200920470 九、發明說明: 【發明所屬之技術領域】 本發明係有關於一種處理廢氣之裝置及方法,特別係 有關於一種處理包含多氟碳化合物之廢氣的裝置及方法。 【先前技術】 多I碳化合物(perfluorinated compound,以下可簡稱 PFC)係含有多個氟原子之碳氫化合物的統稱,其具有極高 f 之化學穩定性(生命週期約超過1〇,〇〇〇年),且為無味及毒 性極低之化合物,用途廣泛。多氟碳化合物之一用途是作 為半導體晶圓廠乾式钱刻及化學氣相沉積(chemical vapor deposition,CVD)設備之清洗劑。由於多氟碳化合物極為 穩定,目前用於晶圓廠之廢氣處理系統皆無法有效將之去 除,導致多氟碳化合物排放至大氣中,造成環境污染及促 進全球溫室效應。雖然多氟碳化合物之總排放量遠低於二 氧化碳(C02),但其對溫室效應的影響卻較二氧化碳超出許 ^ 多,進而衍生出溫室效應問題。京都議定書(Kyoto Protocol)決議工業先進國家應於公元2008至2012年期 間,將包含二氧化碳在内的6種溫室效應氣體之年平均排 放量,減少至低於1990年平均排放量5.2%。由於京都議 定書的簽定將衝擊國内使用含氟化合物之半導體製造產 業,需要一可有效處理含氟化合物之方法及設備。200920470 IX. Description of the Invention: [Technical Field] The present invention relates to an apparatus and method for treating exhaust gas, and more particularly to an apparatus and method for treating exhaust gas containing polyfluorocarbon compounds. [Prior Art] A perfluorinated compound (hereinafter referred to as PFC) is a general term for hydrocarbons containing a plurality of fluorine atoms, and has a chemical stability of extremely high f (life cycle is more than about 1 〇, 〇〇〇 Year), and is a odorless and extremely toxic compound with a wide range of uses. One of the uses of polyfluorocarbons is as a cleaning agent for dry wafer engraving and chemical vapor deposition (CVD) equipment in semiconductor fabs. Due to the extremely stable nature of PFCs, exhaust gas treatment systems currently used in fabs cannot be effectively removed, resulting in the release of PFCs into the atmosphere, causing environmental pollution and promoting global warming. Although the total emissions of polyfluorocarbons are much lower than those of carbon dioxide (C02), their impact on the greenhouse effect is much greater than that of carbon dioxide, which in turn leads to greenhouse effect problems. The Kyoto Protocol has decided that industrial advanced countries should reduce the average annual emissions of six greenhouse gases, including carbon dioxide, to less than 5.2% of the 1990 average emissions between 2008 and 2012. Since the signing of the Kyoto Protocol will impact the domestic semiconductor manufacturing industry using fluorochemicals, a method and equipment for efficiently treating fluorochemicals is needed.
KanKen公司在美國專利第US 6,126,906號描述使用 兩段式濕式洗滌器與熱裂解及燃燒方式進行廢氣處理,廢 5 200920470 氣在通過第一段濕式洗滌器去除粉塵及酸性氣體後,進入 熱裂解反應器將PFC加以裂解,反應温度為600〜1200。(:, 熱源主要由燃燒液化石油氣(LPG)或液化天然氣(LNG)提 供,反應後之氣體再進入第二段洗滌塔或燃燒塔,將可燃 性氣體及熱烈解所產生之化合物加以去除。此系統優點是 可適用大多數製程且技術成熟度高,系統結構簡單,但缺 點是須提供大量LPG或LNG等燃料,增加操作成本,且 LPG或LNG等為易燃***性氣体,增加工安風險。U.S. Patent No. 6,126,906 to KanKen describes the use of a two-stage wet scrubber with thermal cracking and combustion for waste gas treatment. Waste 5 200920470 Gas enters heat after passing through the first wet scrubber to remove dust and acid gases. The cleavage reactor cleaves the PFC at a reaction temperature of 600 to 1200. (:, the heat source is mainly supplied by burning liquefied petroleum gas (LPG) or liquefied natural gas (LNG), and the reacted gas is then sent to the second stage washing tower or the combustion tower to remove the flammable gas and the compound produced by thermal decomposition. The advantage of this system is that it can be applied to most processes and has high technology maturity and simple system structure. However, it has the disadvantage of providing a large amount of fuel such as LPG or LNG, increasing operating cost, and LPG or LNG is a flammable explosive gas, which increases the safety risk. .
Hitachi公司在歐洲專利第EP1103297A1號描述一種主 要應用於處理钱刻製程廢氣之方法,其前段處理使用一含 有塑膠粒之固定床去除固體顆粒,另以水洗塔去除可溶性 氣體,處理過之氣體與空氣及水蒸氣混合後,再進入預熱 段進行預熱後再進入觸媒床,進行水解反應將PFC分解成 SO:、N〇2、(C〇2或CO)及HF,觸媒床反應温度設定為 400〜650°C。分解後之氣體再通過一吸收塔,將氣體中之 HF以驗液加以去除’吸收塔另配有一旋風(CyCi〇ne)集塵設 備以增加吸收效能。 EBARA公司之歐洲專利第EP1129775A1號與Hitachi 公司之歐洲專利第ΕΡ1103297ΑΓ號之專利流程概念接近, 但兩者使用之觸媒系統不同,且反應條件也不盡相同。歐 洲專利第EP1129775A1號是以H2作為觸媒再生之主要來 源’而歐洲專利第EP1103297A1號是以HsO作為觸媒再生 之試劑。此類處理系統優點為PFC破壞率可大於99%且工 作溫度低、省能源,但缺點是需考慮觸媒老化及更換觸媒 6 200920470 所需之費用。In the European Patent No. EP 1 103 297 A1, a method for the treatment of waste gas from a process is described in the prior art. The front stage treatment uses a fixed bed containing plastic pellets to remove solid particles, and a water wash tower to remove soluble gases, treated gas and air. After mixing with water vapor, it enters the preheating section for preheating and then enters the catalyst bed to carry out hydrolysis reaction to decompose PFC into SO:, N〇2, (C〇2 or CO) and HF, and the reaction bed temperature Set to 400~650 °C. The decomposed gas is passed through an absorption tower to remove the HF from the gas by the test solution. The absorption tower is additionally equipped with a cyclone (CyCi〇ne) dust collection device to increase the absorption efficiency. EBARA's European Patent No. EP1129775A1 is similar to the patent process concept of Hitachi's European Patent No. 1103297, but the catalyst systems used are different and the reaction conditions are different. European Patent No. EP1129775A1 is based on H2 as a main source of catalyst regeneration, and European Patent No. EP1103297A1 is a reagent for regeneration of HsO as a catalyst. The advantages of such a treatment system are that the PFC destruction rate can be greater than 99% and the working temperature is low and energy is saved, but the disadvantage is that the cost of catalyst aging and replacement of the catalyst 6 200920470 needs to be considered.
Showa Denko K.K.公司在美國專利第US 6,630,42l號 描述一種處理廢氣之方法,其主要使用之反應劑為乾式反 應劑,不適用於高溼度之反應狀態,因此在於前段及後 皆無需設立濕式洗滌塔’亦不需另外加入水蒸氣以促進水^ 解反應。在Showa Denko K.K.公司之專利中,由飯刻穿』牙。 釋放之氣體在通過一乾式酸性氣體吸附槽後,直接進人 PFC反應槽,反應溫度為400〜650°C,反應後之尾氣不含 Γ HF,可直接對外排放。此處理系統優點最大的優點在於安 全性的提高,因為不需使用可燃性氣體且尾氣無HF產生, 對於半導體廠的廠務維護具有正面之評價。另外,pFC破 壞率可大於99%且工作溫度低、省能源’但最大的缺點是 反應劑更換頻率較高,且無法適用於廢氣中粉塵含量較高 之製程,使其系統之適用性受到限制。一般乾式PFC去除 系統僅適用於含塵量相當低的蝕刻製程廢氣,無法適用於 含塵量南的化學氣相沉積(CVD)之薄膜製程。 k 【發明内容】 本發明一實施例提供一種廢氣處理裝置,包括一洗滌 單元、一連接洗滌單元之除濕單元及一用以去除含氟化合 物之乾式反應單元,連接該除濕單元。本發明一實施例提 供一種處理廢氣之方法,包括以下步驟:提供一包括含氟 化合物之廢氣,使用一洗滌單元處理廢氣,使用—除濕單 元處理洗滌單元處理過之廢氣,使用一乾式反應單元,處 7 200920470 理除濕單元處理過之廢氣。 【實施方式】 本發明提供一種含氟化合物廢氣之處理方法,以觸媒 分解法處理含氟化合物,特別可處理例如化學氣相沉積法 所排放出含有大量微粒且包含多氟碳化合物之廢氣。觸媒 分解法一般可分成濕式水解法及乾式反應法兩種方式。濕 式水解法包括前、後段洗滌塔,用以去除廢氣中之粉塵微 粒及氟化氫(HF),其觸媒為水解型觸媒,需在具有—定濕 度環境下操作。乾式反應系統使用乾式吸附反應劑去除廢 氣中之含氟化合物’由於其採用乾式反應,不利於^、、晨環 境下操作。進入含氟化合物(PFC)去除系統的廢氣中水氣含 量一般不可大於1 wt%,故現行之技術無法於乾式反應系 統中加設濕式洗滌器,以去除廢氣中的粉塵。 本發明之實施例主要是在使用乾式反應系統中增加一 除濕單元,當使用洗滌單元處理廢氣後,應用—除濕單元 處理洗蘇單元處理過之廢氣’以使廢氣進入乾式反應系統 反應有較佳的去除率(destruction removal efficiency, DRE)。第1圖揭示本發明一實施例廢氣之裝置及廢氣處理 之方法。如第1圖所示,首先將一半導體或平面顯示器用 之化學氣相沉積或蝕刻製程排出之廢氣1〇2導入一洗滌單 元104。本實施例廢氣102包括含氟化合物,例如全氟碳 化物(Per:^uorocarb〇ns)、虱鼠碳化物(hydrofluorocarbons)、 三氟化氮(NF3)或六氟化硫(SF6)。含氟化合物之濃度可為約 8 200920470 為0.01〜5mol%,含水率可約為0.1〜3wt%。化學氣相沉積 製程一般會產生相當大量的微粒(particle),造成廢氣102 中包含相當數量的微粒,本實施例採用洗滌單元1〇4(例如 喷霧塔、濕式旋風洗滌器、文式洗滌器或填充塔),去除廢 氣102中之微粒或氟化氫。 接著,使用一除霧單元106處理洗滌單元104處理過 之廢氣102,以去除廢氣102中的水滴。除霧單元106和 洗滌單元104間可以氣體管路連結,氣體管路可設置氣體 〔流量控制器,用以控制和監控氣體之流量(爲簡潔圖式中沒 有繪示氣體管路和氣體流量控制器)。後續使用一除濕單元 108處理除霧單元106處理過之廢氣102,降低廢氣102 之溼度。除霧單元106和除濕單元108間可以氣體管路連 結。除濕單元108可為一吸附裝置、壓縮裝置、冷卻裝置、 昇溫裝置或氣液直接接觸裝置,在一實施例中,除濕單元 108係為一除濕轉輪。 接下來,使用一用以去除含氟化合物之乾式反應單元 < 110,處理除濕單元108處理過之廢氣102。乾式反應單元 110和除濕單元108間可以氣體管路連結。在本實施例中, 乾式反應單元110包括乾式反應劑,例如氧化鈣、碳酸鈣、 碳酸鎂、沸石、三氧化二鋁或上述混合物,其中乾式反應 劑之三氧化二鋁的前驅物可為硝酸鋁、軟水鋁石 (boehmite)、擬薄水銘石(pseudoboehmite)或三氯化銘,請 注意本發明乾式反應劑之組成不限於此,詳細之乾式反應 劑成分請參考96年10月04日申請之中華民國專利申請號 9 200920470 第96137233號,其標題為含氟化合物氣體之處理方、、去A method for treating exhaust gas is described in U.S. Patent No. 6,630,42, the entire disclosure of which is incorporated herein by reference. The scrubber's also does not require additional water vapor to promote the water digestion reaction. In the patent of Showa Denko K.K., the teeth are worn by the teeth. The released gas passes through a dry acid gas adsorption tank and directly enters the PFC reaction tank. The reaction temperature is 400~650 °C, and the tail gas after the reaction does not contain ΓHF, which can be directly discharged to the outside. The advantage of this processing system is that the safety is improved because no flammable gas is required and the exhaust gas is free of HF, which is a positive evaluation of the factory maintenance of the semiconductor factory. In addition, the pFC destruction rate can be greater than 99% and the operating temperature is low, saving energy 'but the biggest disadvantage is that the reagent replacement frequency is high, and can not be applied to the process of high dust content in the exhaust gas, so that the applicability of the system is limited. . The general dry PFC removal system is only suitable for etching process waste gas with a relatively low dust content, and it is not suitable for the chemical vapor deposition (CVD) film process with dust content. According to an embodiment of the present invention, an exhaust gas treatment device includes a washing unit, a dehumidifying unit connected to the washing unit, and a dry reaction unit for removing the fluorine-containing compound, and the dehumidifying unit is connected. An embodiment of the present invention provides a method for treating exhaust gas, comprising the steps of: providing an exhaust gas comprising a fluorine-containing compound, treating the exhaust gas using a washing unit, treating the exhaust gas treated by the washing unit with a dehumidifying unit, using a dry reaction unit, Department 7 200920470 Dehumidification unit treated waste gas. [Embodiment] The present invention provides a method for treating a fluorine-containing compound exhaust gas, which is treated by a catalyst decomposition method, and particularly, for example, a chemical vapor deposition method for discharging an exhaust gas containing a large amount of fine particles and containing a polyfluorocarbon compound. The catalyst decomposition method can be generally divided into two methods: a wet hydrolysis method and a dry reaction method. The wet hydrolysis method includes a front and a rear stage washing tower for removing dust particles and hydrogen fluoride (HF) in the exhaust gas, and the catalyst is a hydrolysis type catalyst, and is operated under a constant humidity environment. The dry reaction system uses a dry adsorption reagent to remove the fluorine-containing compound in the exhaust gas. Because of its dry reaction, it is not suitable for operation in the morning and the environment. The moisture content of the exhaust gas entering the fluorine-containing compound (PFC) removal system is generally not more than 1 wt%, so the current technology cannot add a wet scrubber to the dry reaction system to remove dust from the exhaust gas. The embodiment of the present invention mainly adds a dehumidifying unit to the dry reaction system. When the exhaust unit is used to treat the exhaust gas, the dehumidifying unit is used to treat the exhaust gas treated by the washing unit to make the exhaust gas enter the dry reaction system. Destruction removal efficiency (DRE). Fig. 1 shows a device for exhaust gas and a method for treating exhaust gas according to an embodiment of the present invention. As shown in Fig. 1, first, a waste gas 1 〇 2 discharged from a chemical vapor deposition or etching process for a semiconductor or flat display is introduced into a washing unit 104. The exhaust gas 102 of the present embodiment includes a fluorine-containing compound such as perfluorocarbon (Per: ^uorocarb〇ns), hydrofluorocarbons, nitrogen trifluoride (NF3) or sulfur hexafluoride (SF6). The concentration of the fluorine-containing compound may be from 0.01 to 5 mol% of about 8 200920470, and the water content may be about 0.1 to 3 wt%. The chemical vapor deposition process generally produces a relatively large amount of particles, resulting in a significant amount of particulates in the exhaust gas 102. This embodiment employs a scrubbing unit 1〇4 (eg, a spray tower, a wet cyclone, a literary wash). Or a packed column) to remove particulates or hydrogen fluoride from the exhaust gas 102. Next, the exhaust gas 102 treated by the washing unit 104 is treated using a demisting unit 106 to remove water droplets in the exhaust gas 102. The demisting unit 106 and the washing unit 104 can be connected by a gas pipeline, and the gas pipeline can be provided with a gas [flow controller for controlling and monitoring the flow of the gas (the gas pipeline and the gas flow control are not shown in the simplified diagram). Device). The dehumidification unit 108 is subsequently used to treat the exhaust gas 102 treated by the defogging unit 106 to reduce the humidity of the exhaust gas 102. The demisting unit 106 and the dehumidifying unit 108 may be connected by a gas line. The dehumidifying unit 108 can be an adsorption device, a compression device, a cooling device, a temperature increasing device or a gas-liquid direct contact device. In one embodiment, the dehumidifying unit 108 is a dehumidifying rotor. Next, the exhaust gas 102 treated by the dehumidifying unit 108 is treated using a dry reaction unit <110 for removing the fluorine-containing compound. The dry reaction unit 110 and the dehumidifying unit 108 may be connected by a gas line. In the present embodiment, the dry reaction unit 110 includes a dry reactant such as calcium oxide, calcium carbonate, magnesium carbonate, zeolite, aluminum oxide or a mixture thereof, wherein the precursor of the aluminum oxide of the dry reactant may be nitric acid Aluminum, boehmite, pseudoboehmite or trichlorin, please note that the composition of the dry reactant of the present invention is not limited to this. For detailed dry reactant components, please refer to the application on October 4, 1996. Republic of China Patent Application No. 9 200920470 No. 96137233, entitled "Processing of Fluorinated Compound Gases, Going
後,排放處理過之部份廢氣112,如第1圖所示,& A 而經由 乾式反應單元110處理過的另一部份廢氣114,可乡τ<由 包括冷卻水裝置之熱交換器116降低溫度,再導弓丨至&嘴 轉輪108 ’供除濕轉輪108脫附使用。舉例來說,乾式= 應單元110處理過的廢氣114溫度約為250°C,可將其辨 由熱交換器116降温至約170°C,再供除濕轉輪1〇8脫= 使用,後續將脫附使用之部份廢氣114排出。 第2圖揭示本發明另一實施例廢氣之裝置及廢氣處王里 之方法。如第2圖所示,首先將一半導體或平面顯示器用 之化學氣相沉積或蝕刻製程排出之廢氣202導入_含除| 器206之洗滌單元204。廢氣202可為含氟化合物,例如 全氟碳化物(perfluorocarbons)、氫氟石炭化物 (hydrofluorocarbons)、三氟化氮(NF3)和/或六氟化碟(sp ) 後續,使用一除濕單元208處理含除霧器206之洗務單元 204處理過之廢氣202,降低廢氣202之溼度。除濕單元 208可為一吸附裝置、壓縮裝置、冷卻裝置、昇溫裝置或 氣液直接接觸裝置,在一實施例中,除濕單元2〇8係為— 除濕轉輪。請注意,本實施例各單元間以氣體管路相連接, 爲簡潔,以下不詳述其連接關係。 接下來,以一乾式反應單元210處理廢氣202。在使 用乾式反應單元210處理廢氣202前,先使廢氣2〇2經過 一熱交換器212,此熱交換器212係設計使乾式反應單元 210處理前之廢氣202a和乾式反應單元21〇處理後之廢氣 200920470 202b進行熱交換,以使乾式反應單元21〇處理後之廢氣 202b F牛低至較低之/jnL度,可供除游、轉輪Mg脫附使用,而 乾式反應單το 210處理前之廢氣2〇2a則升高至較高之溫 度。舉例來說,乾式反應單元210處理前之廢氣2〇2a溫度 約為50 C ,乾式反應單元210處理後的廢氣2〇2b溫度約 為250 C,藉由熱父換态212將處理前之廢氣2〇2a和處理 後之廢氣202b進行熱交換,使處理後之廢氣2〇沘降溫至 、’、勺170 C,再供除〉煞轉輪208脫附使用。根據此實施例熱 父換器212之設計和配置,熱交換器212可不需包含例如 冷卻水之冷卻裝置、以降低設備成本。 在此實施例中,乾式反應單元21〇包括乾式反應劑, 例如氧化鈣、碳酸鈣、碳酸鎂、沸石、三氧化二鋁或上述 5物其中乾式反應劑之三氧化二铭的前驅物可為頌酸 銘軟水链石(boehmite)、擬薄水|呂石(pSeud〇b〇ehinite)或 二氯化鋁。之後,排放處理過之部分廢氣2〇2c,將經由熱 父換益212降低溫度之另_部份廢氣2〇2(1導引至除濕單元 208 ’供除濕單元2〇8脫附使用。 以I提供一範例,比較未使用除濕單元(比較範例)和使 用除濕單元(實施範例)對於含氟化合物之去除率。 【比較範例】 ,提彳/、合有六氟化硫(SF6)之氣體,其中六氟化硫之濃 = ’且以含量5%之氧氣㈣和氮氣_乍為平 U組’乳體總流量為17 5L/min。接著,將含有六氣化硫 200920470 之氣體通過一濕式洗滌器,濕式洗滌器處理前之氣體溫度 為30°C ’相對濕度(RH)小於2%,濕式洗務器處理後之氣 體溫度2 9.9 C,相對濕度8 3 %。 後續’將氣體導入用以去除含氟化合物之乾式反應器 中進行處理。乾式反應器直徑為13公分,填充200克去除 含氟化合物之乾式反應劑,乾式反應劑之組成包括:沸石 及鹼土金屬化合物,且沸石和鹼土金屬化合物之重量比約 為1:20至4:6 ’其中鹼土金屬化合物例如為鎂、約、銷或 鋇之碳酸鹽,沸石之比表面積大於400m2/g,沸石之成分 可為Si02和A1203,且Si02和A1203之莫耳比為1〇:1 至100:1,乾式反應劑係為圓柱狀反應劑顆粒,直徑為 4mm,長度為4〜6mm,反應之溫度為650°C。經處理30 分鐘後,將含氟化合物反應器排放出之氣體以傅立葉變換 紅外光譜(FT-IR)進行分析,分析結果得到六氟化硫濃度為 88ppm,去除率(destruction removal efficiency,DRE)為 94.5%。 【實施範例】 提供一含有六氟化硫(SF6)之氣體,其中六氟化硫之濃 度為1600ppm,且以含量5%之氧氣和氮氣作為平衡氣體, 氣體總流量為17.5L/min。接著,將含有六氟化硫之氣體通 過一濕式洗滌器,濕式洗滌器處理前之氣體溫度為3(rc , 相對濕度(RH)小於2%,濕式洗務器處理後之氣體溫度29.9 °C,相對濕度83%。 200920470 將通過濕式洗滌器含有六氟化硫之氣體導入一除濕單 元,降低氣體溼度,除濕單元處理後之氣體溫度33.6°C, 相對溼度34%。 後續,將氣體引入用以去除含氟化合物之乾式反應器 中進行處理,其中乾式反應器直徑13公分,填充200克去 除含氟化合物之乾式反應劑,乾式反應劑之組成包括:沸 石及驗土金屬化合物,且沸石和驗土金屬化合物之重量比 約為1:20至4:6,其中驗土金屬化合物例如為鎂、妈、然 或鋇之碳酸鹽,沸石之比表面積大於400m2/g,沸石之成 分可為Si02和A1203,且Si02和A1203之莫耳比為10:1 至100:1,乾式反應劑係為圓柱狀反應劑顆粒,直徑為 4mm,長度為4〜6mm,反應溫度為650°C。經處理40分鐘 後,將含氟化合物反應器排放出之氣體以傅立葉變換紅外 光譜(FT-IR)進行分析,六氟化硫濃度為15.7ppm,去除率 (DRE)為 99%。 根據上述實施範例和比較範例實驗結果,當沒有使用 除濕單元降低氣體溼度時,其去除率(DRE)為94.5%,而使 用除濕單元降低氣體溼度時,其去除率(DRE)為99%,因 此本實施例使用除濕單元降低降低進入含氟化合物反應器 之氣體溼度,確可有效提高含氟化合物之去除率。 本發明之實施例所提的廢氣處理方法至少具有以下優 點:有效處理化學氣相沉積薄膜製程所排放之廢氣。化學 氣相沉積薄膜製程產生之廢氣一般包含較大量之微粒,需 經由洗滌單元去除微粒,但也因此廢氣中含有較高之水 13 200920470 氣,不適合以乾式含氟化合物去除系統進行去除,本發明 實施例使用洗滌單元去除廢氣中的微粒,在廢氣以乾式反 應單元處理前,使用除濕單元降低通過洗滌單元之廢氣溼 度,使廢氣可進入乾式含氟化合物去除單元進行含氟化合 物處理。因此,本發明實施例之廢氣處理方法,將乾式含 氟化合物去除系統,全面應用在處理蝕刻製程,以及化學 氣相沉積薄膜製程產生之廢氣。 以上提供之實施例係用以描述本發明不同之技術特 徵,但根據本發明之概念,其可包括或運用於更廣泛之技 術範圍。須注意的是,實施例僅用以揭示本發明製程、裝 置、組成、製造和使用之特定方法,並不用以限定本發明, 任何熟習此技藝者,在不脫離本發明之精神和範圍内,當 可作些許之更動與潤飾。因此,本發明之保護範圍,當視 後附之申請專利範圍所界定者為準。 200920470 【圖式簡單說明】 第1圖揭示本發明一實施例廢氣之裝置及廢氣處理之 方法。 第2圖揭示本發明另一實施例廢氣之裝置及廢氣處理 之方法。 【主要元件符號說明】 102〜廢氣; ι· 104〜洗縣:單元; 106〜除霧單元; 108〜除濕單元; 110〜乾式反應單元; 112〜處理後之廢氣; 114〜部份廢氣; 116〜熱交換器; 202〜廢氣; 1 202a〜處理前之廢氣; 202b〜處理後之廢氣; 202c〜部分廢氣; 202d〜部份廢氣; 204〜洗滌單元; 206〜除霧器; 208〜除濕單元; 210〜乾式反應單元; 15 200920470 212〜熱交換器。 \ 16Thereafter, the treated exhaust gas 112 is discharged, as shown in FIG. 1, another portion of the exhaust gas 114 treated by the dry reaction unit 110, and the heat exchanger including the cooling water device is 116 lowers the temperature and redirects the bow to the 'mouth wheel 108' for desorption of the dehumidification wheel 108. For example, the dry type = the temperature of the exhaust gas 114 treated by the unit 110 is about 250 ° C, which can be cooled by the heat exchanger 116 to about 170 ° C, and then used by the dehumidification rotor 1 〇 8 = use, followed by A part of the exhaust gas 114 used for desorption is discharged. Fig. 2 is a view showing a method of exhausting a gas and a method of exhausting gas in another embodiment of the present invention. As shown in Fig. 2, the exhaust gas 202 discharged from the chemical vapor deposition or etching process for a semiconductor or flat panel display is first introduced into the cleaning unit 204 of the separator 206. Exhaust gas 202 can be a fluorochemical, such as perfluorocarbons, hydrofluorocarbons, nitrogen trifluoride (NF3), and/or hexafluoride (sp), followed by a dehumidification unit 208. The exhaust gas 202 treated by the washing unit 204 including the demister 206 reduces the humidity of the exhaust gas 202. The dehumidifying unit 208 can be an adsorption device, a compression device, a cooling device, a temperature increasing device or a gas-liquid direct contact device. In one embodiment, the dehumidifying unit 2 is a dehumidifying rotor. Please note that the units in this embodiment are connected by a gas pipeline. For the sake of brevity, the connection relationship will not be described in detail below. Next, the exhaust gas 202 is treated with a dry reaction unit 210. Before the exhaust gas 202 is treated by the dry reaction unit 210, the exhaust gas 2〇2 is passed through a heat exchanger 212 designed to treat the exhaust gas 202a and the dry reaction unit 21 after the dry reaction unit 210 is processed. Exhaust gas 200920470 202b is heat exchanged so that the exhaust gas 202b F after treatment of the dry reaction unit 21 is low to a lower /jnL degree, and can be used for removing and rotating the Mg, while the dry reaction is το 210 before treatment. The exhaust gas 2〇2a is raised to a higher temperature. For example, the temperature of the exhaust gas 2〇2a before the dry reaction unit 210 is about 50 C, and the temperature of the exhaust gas 2〇2b after the dry reaction unit 210 is about 250 C, and the exhaust gas before the treatment by the hot parent state 212 2〇2a and the treated exhaust gas 202b are subjected to heat exchange, and the treated exhaust gas 2〇沘 is cooled to ', spoon 170 C, and then supplied and removed> 煞 wheel 208 is desorbed. According to the design and configuration of the thermal master 212 of this embodiment, the heat exchanger 212 may not need to include a cooling device such as cooling water to reduce equipment costs. In this embodiment, the dry reaction unit 21A includes a dry reactant such as calcium oxide, calcium carbonate, magnesium carbonate, zeolite, aluminum oxide or the above five substances, wherein the precursor of the dry reactant of the trioxide is颂酸铭软水石石 (boehmite), 拟薄水|吕石(pSeud〇b〇ehinite) or aluminum dichloride. After that, part of the treated exhaust gas 2〇2c is discharged, and the other part of the exhaust gas 2〇2 (1 is guided to the dehumidifying unit 208' for dehumidifying unit 2〇8 to be desorbed by the hot parent exchange benefit 212. I provides an example comparing the removal rate of a fluorine-containing compound without using a dehumidifying unit (comparative example) and using a dehumidifying unit (example). [Comparative example], a gas with sulphur hexafluoride (SF6) , wherein the concentration of sulphur hexafluoride = 'and the content of 5% oxygen (four) and nitrogen _ 乍 as the flat U group 'total total flow of the emulsion is 17 5 L / min. Then, the gas containing six gasified sulfur 200920470 through a Wet scrubber, the temperature of the gas before the wet scrubber treatment is 30 ° C 'relative humidity (RH) is less than 2%, the gas temperature after the wet scrubber treatment is 2 9.9 C, the relative humidity is 83 %. The gas is introduced into a dry reactor for removing fluorine-containing compounds. The dry reactor has a diameter of 13 cm and is filled with 200 g of a dry reactant for removing a fluorine-containing compound. The composition of the dry reactant includes: zeolite and an alkaline earth metal compound. And the combination of zeolite and alkaline earth metal The weight ratio of the material is about 1:20 to 4:6 ' wherein the alkaline earth metal compound is, for example, a carbonate of magnesium, about, pin or bismuth, the specific surface area of the zeolite is more than 400 m 2 /g, and the composition of the zeolite may be SiO 2 and A 120 3 , and The molar ratio of Si02 to A1203 is 1〇:1 to 100:1, and the dry reactant is a cylindrical reactant particle having a diameter of 4 mm, a length of 4 to 6 mm, and a reaction temperature of 650 ° C. After treatment for 30 minutes Thereafter, the gas discharged from the fluorochemical reactor was analyzed by Fourier transform infrared spectroscopy (FT-IR), and the analysis result showed that the sulfur hexafluoride concentration was 88 ppm, and the removal removal efficiency (DRE) was 94.5%. EXAMPLES A gas containing sulfur hexafluoride (SF6) was provided, wherein the concentration of sulfur hexafluoride was 1600 ppm, and the total gas flow rate was 17.5 L/min with a content of 5% oxygen and nitrogen as a balance gas. The gas containing sulfur hexafluoride is passed through a wet scrubber. The temperature of the gas before the wet scrubber treatment is 3 (rc, the relative humidity (RH) is less than 2%, and the gas temperature after the wet scrubber treatment is 29.9 °. C, relative humidity 83%. 200920470 will pass wet The gas containing sulfur hexafluoride in the scrubber is introduced into a dehumidifying unit to reduce the humidity of the gas. The temperature of the gas after the dehumidifying unit treatment is 33.6 ° C, and the relative humidity is 34%. Subsequently, the gas is introduced into the dry reactor for removing the fluorine-containing compound. The treatment is carried out, wherein the dry reactor has a diameter of 13 cm and is filled with 200 g of a dry reactant for removing the fluorine-containing compound. The composition of the dry reactant comprises: zeolite and a soil metal compound, and the weight ratio of the zeolite to the soil metal compound is about 1 : 20 to 4:6, wherein the soil-measuring metal compound is, for example, a carbonate of magnesium, mum, or yttrium, the specific surface area of the zeolite is greater than 400 m 2 /g, the composition of the zeolite may be SiO 2 and A 1203, and the Mo 2 and A 120 3 are Mo The ratio of 10:1 to 100:1 is that the dry reactant is a cylindrical reactant particle having a diameter of 4 mm, a length of 4 to 6 mm, and a reaction temperature of 650 °C. After 40 minutes of treatment, the gas discharged from the fluorochemical reactor was analyzed by Fourier transform infrared spectroscopy (FT-IR), and the sulfur hexafluoride concentration was 15.7 ppm, and the removal rate (DRE) was 99%. According to the above-described embodiment and comparative example experimental results, when the dehumidifying unit is not used to reduce the gas humidity, the removal rate (DRE) is 94.5%, and when the dehumidifying unit is used to reduce the gas humidity, the removal rate (DRE) is 99%, In this embodiment, the dehumidification unit is used to reduce the humidity of the gas entering the fluorine-containing compound reactor, and the removal rate of the fluorine-containing compound can be effectively improved. The exhaust gas treatment method of the embodiment of the present invention has at least the following advantages: effective treatment of exhaust gas discharged from the chemical vapor deposition film process. The exhaust gas generated by the chemical vapor deposition film process generally contains a relatively large amount of particles, and the particles need to be removed through the washing unit, but therefore the exhaust gas contains higher water 13 200920470 gas, which is not suitable for removal by a dry fluorine-containing compound removal system, the present invention The embodiment uses a washing unit to remove particulates in the exhaust gas, and uses the dehumidifying unit to reduce the humidity of the exhaust gas passing through the washing unit before the exhaust gas is treated by the dry reaction unit, so that the exhaust gas can enter the dry fluorine-containing compound removing unit for fluorine-containing compound treatment. Therefore, in the exhaust gas treatment method of the embodiment of the present invention, the dry fluorine-containing compound removal system is fully applied to the treatment of the etching process and the exhaust gas generated by the chemical vapor deposition film process. The embodiments provided above are intended to describe various technical features of the invention, but may be included or applied to a broader range of technical aspects in accordance with the teachings of the invention. It is to be understood that the embodiments are not intended to limit the invention, and the invention is not limited to the scope of the invention. When you can make some changes and retouch. Therefore, the scope of the invention is defined by the scope of the appended claims. 200920470 [Simplified description of the drawings] Fig. 1 discloses a device for exhaust gas and a method for treating exhaust gas according to an embodiment of the present invention. Fig. 2 is a view showing a device for exhaust gas and a method for treating exhaust gas according to another embodiment of the present invention. [Description of main components] 102~Exhaust gas; ι·104~ Washing county: unit; 106~ Defogging unit; 108~Dehumidifying unit; 110~ Dry reaction unit; 112~ Treated exhaust gas; 114~ Partial exhaust gas; ~ heat exchanger; 202~ exhaust gas; 1 202a~ exhaust gas before treatment; 202b~ treated exhaust gas; 202c~ part of exhaust gas; 202d~ part of exhaust gas; 204~ washing unit; 206~ demister; 208~ dehumidifying unit 210~ dry reaction unit; 15 200920470 212~ heat exchanger. \ 16