1；ketly 200909043 再以擠出成型機將其擠出成長條狀（直徑〇.4公分） 後，在110°c下乾燥4小時，再移至高溫爐中以550 C烺燒4小時。將燒結後之白色產物粉碎過筛取 0.3〜0.8公分之柱狀物備用。 【實施例4】 活性吸附劑CaC〇3/ZSM-5-Ze〇Hte (重量比為93/7)的 製備 取碳酸鈣（純度98.6%)170克加入ZSM-5型沸石 { 12克’其中ZSM-5型沸石之成分包括Si〇2和Al2〇3, 且Si〇2和Al2〇3的莫耳比為50 : !，充分混合後加入 黏結劑（54克lwt %曱基纖維素及擬薄水鋁土（pseudc) boehmite) 24.2克）和18.5克的水，以混練機將混合 物充分攪拌及混練約20分鐘，直至混練物呈現麵團 狀，再以擠出成型機將其擠出成長條狀（直徑0.4公 分）後，在11 〇°C下乾燥4小時，再移至高溫爐中以 550°C煅燒4小時。將燒結後之白色產物粉碎過_取 : 0,3〜0.8公分之柱狀物備用。 【比較例1】 活性吸附劑CaC03/Kaolin (70/30)的製備 取碳酸鈣140克加上高嶺土（kaolin)(Showa Chemicals Inc. ’ Si02 含量 72.10% ，Al2〇3 含量 19·57%)60 克，充分 混合後加入54克lwt %甲基纖維素及40克水，以混練機 將混合物充分攪拌及混練約20分鐘，直至混練物呈現麵 團狀，再以擠出成型機將其擠出成長條狀（直徑0.4公分；| 0954-A22114TWCIPF(N2)；P54960008TWC1 ；kelly 200909043 後，在110°c下乾燥4小時，再移至高溫爐中以550°c煅燒 4小時。將燒結後之灰白色產物粉碎過篩取0.3〜0.8公分之 柱狀物備用。 實施例與比較例之觸媒分解PFC的能力測試 利用傳統固定床反應系統，測試上述實施例與比較例 之觸媒分解全氟碳化物（PFC)的分解能力。分別取72毫升 比較例1及實施例1、2、3及4合成之顆粒狀觸媒，置入 内徑2公分之不鏽鋼管中，再利用電熱爐加熱並控制進料 氣體進入不鏽鋼管的入口溫度，進料氣體條件為： l.SF6之濃度為3000 ppm，氧濃度為5mol%，其它為 氮氣。 2. 反應溫度為650°C。 3. 進料氣體空間流速為437小時4，進料氣體總流量約 為525ml/分鐘。 其中，進料氣體中不含水氣。 比較例1及實施例1、2、3及4合成之顆粒狀觸媒對 於全氟碳化物（PFC)的去除率與反應時間的曲線圖如第1 圖所示。 上述之觸媒分解全氟碳化物（PFC)的分解能力如下表1 所列： 0954-A22114TWCIPF(N2)；P54960008TWC1；kelly 200909043 表1活性吸附劑分解PFC的效果 觸媒 初始去除率（°/〇) 去除率達86%之時間（小時） 比較例1 >99 0.1 實施例1 >99 18 實施例2 >99 19 實施例3 >99 24 實施例4 >99 29 由表1的結果可得知，比較例1中使用由高嶺土和碳 酸鈣所構成之活性吸附劑對於PFCs之處理壽命短，幾乎 無法有效處理PFCs氣體。由於高嶺土是由不同比例之Si02 及ai2o3混合而成之混合物，不像沸石具有特殊結構可將 PFCs加以吸附分解。而本發明實施例1、2、3及4為含有 不同種類沸石的活性吸附劑，其初始去除率與比較例1相 當，且其去除率降至86%的時間則更為延長，顯示本發明 含有沸石成分之活性吸附劑具有相當高之初始去除率及處 理壽命，因此可降低吸附劑的更換頻率。 雖然本發明已揭露較佳實施例如上，然其並非用以限 定本發明，任何熟悉此項技藝者，在不脫離本發明之精神 和範圍内，當可做些許更動與潤飾，因此本發明之保護範 圍當視後附之申請專利範圍所界定為準。 0954-A22114TWCIPF(N2)；P54960008TWC1；keliy 14 200909043 【圖式簡單說明】 第1圖為實施例1、2、3及4與比較例1之去除率與 反應時間的曲線圖。 【主要元件符號說明】 無。 0954-A22114TWC1PF(N2)；P54960008TWC1 ；kei!y 15Showa Denko KK, in U.S. Patent No. 6,63,421 B1, describes an adsorptive displacement reaction type adsorbent which is an alkaline earth material containing alumina and a carbonate of magnesium, calcium, barium or strontium. Conversion of fluoride to oxide under the conditions: It is removed, the advantage is that the equipment is simple and does not produce hydrofluoric acid after the reaction, but the disadvantage is that the service life is short and the frequency of adsorbent replacement is high. Therefore, there is a need in the industry for an adsorption displacement reaction type adsorbent for removing a fluorine-containing compound, which can convert a fluoride into a stable compound without water vapor and remove it, and has a long catalyst life. . SUMMARY OF THE INVENTION 0954-A22114TWC!PF(N2); P54960008TWC1; kelly 7 200909043 The present invention provides a method for treating a fluorine-containing compound gas, which comprises contacting a gas containing a fluorine-containing compound with an active adsorbent to cause the fluorine-containing compound to be activated adsorbent. Adsorbing and reacting with the active adsorbent, wherein the composition of the active adsorbent comprises a zeolite and a soil-measuring metal compound, and wherein the weight ratio of the Fossil to the soil-measuring metal compound is 1:20 to 4:6. ▲ In order to make the above objects, features, and advantages of the present invention more obvious, the following is a detailed description of the following: [Embodiment] The purpose of the present invention is to develop a chemical adsorption back that can handle pFC. J, the method for treating a fluorine-containing compound gas of the present invention is to carry out an adsorption displacement reaction using the adsorption reaction type catalyst described below as an active adsorbent, and the specific surface area of the active adsorbent is 6 丨 (8) m 2 /g, which is The gas condition does not need to contain moisture or the moisture content is less than 丨% by weight, so that the initial conversion rate is over 99% and has a long life. The active adsorbent and the treatment method for removing gas-containing compounds in the gas provided by the present invention are: a gas containing a gas-containing compound is passed through an active adsorbent formed by a smectite and an alkaline earth metal compound, a gas The fluoride in the fluoride will be adsorbed by the active adsorbent and reacted with the bean to convert the fluoride into a stable compound, for example, CF4, converted to CO or C〇2, after which the fluorine will be adsorbed by the active adsorbent or adsorbed by the disk. The agent reacts to form a stable compound. The composition of the active adsorbent of the present invention comprises: a stagnation stone and a soil metal compound, and the weight ratio of the zeolite to the alkaline earth metal compound is about 12 〇 to 4:6 ′, wherein the alkaline earth metal compound is, for example, a township pin or 钡Carbonate, 0954-A22114TWCIPF(N2); P54960008TWC1; kelly 200909043 The specific surface area of buddha is more than 400m2/g, the composition of zeolite can be called A1203' and the molar ratio of S1〇2 and Al2〇3 is 1〇:1 To (10), the ratio of the rhythm of the invention to the soil test gold nucleus needs to be in the second: when the composition of the budstone is too low, the effect of rapidly decomposing the fluorinated sputum cannot be achieved; When low, it will reduce the adsorption of gluten. In general, in the composition of the above active sorption, the zeolite is about 4 to 40% by weight of the 'alkaline earth metal compound, and is about 9 〇 by weight. In addition to the phoenix and the soil metal compound, the granule of the present invention The active adsorbent may additionally include a binder (mn (four) to help shape the proper binder in the active adsorbent in a weight ratio of 0.5% to 9%. Here, the (4) binder is not particularly limited, It is understood that the skilled person may arbitrarily select an appropriate adhesive as needed. The adhesive may be an organic or inorganic compound, and the organic compound thereof is, for example, methyl cellulose, polyviny alcohol, polycaprite (p) 〇iycarb_te) or polyaerylie add, inorganic compounds such as second sol and alumina or its precursors aluminum nitrate, bauxehmite, pseudoboehmite or tri-aluminized, Commonly used adhesives include, but are not limited to, sodium citrate, aluminum oxide, sodium citrate, sodium hydroxide, decyl cellulose, polyethylene glycol, etc. The binder generally accounts for about 4·4~1 吸附weight The amount of fluorine, preferably about 0.5 to 3% by weight. The fluorine-containing compound which can be removed by the treatment method of the present invention includes perfluorocarbons, hydrofluorocarbons, NF3 or SF6, etc. The concentration in the intake gas may be 0.01 to 5 mol% (mol%), and the concentration of oxygen in the intake gas may be 2 to 20 0954-A22114TWCIPF (N2); P54960008TWC1; Kel!y 9 200909043 mol% (mol%). The system of the present invention, the above-mentioned particles are large, and the treatment method can be carried out by using a conventional fixed bed reaction Μ ml into an active sorbent having an inner diameter of 2 mils and a 〇3 to 0·8 cm. The feed gas is controlled to enter the stainless steel tube of the knife, and is heated by the electric furnace, and the empty inlet temperature of the intake gas is about 300 峨, the flow rate is about 525 ml/min, about 437 hours, The gas is generally tested according to the invention (10). The body photoelectric and active adsorbents are particularly suitable for treating semi-conductive gases. Furthermore, the treatment method of the present invention is not limited to the semiconductor or photovoltaic industry, and vice versa. , 任Π 3 4. The composition of the ingredients The exhaust gas of the present invention can be treated by the active adsorbent and the treatment method of the present invention. At the same time, since the treatment of the present invention adopts a suction-replacement reaction, unlike the hydrolysis reaction, a disorderly acid is generated, so that no wet type is required. The scrubber is used to remove hydrofluoric acid. The following is an example of the preparation and treatment of a helium gas of the active adsorbent of the present invention, and a comparative example of a conventional method for producing an adsorption reaction type catalyst and a fluorine-containing compound gas. [Example 1] Preparation of active adsorbent CaCC^/Y-Zeolite (weight ratio 70/30) was taken as carbonic acid #5 (purity 98.6%) 140 g plus γ-type zeolite 6 g, wherein the composition of Y-type zeolite included Si〇2 and a12〇3, and the Moor ratio of SiO 2 and Al 2 〇 3 is 30: 1, after thorough mixing, 54 g of lwt % thiol cellulose and 42 g of water are added, and the mixture is fully disturbed by a kneading machine. Mix for about 20 minutes' until the kneaded material is in the form of dough, and then extrude it into strips (diameter 〇 4 cm) with 0854-A22114TWCIPF(N2); P54960008TWC1 ikelty 10 200909043 machine, then dry 4 hours: 4:4 , then move to the high temperature furnace to forge " ; Standing. The sintered white product was pulverized and sieved to a column of 0.3 to 0.8 cm for use. [Example 2] The active adsorbent CaC〇3/ZSM_5_Z_te (weight ratio is 〇) was prepared by taking 157.5 g of calcium carbonate (purity 98.6%) and 67.5 g of ZSM_5 type zeolite, wherein the composition of the ZSM-5 type zeolite includes and AhO3. And the molar ratio of Si〇2 and gossip 2〇3 is 5〇: after fully mixing, add 54g of lwt% mercapto cellulose and 4g of water, stir the mixture thoroughly and mix about 2〇 with a kneading machine. Minutes until the kneaded material is in the form of a dough, and then extruded into a strip shape (0.4 cm in diameter) by an extrusion molding machine, dried at 〖i (TC for 4 hours, and then transferred to a high temperature furnace at 55 (TC calcination). 4 hours. The white product after sintering was pulverized and sieved, and a column of 3 to 0.8 cm was used. [Example 3] Preparation of active adsorbent CaCCVY-Zeolite (weight ratio of 24) Calcium carbonate (purity) 98.6%) 130 g added γ-type Fossil 4 gram 'When Y-type) phoenix composition includes Si 〇 2 and AI 2 O 3 , and the molar ratio of Si 〇 2 and Al 2 〇 3 is 30 : 1 ' Adhesive (54g lwt% thiol cellulose and pseudo-bauxite (pseud〇boehmite) 15g) and 35g of water' will be mixed The mixture was thoroughly stirred and kneaded for about 20 minutes' until the kneaded material was in the form of dough, 0954-A22114TWCIPF (N2); P54960008TWC1; ketly 200909043 and then extruded into strips (diameter 4.4 cm) by an extrusion molding machine. Dry at 110 ° C for 4 hours, then move to a high temperature furnace and simmer for 4 hours at 550 C. The sintered white product is pulverized and sieved to a column of 0.3 to 0.8 cm for use. [Example 4] Active adsorbent Preparation of CaC〇3/ZSM-5-Ze〇Hte (weight ratio of 93/7) 170 g of calcium carbonate (purity 98.6%) was added to ZSM-5 type zeolite {12 g' wherein the composition of ZSM-5 type zeolite included Si〇2 and Al2〇3, and the molar ratio of Si〇2 and Al2〇3 is 50:!, and the binder is added after mixing (54 g of lwt% mercapto cellulose and pseudo-alumina (pseudc) boehmite 24.2 g) and 18.5 g of water, the mixture was thoroughly stirred and kneaded in a kneading machine for about 20 minutes until the kneaded material was in the form of a dough, and then extruded into a strip shape (0.4 cm in diameter) by an extrusion molding machine. It was dried at 11 ° C for 4 hours and then transferred to a high temperature furnace and calcined at 550 ° C for 4 hours. The white product after sintering was pulverized to take: 0, 3 to 0.8 cm of the column for use. [Comparative Example 1] Preparation of active adsorbent CaC03/Kaolin (70/30) 140 g of calcium carbonate plus kaolin (Showa Chemicals Inc. 'Si02 content 72.10%, Al2〇3 content 19.57%) 60 Grams, after mixing thoroughly, add 54 g of lwt% methylcellulose and 40 g of water, stir the mixture thoroughly and mix for about 20 minutes with a kneading machine until the kneaded material is in the form of dough, and then extrude it by an extruder. Strip (diameter 0.4 cm; | 0954-A22114TWCIPF (N2); P54960008TWC1; kelly 200909043, dried at 110 ° C for 4 hours, then transferred to a high temperature furnace and calcined at 550 ° C for 4 hours. The sintered grayish white product The column was pulverized and sieved for 0.3 to 0.8 cm. The ability of the catalyst of the examples and the comparative examples to decompose the PFC was tested by using a conventional fixed bed reaction system to test the catalyst decomposition perfluorocarbon of the above examples and comparative examples ( PFC) Decomposition ability: Take 72 ml of the particulate catalyst synthesized in Comparative Example 1 and Examples 1, 2, 3 and 4, place it in a stainless steel tube with an inner diameter of 2 cm, and then use an electric furnace to heat and control the feed. Gas entering the stainless steel tube The mouth temperature and feed gas conditions are: l. The concentration of SF6 is 3000 ppm, the oxygen concentration is 5 mol%, and the others are nitrogen. 2. The reaction temperature is 650 ° C. 3. The feed gas space flow rate is 437 hours 4, into The total gas flow rate is about 525 ml/min. Among them, there is no water in the feed gas. The removal rate of the perfluorocarbon (PFC) by the particulate catalyst synthesized in Comparative Example 1 and Examples 1, 2, 3 and 4. The graph of the reaction time is shown in Fig. 1. The decomposition ability of the above catalyst decomposition perfluorocarbon (PFC) is listed in Table 1 below: 0954-A22114TWCIPF(N2); P54960008TWC1; kelly 200909043 Table 1 Active adsorbent Effect of decomposition of PFC Initial removal rate of catalyst (°/〇) Time of removal of 86% (hours) Comparative Example 1 > 99 0.1 Example 1 > 99 18 Example 2 > 99 19 Example 3 > 99 24 Example 4 > 99 29 It can be seen from the results of Table 1 that the active adsorbent composed of kaolin and calcium carbonate in Comparative Example 1 has a short treatment life for PFCs, and it is almost impossible to effectively treat PFCs gas. It is a mixture of different proportions of Si02 and ai2o3. Unlike the zeolite, which has a special structure, the PFCs can be adsorbed and decomposed. However, in the present invention, Examples 1, 2, 3 and 4 are active adsorbents containing different kinds of zeolites, and the initial removal rate is comparable to that of Comparative Example 1, and the removal thereof is carried out. The time to fall to 86% is further extended, indicating that the active adsorbent containing the zeolite component of the present invention has a relatively high initial removal rate and treatment life, thereby reducing the frequency of replacement of the adsorbent. Although the present invention has been disclosed in its 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 protection is subject to the definition of the scope of the patent application attached. 0954-A22114TWCIPF(N2); P54960008TWC1; keliy 14 200909043 [Simplified description of the drawings] Fig. 1 is a graph showing the removal rates and reaction times of Examples 1, 2, 3 and 4 and Comparative Example 1. [Main component symbol description] None. 0954-A22114TWC1PF(N2); P54960008TWC1 ;kei!y 15