523491 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（f ) [發明的詳細說明] [發明所屬的技術領域] 本發明僳有關含氟鹵素的排氣之處理方法、處理劑及 處理裝置，更詳細地説，乃是有關在製造半導體或薄膜 電晶體液晶顯示元件等製程中波排出的含有氟化鹵素氣 體的排氣，有效率且安全地加以處理的含氟化鹵素之排 氣的處理方法、處理劑及處理裝置。 [習知技術] 以半導體製造而言，薄膜形成製程在薄膜電晶體液晶 顯示元件製造等中心領域偽相當普遍，薄膜形成裝置的 乾洗氣體大量被使用著。在這些乾洗氣體中，氟化鹵素 氣體由於得以在非電漿條件下使用和並無地球溫室效應 ，乃日益普及。 但是，氟化鹵素氣體因毒性和危險性高，故必須使含 氟化鹵素的排氣被排出而無害化。其各種處理方法提案 如下： 在日本特開平3-27217公報掲示著用鹸和亞硫酸鹽或 重亞硫酸鹽的混合水溶液洗淨的濕式處理方法，和使固 形中和劑和固形亞硫酸鹽或重亞硫酸鹽接觸的乾式處理 方法，特開平3 - 2 2 9 6 1 8號公報乃刊載了以常溫使其與鐵 的氧化物接觸的乾式處理方法，及以常溫使其與鐵氧化 物接觸後，再和鹼劑接觸的乾式處理方法。 又在日本特開平4-94723號公報掲示著使固體狀鹼及 吸附劑接觸的乾式處理方法，在持開平6-7637號公報即 本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---------線赢 523491 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（> ) 刊載著使鹼石灰擔負銅（II)化合物所構成的淨化劑接觸 之乾式處理方法。 此外，使氫氧化鈣和氫氫化鉀的混合物反應，而作為 固體鹵化物使其固定化的乾式處理方法（特開平8-215538 號公報）或使氫氧化鈣、氫氧化鈉及氫氧化钾3種混合 物反應，作為固定鹵化物使其固定化的乾式處理方法（待 開平8-215539號公報）等被公開掲示。 更在持開平9 - 2 3 4 3 3 6號公報掲示著，使其與一種在以 氧化銅（II)及氧化錳（IV)為主成分的金羼氧化物添加硫 代硫酸鈉而成的淨化劑接觸的乾式處理方法。 [發明擬解決的課題] 但是，上述所掲示的這些氟化鹵素氣體的處理方法之 濕式處理方法，在處理後必須加以廢水處理，不僅僅會 使裝置複雜及大型化，並有需要鉅額費用設備及保養上 的問題。 另方面，就乾式處理方法而言，以鹼石灰（氫氣化鈣 和氫氣化鈉的混合物）、氫氣化鈣、氫氧化鈉、氫氧化 鉀等固體驗接觸的乾式處理方法，傜因處理反應的發熱 量大而危險性高，又且氟化鹵素和這些固體鹸反應而生 成水，則該固體鹼溶解或潮解，使得填充有處理劑的處 理筒閉塞而具有危險性，更且，當在固體鹸為乾燥情況 時，會有處理能力大為降低等問題。 而且，使其與亞硫酸鹽或重亞硫酸鹽或鐵、錳及銅氧 化物接觸的_方结，則有單位體積處理劑之處理能力小的 本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) 1T---------. 523491 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（々） 問題。 從而，本發明擬解決的課題傺在於提供一種單位體積 處理能力優越、發熱量小而使因水之生成的處理筒閉塞 的危險性少而安全性高之處理劑，更在其處理劑為乾燥 狀況時也不會降低其處理含氟化鹵素的排氣之能力的處 理方法，處理劑及處理裝置者。 [為解決課題的手段] 本發明人等為了解決上述課題，屢經刻意檢討而發現 :鹼土類金屬的磺酸鹽得以選擇性地和有效率地與氟化 鹵素的氟成分反應，如此則反應時發熱量小又不會産生 水，接著，藉由鹼基金屬磺酸鹽使氟化鹵素和鹼土類金 颶的碩酸鹽之反應而遊離的鹵素，得以有效率地加以處 理。 亦即，發現以金颶化合物處理含氟化鹵素的排氣藉使 其成為金屬氟化物及金屬鹵化物而固定之乾式處理法上 ，若將氟成分和鹵素成分同時反應處理之情況則發熱量 非常大，但將氟成分和鹵素成分分別與個別的反應處理 劑接觸而各自加以處理者，可抑制個別反應處理時的發 熱，且可提高其單位體積的反應處理劑之處理能力。更 發現了，在具有雙，重筒構造的處理裝置之内筒，填充反 應處理時發熱量多的氟成分之反應處理劑，外筒镇充發 熱量少的鹵素成分之反應處理劑，接著含氟化鹵素的排 氣自内筒流通到外筒，因抑制了由發熱所引起的影響， 而高效率且安全地處理含氟化鹵素的排氣，終於完成了 -5- 本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* ^23491 A7 ____2Z___ 五、發明說明（4 ) 本發明之開發。 據日本特開平3 - 2 2 9 6 1 8號公報所掲示者，首先使含有 ^氟化氛的氣體與第一鐵的氣化物接觸，使排氣成分成 為鐵的氟化物及氛化物而固定之，接著，以鹼劑去除所 産生的氣體狀氟化物或氯^物副産物之方法，又在特開 平4- 9 4 7 2 3號公報掲示著，使含有三氟化氯的氣體和固 體狀鹼劑接觸，使大部分的氟、氣進行固定化處理之後 ，再以氯氣吸收劑吸收並除去該未處理的極少氣之方法 。但是，分別將三氟化氣等的氟化鹵素的氟成分和鹵素 成分，個別的與反應處理劑選擇性地反應，使成為金屬 氟化物或金屬鹵化物而固定化的方法，傺為從未被掲示 的完全新穎的方法。 亦即，本發明俗提供下列（1)〜U3)所示的方法者。 (1) 一種含氟化鹵素的排氣之處理方法，其特徽為首 先使氟化鹵素與氟成分的反應處理劑接觸，接著，使其 與齒素成分的反應處理劑接觸者。 (2) 如上述第1項所記載之含氟化鹵素約排氣之處理 方法，其中前逑氟成分的反應處理劑乃含有驗土類金屬 (請先閱讀背面之注意事項再填寫本頁)523491 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (f) [Detailed description of the invention] [Technical field to which the invention belongs] The present invention relates to a method, a treatment agent and a treatment agent for fluorine-containing halogen-containing exhaust gas. The processing device is, in more detail, a halogen-fluoride-containing exhaust gas that is efficiently and safely processed by the exhaust gas containing halogen-fluoride gas emitted during a process such as manufacturing a semiconductor or a thin-film transistor liquid crystal display element. Gas processing method, processing agent and processing device. [Conventional Technology] As far as semiconductor manufacturing is concerned, thin film forming processes are quite common in central areas such as the manufacture of thin film transistor liquid crystal display elements, and a large amount of dry cleaning gas is used in thin film forming apparatuses. Among these dry-cleaning gases, halogen fluoride gas has become increasingly popular because it can be used under non-plasma conditions and has no global warming effect. However, since halogen fluoride gas is highly toxic and dangerous, exhaust gas containing halogen fluoride must be discharged without harming it. Various treatment methods are proposed as follows: Japanese Patent Application Laid-Open No. 3-27217 discloses a wet treatment method of washing with a mixed aqueous solution of gadolinium and sulfite or bisulfite, and a solid neutralizer and solid sulfite. Or bisulfite contact dry treatment method, Japanese Patent Application Laid-Open No. 3-2 2 9 6 1 8 discloses a dry treatment method in which it is brought into contact with iron oxides at room temperature, and it is made into contact with iron oxides at room temperature. After contacting, dry treatment method of contacting with alkali agent. In Japanese Patent Application Laid-Open No. 4-94723, a dry treatment method for bringing a solid alkali and an adsorbent into contact is shown. In Japanese Patent Application Laid-Open No. 6-7637, the Chinese paper standard (CNS) A4 (210 X 297) is applied to this paper standard. (Mm) (Please read the notes on the back before filling this page) Order --------- Online Win 523491 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (>) Publication A dry treatment method for contacting a soda lime with a purifying agent composed of a copper (II) compound. In addition, a dry treatment method in which a mixture of calcium hydroxide and potassium hydride is reacted and immobilized as a solid halide (Japanese Patent Application Laid-Open No. 8-215538) or calcium hydroxide, sodium hydroxide, and potassium hydroxide 3 This type of mixture is disclosed as a dry treatment method (to be published in Japanese Unexamined Publication No. 8-215539) and the like in which a halide is immobilized. In addition, it is disclosed in Hokkaikai 9-2 3 4 3 3 6 that it is made by adding sodium thiosulfate to gold tin oxide containing copper (II) oxide and manganese (IV) oxide as a main component. Dry treatment method for cleaning agent contact. [Problems to be Solved by the Invention] However, the wet treatment methods of the above-mentioned treatment methods of the halogenated halogen fluoride gas must be treated with waste water after the treatment, which not only complicates and enlarges the device, but also requires huge costs. Equipment and maintenance problems. On the other hand, in terms of dry treatment methods, dry treatment methods such as soda lime (mixture of calcium hydride and sodium hydride), calcium hydride, sodium hydroxide, potassium hydroxide, etc., are exposed to solid contact. The calorific value is large and dangerous, and the halogen fluoride reacts with these solid rhenium to form water. The solid base dissolves or deliquesces, which makes the treatment cylinder filled with the treatment agent occluded and dangerous. Moreover, When it is dry, there is a problem that the processing capacity is greatly reduced. In addition, the square junction that makes it in contact with sulfite or bisulfite or iron, manganese and copper oxides has a small processing capacity per unit volume of the treatment agent. This paper standard is applicable to China National Standard (CNS) A4 specifications. (210 X 297 mm) (Please read the precautions on the back before filling out this page) 1T ---------. 523491 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (々 ) Problem. Therefore, the problem to be solved by the present invention is to provide a treatment agent with excellent processing capacity per unit volume, low heat generation, and low risk of occlusion of the treatment cylinder due to water generation, and high safety, and the treatment agent is dry. Treatment methods, treatment agents, and treatment devices that do not reduce their ability to handle exhaust gas containing halogen fluoride under conditions. [Means for solving the problem] In order to solve the above-mentioned problems, the present inventors have repeatedly deliberately reviewed and found that the sulfonates of alkaline earth metals can selectively and efficiently react with the fluorine component of halogen fluoride, and thus react When the calorific value is small and water is not generated, the free halogen can be efficiently treated by reacting the halogenated fluorinated halogen and the alkaline earth gold salt with the base metal sulfonate. In other words, it was found that in the dry processing method in which the fluorinated halogen-containing exhaust gas is treated with a golden hurricane compound to become a metal fluoride and a metal halide, heat is generated if the fluorine component and the halogen component are simultaneously reacted and treated. It is very large, but if a fluorine component and a halogen component are brought into contact with an individual reaction treatment agent and treated separately, heat generation during the individual reaction treatment can be suppressed, and the processing capacity of the reaction treatment agent per unit volume can be improved. Furthermore, it was found that the inner tube of the processing device having a double and heavy tube structure was filled with a reaction treatment agent containing a fluorine component that generates a large amount of heat during the reaction process, and an outer tube was filled with a reaction agent containing a halogen component that has a small amount of heat, and then contained The exhaust gas of halogen fluoride flows from the inner cylinder to the outer cylinder. Because the influence caused by heat is suppressed, the exhaust gas containing halogen fluoride is processed efficiently and safely, and finally completed. -5- This paper is applicable to China National Standard (CNS) A4 Specification (210 X 297 mm) (Please read the precautions on the back before filling this page) -------- Order --------- Line * ^ 23491 A7 ____2Z___ 5. Description of the invention (4) Development of the invention. According to Japanese Patent Application Laid-Open No. 3-2 2 9 6 1 8, first, a gas containing a fluorinated atmosphere is brought into contact with the vapor of the first iron, and the exhaust gas component is fixed to the fluoride and the atmosphere of iron. Then, a method for removing the generated gaseous fluoride or chlorine by-products with an alkaline agent is disclosed in Japanese Patent Application Laid-Open No. 4- 9 4 7 2 3 to make a gas containing chlorine trifluoride and a solid After the alkali agent is contacted, most of the fluorine and gas are immobilized, and then the untreated little gas is absorbed and removed by a chlorine gas absorbent. However, the method of separately reacting the fluorine component and halogen component of a fluorinated halogen such as trifluorinated gas with a reaction treatment agent individually to immobilize it as a metal fluoride or a metal halide has never been done before. A completely novel method that has been shown. That is, the present invention provides the following methods (1) to U3). (1) A treatment method for exhaust gas containing halogen fluoride. The special emblem is the person who first contacts the halogen fluoride with the reaction treatment agent of the fluorine component, and then contacts the halogen treatment reaction agent with the tooth treatment component. (2) The method for treating exhaust gas containing fluorinated halogens as described in item 1 above, in which the reaction treatment agent of the former fluorine component contains soil inspection metals (please read the precautions on the back before filling this page)
Li 訂---------生 經濟部智慧財產局員工消費合作社印製 屬第述 金u ® Π 述 ΐ ih_ 4 SIOJ其 酸5 ， 磺(3法 的方 氫項鹵 者 物 化 氧 mn 理 處 之 氣 排 的 素 鹵 化 氟 含 之 钱 Hi 記 所 的 屬 金 鹼 含 包 乃 劑 m 二 理 處 應 反 的 分 成 素 // βε 夕 ¾、 鹽)-内 酸(4有 磺 具 的 分 成 氟 充 镇 筒 内 置 裝 ml 理 處 的者㈡造 ® 素P0 0 0 酸：重 法 方 m: 理 處 之 氣 排 的 素 鹵 化 在 為 徵 特 其 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 523491 經濟部智慧財產局員工消費合作社印製 A7 B7_ 五、發明說明U ) 反應處理劑，於外筒填充鹵素成分的反應處理劑，且將 含氟化鹵素的排氣供應給内筒，使其依自内筒以至外筒 的順序流通後，再從外筒排出者。 (5) —種上述第1項所記載的含氟化鹵素的排氣之處 理方法所使用的氟成分之反應處理劑，其特徽為；含有 鹼土類金屬的碩酸鹽和金屬氫氧化物者。 (6) 如上述第5項所記載的氟成分之反應處理劑，其 中鹼土類金靥的磺酸鹽為磺酸鈣及/或碩酸鎂，金颶氫 氣化物係為自氫氣化鈣，氫氧化鈉，氫氫化鉀，氫氧化 鋁所選擇的一種或兩種。 (7) 如上逑第5項或第6項所記載的氟成分之反應處 理劑，其中鹼土類金屬的碩酸鹽和金屬氫氧化物含有比 率，以重量比為1 : 1〜9 9 : 1。 (8) 如上述第1項所記載之含氟化鹵素的排氣之處理 方法所使用的鹵素成分之反應處理劑，其特徽為；含有 鹼金屬的碩酸鹽及/或碩酸氫鹽者。 (9) 如上述第8項所記載之鹵素成分的反應處理劑， 其中鹼金屬碩酸鹽為磺酸鈉及/或碩酸鉀，而鹼金屬的 碩酸氫鹽即為磺酸氫鈉及/或碩酸氫鉀。 (10) 如上述第8項或第9項所記載之鹵素成分的反應 處理劑，其中鹼金屬碩酸鹽及/或磺酸氫鹽的含有率為 6 0重量％以上者。 (11) 一種含氟化鹵素的排氣之處理劑，其持徽為乃是 由上述（5)〜（7)中任何一項所記載的氟成分的反應處理 本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Li Order --------- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Health and Economics, which is the first gold u ® Π ΐ ΐ ih_ 4 SIOJ, its acid 5, sulphur (3 way hydrogen hydrogen halogenated person physical oxygen mn The gas exhausted from the halogens of the halogens and the halogens contained in the hi. The Hi-based metallurgical base contains the agent m. The secondary ingredients should be divided into the primes // βε (even, salt) -endoic acid (4 with sulfur) Divided into a fluorine-filled ball cylinder with a built-in ml processing unit. Made of P0 0 0 Acid: Gravimetric method m: The halogenation of the exhaust gas of the processing unit is subject to the Chinese National Standard (CNS) A4. Specifications (210 X 297 mm) 523491 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7_ V. Description of the invention U) The reaction treatment agent is filled with a halogen-containing reaction treatment agent in the outer cylinder, The gas is supplied to the inner cylinder so that it circulates in the order from the inner cylinder to the outer cylinder, and then discharged from the outer cylinder. (5) A kind of reaction treatment agent for fluorine component used in the method for treating halogen-containing fluorinated exhaust gas described in the above item 1, its special emblem is: auspicious salt and metal hydroxide containing alkaline earth metals By. (6) The reaction treatment agent for fluorine component as described in the above item 5, wherein the sulfonate salt of alkaline earth metal dysprosium is calcium sulfonate and / or magnesium sulfonate, and the Golden Hurricane Hydrogenate is self-calcium hydride, hydrogen Sodium oxide, potassium hydride, and aluminum hydroxide are one or two. (7) The reaction treatment agent for fluorine component according to item 5 or item 6 above, wherein the content ratio of the alkaline earth metal's sulphate and metal hydroxide is 1: 1 to 9 9: 1 by weight . (8) The special treatment of the halogen component reaction treatment agent used in the method for treating fluorinated halogen-containing exhaust gas as described in the above item 1, is a master acid salt and / or a hydrogen acid salt containing an alkali metal By. (9) The reaction treatment agent for the halogen component as described in the above item 8, wherein the alkali metal master salt is sodium sulfonate and / or potassium master acid, and the alkali metal hydrogen salt is sodium hydrogen sulfonate and / Or potassium hydrogen sulphate. (10) The reaction treatment agent for a halogen component as described in the above item 8 or 9, wherein the content rate of the alkali metal master salt and / or hydrogen sulfonate is 60% by weight or more. (11) A treatment agent for exhaust gas containing halogen fluoride, the emblem of which is treated by the reaction of the fluorine component described in any one of the above (5) to (7) CNS) A4 size (210 X 297 mm) (Please read the precautions on the back before filling this page) Order --------- Line 1
五、發明說明u ) 翔1和上述（8)〜（1Q)項中任何一項所記載的鹵素成分之 反應處理劑所構成者。 (12) 一種含氟化鹵素的排氣之處理裝置，其特擻為具 有雙重筒構造，在内筒容納氟成分的反應處理劑，外筒 容納鹵素成分的反應處理劑，另外具有將排氣導入内筒 的入口；自内筒至外筒的排氣之通路；和將處理後之排 氣從外筒排出於外的出口者。 (13) 如上逑第（12)項所記載的含氟化鹵素的排氣之處 理裝置，其中内筒的氟成分處理劑和外筒的鹵素成分處 理劑之填充量比，以體積比即為1:0.5〜1:3者。 [發明的實施形態] 作為本發明的排氣處理方法、處理劑及處理對象的氟 化鹵素像為含氟鹵素間化合物，例如以C1F, C1F3， ClFs形態所表示的氟化氯，以BrF, BrF3，BrF5形態 所表示的氟化溴，以I F 3，I F 5 , I F 7形態所表示的氟 化碘。本發明在製造半導體或薄膜電晶體液晶顯示元件 等領域上，薄膜形成裝置的乾洗所使用的，尤其對含有 三氟化氣等和三氟化溴等氟化溴類的排氣處理，最可適 合被使用。 以下雖擬就本發明加予說明，在此例舉氟化齒素之三 氟化氯為代表例舉而就含氟化鹵素的排氣之處理方法、 處理劑及處理裝置加予説明。 從來，作為將三氟化氛等氟化鹵素之氟成分和鹵素成 分同時處理的尽應處理劑，使用了鹼石灰（氫氣化•鈴和 氫氫化鈉的混合物），氫氧化鈣等固體鹼。 ~ 8 - 本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---------％ 經濟部智慧財產局員工消費合作社印製 523491 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（7) 用氫氫化鈣作為固體鹸使其與三氟化氛反應的場合， 其相當於一摩爾單位三氟化氣的反應熱偽如下式； C1F 3 +2Ca(0H) 2 — 3/2CaF2 +l/2CaCl 2 +2H 2 〇 + 〇 2 ..,575kJ/»ol 如上述氫氧化鈣的金颶氫氧化物之反應處理，雖有可 同時處理氟化鹵素的氟成分和_素成分的優點，但反應 處理時其發熱大，例如三氟化氣之場合，相當於其1摩 爾單位生成2摩爾的水而發生處理劑溶解、潮解而使得 處理筒閉塞等問題而危險，於反應處理劑乾燥的場合， 就有其處理能力因而大大降低等問題。 一方面，若按照本發明者可以使用鹸土類金颶的磺酸 鹽和金屬氫氣化物作為氟化鹵素的氟成分之反應處理劑 ，且可使用鹼金屬的碩酸鹽及/或磺酸氫鹽作為氟化齒 素的鹵素成分之反應處理劑。 使用鹼土類金屬的碩酸鹽將氟化鹵素加以反應處理的 場合，可只使氟化鹵素中的氟成分以選擇性地反應而加 以固定化，且有在反應處理時發熱少，不生成水的優點。 作為三氟化氣的氟成分之反應處理劑，例如使用碩酸 鈣的場合，和1摩爾單位三氟化氯反應的反應熱，如下 式。 C 1 F 3 +3/2CaC0 3 3 / 2 C a F 2 + 1 /2 C 1 2 +3/2C 0 2 + 3 / 4 0 2 .....445kJ/ffl〇l 亦即，使用磺酸鈣而將三氟化氛的氟成分加以反應處 理時的反應熱，較諸使用氫氧化鈣而將三氟化氯的氟成 分同時加以反應處理的場合，偽約小130KJ/mol。 本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) --------IT---------^一 經濟部智慧財產局員工消費合作社印製 523491 A7 B7_ 五、發明說明（〗） 在此，因鹼土類金屬的碩酸鹽和氟化鹵素的反應而遊 離的鹵素，向來係以過去一直使用之活性磺或沸石等吸 附劑而吸附之，但是，經吸附鹵素之處理筒因排除脫附 氣體而危險，使用活性碩時也有和氟化鹵素反應而燃燒 ，爆炸等危險問題，故使用活性碩或沸石等吸附劑的方 法，不太理想。 從而，按照本發明遊離的齒素最好採用鹸金屬的磺酸 鹽及/或碩酸氫鹽加以反應處理，使成為鹼金屬的鹵化 物，使固定化為宜。例如，採用磺酸鈉的反應作為氯成 分的反應處理劑之場合時，相當於1摩爾三氟化氯之氛 當量的反應熱，即如下式： 1/2C1 2 +l/2Na 2 CO 3 NaCl + l/ 2C02 + 1 / 4 0 2 .....43kJ/ffl〇l 亦即，得知了使用磺酸鈉將三氟化氣的氟成分加以反 應處理時的反應熱，較諸於將三氟化氣的氟成分加以反 應處理時的反應熱僳為非常小。 而且，藉以上述鹼金屬的碩酸鹽及/或碩酸氫鹽對氟 化鹵素的鹵素成分之反應處理，再添加適量的水，就可 提髙與鹵素成分的反應性，而提高處理劑按每一單位體 積之處理能力。但是，要是添加必要以上的水者，恐怕 會在與鹵素成分的反應之際，因水的遊離使得反應處理 劑因潮解而阻塞反應理筒。 藉添加水分於以鹼金屬的磺酸鹽及/或碩酸氫鹽處理 氟化鹵素中_鹵素成分的反應處理效果，例如使用硪酸鈉 處理三氟化氯中氛成分之反應具有觸媒效果如下式推定 -10- 本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--------- 經濟部智慧財產局員工消費合作社印製 523491 A7 B7_ 五、發明說明（？） 反應式：5. Description of the invention u) Xiang 1 and the reaction treatment agent of the halogen component described in any one of the items (8) to (1Q) above. (12) A processing device for exhaust gas containing halogen fluoride, which has a double-barrel structure, which contains a reaction treatment agent for the fluorine component in the inner tube, a reaction treatment agent for the halogen component in the outer tube, and an exhaust gas The inlet of the inner cylinder; the path of the exhaust gas from the inner cylinder to the outer cylinder; and the outlet that discharges the treated exhaust gas from the outer cylinder. (13) As described in the item (12) above, the processing ratio of the fluorine-containing halogen-containing exhaust gas is the volume ratio of the fluorine component treating agent in the inner cylinder and the halogen component treating agent in the outer cylinder. 1: 0.5 ~ 1: 3. [Embodiments of the invention] The fluorinated halogen image as the exhaust gas treatment method, the treatment agent, and the treatment object of the present invention is a fluorine-containing halogen compound, such as C1F, C1F3, and ClFs, and BrF, Bromine fluoride represented by the forms BrF3 and BrF5 is iodine fluoride represented by the forms IF 3, IF 5 and IF 7. In the field of manufacturing a semiconductor or a thin-film transistor liquid crystal display element, the present invention is used for dry cleaning of a thin-film forming device, and is particularly suitable for treating exhaust gas containing bromide fluoride such as trifluoride gas and bromine trifluoride. Suitable to be used. Although it is intended to explain the present invention below, here is an example of the treatment method, treatment agent, and treatment device for halogen-containing exhaust gas including chlorine fluoride as a representative example and chlorine fluoride. As an appropriate treatment agent for simultaneously processing the fluorine component and halogen component of a fluorinated halogen such as trifluorinated atmosphere, soda lime (a mixture of hydrogenation, bell and sodium hydride), and solid alkali such as calcium hydroxide have been used. ~ 8-This 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 ---------% Intellectual Property of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Bureau of Staff 523491 Printed by the Consumer Cooperative of the Bureau of Intellectual Property of the Ministry of Economic Affairs A7 B7 V. Description of the invention (7) Where calcium hydride is used as a solid and reacted with trifluoride atmosphere, it is equivalent to one mole unit The reaction heat of the trifluoride gas is as follows: C1F 3 + 2Ca (0H) 2 — 3 / 2CaF2 + l / 2CaCl 2 + 2H 2 〇 + 〇2 .. 575kJ / »ol Although the reaction treatment of hydroxide has the advantage of being able to process both the fluorine component and halogen component of halogen fluoride, it has a large heat generation during the reaction treatment. For example, in the case of trifluoride gas, it is equivalent to 2 moles per 1 mole unit. It is dangerous to cause problems such as dissolution of the treatment agent, deliquescence, and occlusion of the treatment cylinder. In the case where the reaction treatment agent is dried, there is a problem that its treatment capacity is greatly reduced. On the one hand, if the inventors according to the present invention can use the sulfonates and metal hydrides of the arsenic type as the reaction treatment agent for the fluorine component of the halogen fluoride, and can use alkali metal sulfonates and / or hydrogen sulfonates The salt acts as a reaction treatment agent for the halogen component of fluorinated dentin. When an alkaline earth metal master salt is used for the reaction treatment of fluorinated halogen, only the fluorine component in the fluorinated halogen can be selectively reacted and fixed, and there is less heat generation during the reaction treatment and no water is generated. The advantages. As the reaction treatment agent for the fluorine component of trifluoride gas, for example, when calcium sulfonate is used, the reaction heat of reaction with 1 mole of chlorine trifluoride is as follows. C 1 F 3 + 3 / 2CaC0 3 3/2 C a F 2 + 1/2 C 1 2 + 3 / 2C 0 2 + 3/4 0 2 ..... 445kJ / ffl〇l that is, The reaction heat when calcium fluoride is used to react the fluorine component of the trifluorinated atmosphere is about 130KJ / mol smaller than when the fluorine component of chlorine trifluoride is simultaneously treated with calcium hydroxide. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -------- IT --------- ^ Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 523491 A7 B7_ V. Description of the Invention (〖) Here, the free halogen due to the reaction of the alkaline earth metal sulphate and halogen fluoride has always been used in the past. It is adsorbed by adsorbents such as activated sulfonate or zeolite. However, the treatment cylinder that adsorbs halogen is dangerous because it desorbs the desorbed gas. When it is used, it may also react with halogen fluoride to burn and explode. Or zeolite and other adsorbent methods are not ideal. Therefore, it is preferred that the free dentition according to the present invention be treated with a sulfonate and / or a hydrogen acid salt of a rhenium metal to make it a halide of an alkali metal and to immobilize it. For example, when the reaction of sodium sulfonate is used as a reaction treatment agent for chlorine component, the reaction heat equivalent to 1 mole of chlorine trifluoride in atmospheric equivalent is as follows: 1 / 2C1 2 + l / 2Na 2 CO 3 NaCl + 1 / 2C02 + 1/4 0 2 ..... 43kJ / ffl0l In other words, it is known that the reaction heat when the fluorine component of trifluoride gas is treated with sodium sulfonate is more than that of The reaction heat when the fluorine component of the trifluoride gas is subjected to a reaction treatment is very small. In addition, by the reaction treatment of the above-mentioned alkali metal salt and / or hydrogen acid salt to the halogen component of halogen fluoride, and adding an appropriate amount of water, the reactivity of halogen and halogen component can be improved, and the treatment agent can be improved. Processing capacity per unit volume. However, if more than necessary water is added, the reaction treatment agent may block the reaction cartridge due to deliquescence due to the release of water during the reaction with the halogen component. By adding water to the reaction treatment effect of the halogen component in the fluorinated halogen with the sulfonate and / or hydrogen sulfonate of the alkali metal, for example, the reaction of treating the odor component in the chlorine trifluoride with sodium gallate has a catalyst effect It is estimated as follows -10- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page)-Order --------- Economy Printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau 523491 A7 B7_ V. Description of the invention (?) Reaction formula:
Cl 2 +H 2 0-► 2HC1 + 1/20 2 2HC1 + Na 2 CO 3 —2NaCl + C02 +H 2 〇 在此，水的添加方法，舉例而言，如以作為氟化鹵素 的_素成分的反應處理劑之吸附水或結晶水添加，但因 在使用或保存於這些方法中之所添加的水蒸發，而恐會 降低氟化鹵素的鹵素成分之反應處理劑的處理能力。於 是，預先備妥相當於對氟化鹵素中氟成分的反應處理劑 所産生之水量，且在反應處理時不會顯箸提高發熱的範 圍内添加金屬氫氣化物，該方法較宜為氟化鹵素中氟成 分反應時新産生的水，作為下一段鹵素成分的反應處理 之觸媒使用。而且，與其將金屬氫氧化物添加在氟化鹵 素中鹵素成分的反應處理劑之場合，不如添加在氟成分 的反應處理劑之場合，可較有效地利用反應處理時所産 生的水，而可提高鹵素成分的反應處理劑之處理能力。 在本發明中，氟化鹵素中氟成分的反應處理劑所使用 的鹼土類金屬磺酸鹽者，可舉例如磺酸波、磺酸鎂、磺 酸鈣、碩酸緦、碩酸鋇等。在這些中尤其以碩酸鈣、碩 酸鎂為宜。這些鹼土類金屬的碩酸鹽可單獨使用，亦可 將兩種以上任意的比率混合使用〇 又本發明中，氟化鹵素的氟成分反應處理劑所使用的 金屬氫氧化物，只要是在與氟成分反應時會産生水者， 並無特別限制，卽不至於使氟成分的反應處理能力降低 ，可適予使用。例如，氫氧化鈉、氫氫化鉀那樣的鹼金 -1 1 - 本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) - 523491 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（”） 屬的氫氧化物，氫氣化鈣那樣的鹼土類金屬之氫氧化物 ，氫氧化鋁那樣的金屬氫氧化物。又這些氫氣化物可單 獨使用，亦可將二種以上以任意比例混合使用。 本發明的氟成分之反應處理劑中，鹼土類金屬的碩酸 鹽和金屬氫氧化物之含有j:b率以重量比計為1:1〜99:1 較佳，3: 2〜99:1更宜，4:1〜19:1為最理想。 在本發明中，用於氟化鹵素的鹵素成分之反應處理劑 的鹸金屬碩酸鹽，可舉例如磺酸鋰，磺酸鈉，磺酸鉀， 磺酸铷，磺酸鉋，磺酸氫鹽可舉例如磺酸氫鈉，碩酸氫 鉀，磺酸氫铷，磺酸氫絶等。其中，碩酸鹽以磺酸鈉， 磺酸鉀為宜，碩酸氫鹽以磺酸氫鈉，磺酸氫鉀為佳。又 這些鹼金屬的磺酸鹽及/或磺酸氫鹽可單獨使用，亦可 將兩種以上以任意的比例混合使用之。而且，當本發明 的排氣處理劑成型之際，以提高其成型性為目的，亦可 在不影響該處理劑性能的範圍内添加氧化鋁，氣化矽， 氧化鎂，硫酸鈣等黏合劑成分，在此情況下，鹼金屬的 磺酸鹽及/或磺酸氫鹽的含有率最好為反應處理劑的60 重量％以上，以8 G重量％以上為更理想。 接著，本發明的含氟化鹵素的排氣處理劑，其粒徑大 小為0.5〜ΙΟιηιη，尤其以使用1〜5fflm的大小為最佳，為 使能達成這種寸尺，通常成型後才使用。處理劑的成型 方法並無特別限制，但成型方法可舉例如壓出成型法， 打造錠劑成型法，或以這些方法等成型者再予破碎的方 法等。 _ _ · -1 2- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ---1--£---,------------訂--------- (請先閱讀背面之注意事項再填寫本頁) 523491 I Γ A7 _B7_ 五、發明說明（"） 本發明中處理含氟化鹵素的排氣之反應處理劑中的氟 成分和反應處理劑中鹵素成分之比例，以體積比計為 1:0.5〜1:3較宜，1:1〜1:2程度更佳。若此體積比若小 於1:0.5時，則不能將氟化鹵素中經反應處理劑的氟成 分處理後之鹵素成分予以充分處理，若大於1:3者，反 應處理劑的鹵素成分將過剩。 此外，由於本發明含氟化鹵素排氣之處理劑在常溫下 就有充分的處理能力，故不必特別加熱，可在常溫附近 (5〜4 0 °C )使用。 又處理對象氣體中的氟化鹵素濃度，通常以0.01〜1〇 體積％為宜。又且，此處理對象氣體的流速，通常以空 筒基準線速度（LV)O.l〜5ro/s較佳。 接著，就本發明氟化_素的處理裝置加予説明〇 按照本發明，如第1圖所示為雙重筒構造的處理筒， 分別填充處理劑以抑制發熱的影饗，可更加安全地處理 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 筒，理發面锈 3 的 理劑處的平不筒 3 。 處理當劑的為外筒向 的處於理圖傺及外流 造應由處 1 部 2 ，氣 構反 ，應第内筒 5 排 筒之者反 。1 内口示 重分劑之果筒的入表 雙成理分效理劑氣頭 有氟處成的處理排箭 具中應素色的處為以 在素反鹵角造應部中 ~ ，鹵之的料構反上圖3-即化分筒材筒容的 。-1 亦氟成外熱圓收 26 C 的素在隔重成筒口 氣明鹵充具雙構内出 排發充填兼，而，體 之本瑱 ，有中因且、氣 素充 3 時故圖，而理 齒填筒分 ，面 4 。處 化筒外成小剖網部為 氟内於素量及製底部 含 1 再鹵熱圖銅之上 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 經濟部智慧財產局員工消費合作社印製 523491 A7 B7_ 五、發明說明（π) 内筒的氟反應處理劑和外筒的鹵素反應處理劑之填充 比率，以體積比計為1:0.5〜1:3為宜，更佳的是1:1〜 1 : 2 〇 本發明含氟鹵素的排氣處理筒之大小或縱横比，得配 合按每一單位時間想要處#的含氟化鹵素之排氣量或欲 設置的空間，可任意加以選擇，而且，由於本發明的排 氣處理劑處理排氣時的發熱量小，故填充於所使用具有 兼備隔熱效果之雙重筒構造處理筒時，不必另外裝設冷 卻設備。 本發明的排氣處理劑，傺與習知的鹼石灰，氫氧化鈣 ，氫氧化鉀，氫氣化鈉等固體鹼作為排氣處理劑使用的 情況不同，由於處理含氟化鹵素的排氣時所産生的水份 量少，故並無因水使處理劑融解、潮解而導致處理筒閉 塞、降低除害能力等問題。 更依照本發明而將氟化鹵素中的氟成分和鹵素成分分 別與其選擇性反應之反應處理劑來處理，較諸將氟化鹵 素中氟成分和鹵素成分同時加以處理的習知技術，則可 提高每一處理劑單位體積的處理能力。 但是，以固體鹼同時處理氟化鹵素的氟成分和鹵素成 分的場合，以使用氫氧化鈣處理三氟化氯之情況為例加 以說明者，在三氟化氮中氯成分較諸氟成分其與反應處 理劑的反應性低（H以下式表示如后），因進行齒素交換 反應而産生的氛化鈣和三氟化氯，當排氣中三氟化氯濃 度低時或處，理劑已乾燥掉時等情況，使得氛成分的處理 -1 4 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） —·—一—《—--------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 523491 I f A7 _B7_ 五、發明說明（^ ) 會變成不夠充分而顯著地降低處理能力。 C 1 F 3 +3/2CaCl 2 3 / 2 C a F 2 +2C1 2 (請先閱讀背面之注意事項再填寫本頁) 再者，本發明含氟化鹵素的排氣處理劑及其處理方法 ，較諸上述使用固體鹼以同時處理氟成分和鹵素成分的 場合，因排氣處理反應時的發熱小，而得以安全且有效 率地將含氟化鹵素的排氣加以處理。 [實施例】 以下實施例用以更加詳細地說明本發明，但本發明並 非限定於這些實施例。 (實施例1〜3 ) 在第2圖所示内徑為22ram，長度為1 2 0 0 mni的圓筒形4 處理筒1 1，於（距處理筒入口部3 0 0诅m、6 Ο Ο ®祖、9 0 0扭m三 處）等3個場所，裝設熱電偶式溫度感測器1 2，1 3，1 4 , 將以表1所示的組成及粒徑為1〜3IB1H的氟成分之反應處 理劑150cc瑱充於入口部，又將表1所示的組成及粒徑 為1〜3ηιιη的氯成分之反應處理劑250cc填充於出口部。 自處理筒入口將之氟化氯用氮稀釋為7. 5體積％濃度 之氣體，以空洞基準線速度3.0m/分，室溫（25°C)，使 經濟部智慧財產局員工消費合作社印製 時度 S溫 1P熱 過發 超大 度最 濃的 。 氮時果 的理結 口處的 出應好 筒反良 理和為 處量像 俟理示 ，處所 通的 2 流氯表 下化如 壓氟 ， 氣三果 大出結 在求其 其，ο 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 523491 A7 __B7 五、發明說明（^ ) 表1 經濟部智慧財產局員工消費合作社印製 實施例1，4,7，10 實施例2,5 ,8 實施例3,6,9 組成（重量％ ) 組成（重量％ ) 組成（重量％ ) 氟成分的反 磺酸鈣 95 碩酸鈣 90 磺酸鈣 80 應處理劑 氫氣化鈣 5 氫氣化鈣 10 氫氧化錄 20 氛成分的反 磺酸鈉 90 磺酸鈉 90 碩酸鈉 90 應處理劑 氧化鋁 10 氣化鋁 10 氧化鋁 10Cl 2 + H 2 0-► 2HC1 + 1/20 2 2HC1 + Na 2 CO 3 — 2NaCl + C02 + H 2 〇 Here, the method of adding water, for example, as the element of halogen fluoride The adsorption water or crystallization water of the reaction treatment agent is added, but the water added in the methods used or stored in these methods evaporates, which may reduce the treatment ability of the reaction treatment agent of the halogen component of the fluorinated halogen. Therefore, the amount of water generated by the reaction treatment agent corresponding to the fluorine component in halogen fluoride halogen is prepared in advance, and metal hydride is added in a range that does not significantly increase heat generation during the reaction treatment. This method is more suitable for halogen fluoride The water newly generated during the reaction of the intermediate fluorine component is used as a catalyst for the reaction treatment of the halogen component in the next stage. Moreover, instead of adding a metal hydroxide to a reaction treatment agent of a halogen component in a halogen fluoride, it is not as effective as adding a reaction treatment agent of a fluorine component to use water generated during the reaction treatment. Improve the processing capacity of the halogen component reaction treatment agent. In the present invention, examples of the alkaline earth metal sulfonate used as the reaction treatment agent for the fluorine component in the fluorinated halogen include sulfonate, magnesium sulfonate, calcium sulfonate, europium sulfonate, and barium sulfonate. Among these, calcium sulphate and magnesium sulphate are particularly suitable. These alkaline earth metal master salts may be used alone, or two or more of them may be used in any ratio. In the present invention, the metal hydroxide used in the fluorine component reaction treatment agent of halogen fluoride is only used in combination with Those who generate water during the reaction of the fluorine component are not particularly limited, and do not reduce the reaction treatment ability of the fluorine component, and can be suitably used. For example, basic gold such as sodium hydroxide and potassium hydride-1 1-This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)- 523491 Printed by A7 B7, Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention (") hydroxides, hydroxides of alkaline earth metals such as calcium hydroxide, metal hydroxides such as aluminum hydroxide. These hydrides can be used singly, or two or more kinds can be mixed and used in any ratio. In the reaction treatment agent for fluorine component of the present invention, the content of j: b ratio of the alkaline earth metal master salt and metal hydroxide is in weight. The ratio is preferably 1: 1 to 99: 1, more preferably 3: 2 to 99: 1, and most preferably 4: 1 to 19: 1. In the present invention, the halogen component is used for the reaction treatment of the halogenated fluoride. Examples of sulfonium metal master salts include lithium sulfonate, sodium sulfonate, potassium sulfonate, europium sulfonate, sulfonate, and hydrogen sulfonate salts such as sodium hydrogen sulfonate, potassium hydrogen sulfonate, and sulfonic acid Hydrogen hydrazone, hydrogen sulfonate, etc. Among them, sodium sulfonate and potassium sulfonate are suitable as the sulfonate, and hydrogen sulfonate The salts are preferably sodium hydrogen sulfonate and potassium hydrogen sulfonate. These alkali metal sulfonates and / or hydrogen sulfonates can be used alone, or two or more of them can be mixed and used at any ratio. Moreover, when When the exhaust treatment agent of the present invention is molded, for the purpose of improving its moldability, it is also possible to add a binder component such as alumina, siliconized gas, magnesium oxide, calcium sulfate, etc. within a range that does not affect the performance of the treatment agent. In this case, the content of the alkali metal sulfonate and / or hydrogen sulfonate is preferably 60% by weight or more of the reaction treatment agent, and more preferably 8G% by weight or more. The halogen exhaust gas treatment agent has a particle size of 0.5 to 10 μm, especially the use of 1 to 5 fflm is the best. In order to achieve this size, it is usually used after molding. There is no molding method for the treatment agent. It is particularly limited, but the molding method can be, for example, an extrusion molding method, a tablet molding method, or a method in which the molder breaks the crusher. _ _ · 1-2 2-This paper size applies to Chinese national standards (CNS ) A4 size (210 X 297 mm)- -1-- £ ---, ------------ Order --------- (Please read the notes on the back before filling this page) 523491 I Γ A7 _B7_ Five 2. Description of the invention The proportion of the fluorine component in the reaction treatment agent for treating the fluorinated halogen-containing exhaust gas and the halogen component in the reaction treatment agent in the present invention is preferably 1: 0.5 to 1: 3 in volume ratio. The ratio of 1: 1 to 1: 2 is better. If the volume ratio is less than 1: 0.5, the halogen component of the fluorinated halogen that has been treated with the fluorine component of the reaction treatment agent cannot be fully processed. If it is greater than 1: 3, the halogen component of the reaction treatment agent will be excessive. In addition, since the treatment agent containing halogenated fluorinated exhaust gas of the present invention has sufficient processing ability at normal temperature, no special heating is required, and it can be near normal temperature (5 ~ 40) ° C). The concentration of halogen fluoride in the target gas is usually 0.01 to 10% by volume. In addition, the flow velocity of the gas to be processed is usually preferably at a reference linear velocity (LV) of 0.1 to 5 ro / s. Next, the processing apparatus of the fluorinated element of the present invention will be explained. According to the present invention, as shown in FIG. 1, the processing cylinder having a double-cylinder structure is separately filled with a processing agent to suppress the effect of heat generation, and can be processed more safely. (Please read the precautions on the back before filling out this page.) The employee's cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the tube, and the flat surface of the rust 3 on the hairdressing surface 3. The processing agent is in the direction of the outer cylinder, and the outflow is to be made by the department 1 2. The gas structure is reversed, and the one in the 5th inner cylinder is reversed. 1 The inner mouth shows the re-dispersed fruit tube into the table. The double-synthetic split-effect agent has a fluorine head. The treatment of the arrowhead should be plain in the prime antihalogen angle response section. The structure of the halogen material is shown in Figure 3 above, which is the volume of the divided tube. -1 Fluoride into the outer heat circle to receive 26 C of the element at the weight of the tube into the mouth tone bright halogen filling with dual structure internal discharge and filling, and, the essence of the body, there is a medium cause, and the gas filling 3 diagram , And the teeth filling cylinder points, surface 4. The small section of the net is made of fluorine, and the bottom is made of copper. The paper size is on top of copper. This paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). The intellectual property of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives 523491 A7 B7_ 5. Description of the Invention (π) The filling ratio of the fluorine reaction treatment agent in the inner cylinder and the halogen reaction treatment agent in the outer cylinder is preferably 1: 0.5 ~ 1: 3 in volume ratio. More preferably, the size or aspect ratio of the fluorinated halogen-containing exhaust treatment cylinder of the present invention is 1: 1 ~ 1: 2. The amount of fluorinated halogen-containing exhaust or The installation space can be arbitrarily selected. Moreover, the exhaust gas treatment agent of the present invention has a small amount of heat generation when processing exhaust gas, so it is not necessary to separately install the dual-cylinder structure processing cylinder used for heat insulation. Cooling equipment. The exhaust gas treatment agent of the present invention is different from the conventional solid alkali such as soda lime, calcium hydroxide, potassium hydroxide, sodium hydride and the like as an exhaust gas treatment agent. The amount of water produced is small, so there are no problems such as blockage of the treatment cylinder due to the melting and deliquescing of the treatment agent by water, and reduction of the harm removal ability. According to the present invention, the fluorine component and the halogen component in the fluorinated halogen are separately treated with a reaction treatment agent that selectively reacts with them. Compared with the conventional technology of processing the fluorine component and the halogen component in the fluorinated halogen at the same time, Increase the processing capacity per unit volume of each processing agent. However, when a solid base is used to process both the fluorine component and the halogen component of a halogen fluoride, and the case of using calcium hydroxide to treat chlorine trifluoride will be described as an example, the chlorine component in nitrogen trifluoride is more important than the fluorine components. The reactivity with the reaction treatment agent is low (H is represented by the following formula as follows). The atmospheric calcium and chlorine trifluoride generated by the tooth exchange reaction are performed when the concentration of chlorine trifluoride in the exhaust gas is low. When the agent has been dried, etc., the treatment of the atmosphere component is made. 1 4-This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) — · — 一 — 《—------- -Order --------- line (please read the precautions on the back before filling this page) 523491 I f A7 _B7_ V. The description of the invention (^) will become insufficient and significantly reduce the processing capacity. C 1 F 3 + 3 / 2CaCl 2 3/2 C a F 2 + 2C1 2 (Please read the notes on the back before filling this page) Furthermore, the exhaust treatment agent containing halogen fluoride of the present invention and its treatment method Compared with the above-mentioned case where a solid base is used to simultaneously process a fluorine component and a halogen component, the heat generated during the exhaust gas treatment reaction is small, so that the exhaust gas containing halogen fluoride can be safely and efficiently processed. [Examples] The following examples are used to describe the present invention in more detail, but the present invention is not limited to these examples. (Examples 1 to 3) As shown in FIG. 2, a cylindrical 4 treatment cylinder 11 having an inner diameter of 22 ram and a length of 1 2 0 0 mni was placed at a distance of 3 0 0 from the entrance of the treatment cylinder. 〇 ® ancestors, 9 0 0 m 3) and other three places, thermocouple temperature sensors 1 2, 1 3, 1 4 will be installed, the composition and particle size shown in Table 1 will be 1 ~ 3IB1H 150cc of the fluorine-containing reaction treatment agent was filled in the inlet portion, and 250cc of the chlorine-containing reaction treatment agent having the composition and particle size shown in Table 1 was charged in the outlet portion. From the inlet of the processing cylinder, the chlorine fluoride was diluted with nitrogen to a gas having a concentration of 7.5% by volume, and at a hollow reference line speed of 3.0m / min and room temperature (25 ° C), it was printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. When the temperature is 1 ° P, the overheating is the thickest. The output of the fruit of the nitrogen when the fruit is in the mouth should be counter-intuitive, and the amount of the image should be shown. The flow of chlorine in the 2 places under the surface is like fluorine, and the three fruits of the gas are in great demand. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 523491 A7 __B7 V. Description of the invention (^) Table 1 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy Example 1, 4, 7, 10 Example 2,5,8 Example 3,6,9 Composition (% by weight) Composition (% by weight) Composition (% by weight) Fluorine calcium sulfonate 95 Calcium sulfonate 90 Calcium sulfonate 80 Hydrogenation of the treatment agent Calcium 5 Calcium Hydrogen 10 Hydroxide 20 Sodium transsulfonate with atmospheric components 90 Sodium sulfonate 90 Sodium sulfonate 90 Application agent alumina 10 Aluminium vapor 10 Alumina 10
表2 實施例1 實施例2 實施例3 三氟化氣處理量 1 0 1 g 90g 85g 最高逹到的溫度 3 0 0 °C 3 10°C 3 3 0 °C -16- ---.--,---.------------訂--------- ΜΨ (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 523491 A7 _B7_ 五、發明說明（心） (實施例4〜6) 除了使在處理筒的用氮加以稀釋三氟化氣氣體，以空 筒基準線速度1.41»/分流通之外，其餘均與實施例1〜3 同樣之方式實施實施例4〜6。其結果，如表3所示顯示 良好的結果。 表3Table 2 Example 1 Example 2 Example 3 The amount of trifluoride gas treatment 10 1 g 90 g 85 g The highest temperature reached 3 0 0 ° C 3 10 ° C 3 3 0 ° C -16- ---.- -, ---.------------ Order --------- ΜΨ (Please read the precautions on the back before filling out this page) This paper size applies to Chinese national standards ( CNS) A4 specification (210 X 297 mm) 523491 A7 _B7_ V. Description of the invention (heart) (Examples 4 to 6) Except that the trifluoride gas is diluted with nitrogen in the processing cylinder, and the reference linear velocity of the empty cylinder is used. Except for 1.41 »/ min, the rest are implemented in the same manner as in the first to third embodiments. As a result, as shown in Table 3, good results were shown. table 3
實施例4 實施例5 實施例6 三氟化氣處理量 97g 84g 78g 最高逹到的溫度 16 0°C 180°C 2 0 0 °C (實施例7〜9 ) 除了使在處理筒的用氮加以稀釋三氟化氯氣體，該三 氟化氣濃度定為0.7體積％，以空筒基準線速度1.6m/分 流通之外，其餘均與實施例1〜3同樣之方式實施實施例 7〜9。其結果，如表4所示般顯示了良好的結果。 表4 (請先閱讀背面之注意事項再填寫本頁) 訂---------線一 經濟部智慧財產局員工消費合作社印製 實施例7 實施例8 實施例9 三氟化氛處理量 76g 73g 69g 最高達到的溫度 10 0°C 1 0 5°C 1 2 0°C 本紙張尺度適用中國國家標準（CNS)A4規格（210^97公釐） 523491 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（4 ) (實施例1 0 ) 在第3圖所示，係為不锈鋼製處理筒（高8001B1I,不锈 銅製網的深度達78Gmffl)，於外筒表面和内筒處安裝熱電 偶式溫度絨測器8 ，該内筒（内徑28 Omni)和外筒（内徑 4 6 01H1B)，分別瑱充表1所f的組成及粒徑為3〜5βιιβ之氟 成分反應處理劑40 L和氯成分反應處理劑70L。 自處理筒入口，將三氟化氛用氮稀釋為7. 5體積％的 濃度之氣體，以空筒基準線速度1.4m/分，室溫（25°C) ，在大氣壓下使其流通，俟處理筒出口的氟或氯濃度超 過lppm時，求出三氟化氯的處理量和反應處理時的最高 到逹溫度。 結果，三氟化氯的處理量為25kg。且内筒最高到達溫 度傺25 °C，外筒表面最高可到達50 °C，確認該具有雙重 筒構造之處理筒的效果。 (比較例1 ) 在第2圖所示係為已安裝熱電偶式溫度感測器，而填 充鹼石灰4 0 0 cc,之内徑22m a,長120 Omni之圓筒形處理 筒，自處理筒入口將三氟化氯用氮稀釋為7. 5體積％的 濃度之氣體，以空調基準線速度3.0m/分，室溫（25 °C) ,使其在大氣壓下流通，俟處理筒出口的氟或氣濃度超 越lppin時，求出三氟化氯的處理量和反應處理時之最大 發熱溫度。 但是，處理筒入口的壓力在中途上舁，致使處理筒閉 塞。處理筒_閉搴前的三氟化氯的處理量為60公克。•又直 _ 1 8 _ 本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{ 523491 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（^ ) 到處理筒閉塞前可到達的最大溫度為400 °C以上。 (實施例1 1 ) 在内徑為22mm,長為1 2 0 0 niffl的圓筒形之處理筒中三處 (距自處理筒入口部3 0 0 m m，6 0 Q m ro，9 0 0 in m )安裝第2圖 所示的熱電偶式溫度絨測器12, 13，14其只填充表1所 示和實施例1同樣的組成，粒徑也同樣的1〜3βιβ之氟成 分的反應處理劑400cc,以調査氟成分的反應處理劑之 反應。 自處理筒入口，將三氟化氛用氮稀釋為7. 5體積％的 濃度之氣體，以空洞基準線速度1.41Π/分，室溫（25°C) ,使其在大氣壓下流通，將處理筒出口氣體中的氯化物 離子及氟化物離子的濃度，用離子層析儀加以測定，而 將處理前之氣體所包含的氟成分和氛成分比率（％)，表 示於第4圖。 如第4圖所示，在出口氣體中自起始至某一時刻完全 不含有氟成分，到某一時刻才包含氟成分，因而確認氟 成分的反應處理劑只將三氟化氯的氟成分選擇性的被處 理。將完成處理後的氟成分之反應處理劑分析，結果其 主成分為氟化鈣。 直到處理筒出口氣體中氟化物離子濃度超過1 ppm時的 三氟化氯之處理量為26Qg。第5圖傺表示三個溫度烕測 器12， 13, 14的溫度，最高可到達的溫度為150°C。處 理筒入口的壓力如第6圖所示為保持一定值G.Q1〜0.02 公斤/平方公分。 -1 9- 本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) ii 訂---------線€1^-· 523491 i t Α7 _Β7_ 五、發明說明（〃） (比較例2 ) 除了將取代氟成分反應處理劑的市面銷售之鹼石灰 4 0 0 cc填充於處理筒之外，和實施例11相同，測定處理 筒出口氣體中的氛化物離子及氟化物離子的濃度，將各 溫度感測器的最高可到達p度，處理筒入口壓力加以測 定後，將對處理前的氣體所包含的氟成分和氣成分之比 率（％ )在第7圖表示之。 如第7圖所示，雖自起始以至某一時刻同時處理了三 氟化氮的氯成分和氟成分，但在處理筒出口氣體比氟化 物離子較先檢測出氯化物離子。 處理筒出口氣體中的氣化物離子濃度直到超過1PPB!前 的三氟化氯的處理量為、60公克，氟化物離子濃度直到超 過lppm前的三氟化氣處理量即為110公克。又見如第8 圖所示各溫度感測器，可到達的最高溫度為2 0 0 °C。處 理筒入口的壓力如第9圖所示，確認和反應處理進行的 同時上昇到0.02公斤/平方公分。 [發明效果] 按照本發明的含氟化鹵素的排氣之處理方法，處理劑 (請先閱讀背面之注意事項再填寫本頁) -------訂---------•^座 經濟部智慧財產局員工消費合作社印製 至危造其時 不等製尤漏 且塞件，洩· ，閉元法筒 地筒晶淨體 率理液清氣 效處體式素 有使晶乾鹵 氣而電的化 一排生膜置氟 fif'産薄裝或 。 素之或成理用 鹵水造形處有0-化因製膜氣其-2 氟或體薄排極 含昇導在的上 將上半用素業 可度在使鹵X ，溫。被化等 置的理，，氟害_ 裝熱處上含除 理：發以域於急 處因得領用緊 及於險等是的 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 523491 A7 B7 五、發明說明（'?) 明 說 單 簡 的 面 圖 面 平 之 置 裝 ml 理 處 之 造 構 筒 B Ϊ 〇 雙 筒 的 理 明 處 發 的 本 例 照。施 按圖實 俗面偽 圖剖圖 1 縱 2 第及第 圖 第第第第第第第 例例例例例例 施施施較較較 實實實比比比 示示示示示示 表表表表表表 傺傺 僳僳偽 傺 傺 圖圖圖圖圖圖圖 號 符 考 參 造 構 筒 S 雙 例 施 實 表 C 表 C 圖表 圖表 之圖。之画 ❶ 。值之表值之表 置析度圖析度圖 裝分溫之分溫之 理體内力體内力 處氣筒壓氣筒壓 之 口理口 口理口 出處入出處入 的的的的的的 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 8 處内外不排處熱 明 說筒 之理 筒筒銹氣理電 _14 網 銅 入氣偶 口 器 測0 口度 出溫 體式 筒 mu 理 器 測0 度 溫 式 «% 電 熱 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） IP-------- 訂---------線‘Example 4 Example 5 Example 6 The amount of trifluoride gas treatment 97g 84g 78g The highest temperature reached 160 ° C 180 ° C 2 0 0 ° C (Examples 7 to 9) In addition to using nitrogen in the processing cylinder Chlorine trifluoride gas was diluted, and the concentration of the trifluoride gas was determined to be 0.7% by volume. Except for circulating at a reference linear velocity of 1.6 m / min, the rest were carried out in the same manner as in Examples 1 to 3 except that Examples 7 to 3 were implemented. 9. As a result, as shown in Table 4, good results were shown. Table 4 (Please read the precautions on the back before filling out this page) Order --------- Printed by Line 1 Intellectual Property Bureau of the Ministry of Economic Affairs Employee Cooperatives Printed Example 7 Example 8 Example 9 Trifluoride atmosphere Handling capacity 76g 73g 69g The highest temperature reached 10 0 ° C 1 0 5 ° C 1 2 0 ° C This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 ^ 97 mm) 523491 Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 printed by the cooperative V. Description of the invention (4) (Example 10) As shown in Figure 3, it is a stainless steel processing cylinder (high 8001B1I, stainless copper mesh with a depth of 78Gmffl). A thermocouple type temperature sensor 8 is installed at the inner cylinder. The inner cylinder (inner diameter 28 Omni) and the outer cylinder (inner diameter 4 6 01H1B) are respectively filled with the composition and particle size of f in Table 1 in the range of 3 ~ 5βιιβ. 40 L of a fluorine component reaction treatment agent and 70 L of a chlorine component reaction treatment agent. From the inlet of the treatment cylinder, the trifluoride atmosphere was diluted with nitrogen to a concentration of 7.5% by volume, and was circulated at an atmospheric pressure of 1.4 m / min at a reference linear velocity of the empty cylinder at room temperature (25 ° C). When the concentration of fluorine or chlorine at the outlet of the thorium treatment cylinder exceeds 1 ppm, the treatment amount of chlorine trifluoride and the maximum temperature during the reaction process to the thorium temperature are obtained. As a result, the treated amount of chlorine trifluoride was 25 kg. The maximum temperature of the inner cylinder is 傺 25 ° C, and the maximum surface temperature of the outer cylinder can reach 50 ° C. Confirm the effect of the treatment cylinder with double cylinder structure. (Comparative Example 1) The figure 2 shows a cylindrical processing cylinder filled with soda lime 4 0 0 cc, inner diameter 22 m a, and 120 Omni length, which is installed with a thermocouple type temperature sensor. The inlet of the cylinder diluted chlorine trifluoride with nitrogen to a concentration of 7.5% by volume, and the reference linear velocity of the air conditioner was 3.0 m / min and the room temperature (25 ° C) was allowed to circulate at atmospheric pressure. When the concentration of fluorine or gas exceeds lppin, the treatment amount of chlorine trifluoride and the maximum heating temperature during the reaction treatment are obtained. However, the pressure at the inlet of the process cartridge was halted midway, causing the process cartridge to become blocked. The processing capacity of the treatment tube_chlorine trifluoride before closing was 60 g. • And straight _ 1 8 _ This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) -------- Order-- ------- Line {523491 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (^) The maximum temperature that can be reached before the processing tube is blocked is above 400 ° C. (Example 1 1) Three places in a cylindrical processing tube having an inner diameter of 22 mm and a length of 1 2 0 niffl (30 mm from the inlet of the processing tube, 6 0 Q m ro, 9 0 0 in m) The thermocouple type temperature detectors 12, 13, and 14 shown in Fig. 2 are installed, and they are filled with only the fluorine components of 1 ~ 3βιβ which have the same composition as in Example 1 and have the same particle diameter as shown in Table 1. 400cc agent to investigate the reaction of the fluorine component reaction treatment agent. From the inlet of the processing cylinder, the trifluoride atmosphere was diluted with nitrogen to a gas concentration of 7.5 vol%, and was circulated at atmospheric pressure at a reference linear velocity of 1.41 Π / min at room temperature (25 ° C). The concentration of chloride ions and fluoride ions in the outlet gas of the treatment cylinder was measured with an ion chromatograph, and the ratio (%) of the fluorine component and the atmosphere component contained in the gas before the treatment is shown in FIG. 4. As shown in Figure 4, since the outlet gas does not contain fluorine at all from the beginning to a certain time, it does not contain fluorine at a certain time. Therefore, it is confirmed that the reaction treatment agent for fluorine contains only the fluorine of chlorine trifluoride. Selective processing. Analysis of the reaction treatment agent for the fluorine component after the completion of the treatment revealed that the main component was calcium fluoride. The amount of chlorine trifluoride treated until the fluoride ion concentration in the outlet gas of the processing cylinder exceeded 1 ppm was 26 Qg. Figure 5 shows the temperature of the three temperature detectors 12, 13, 14 and the maximum reachable temperature is 150 ° C. The pressure at the inlet of the processing tube is shown in Figure 6 to maintain a certain value G.Q1 ~ 0.02 kg / cm2. -1 9- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) ii Order --------- line € 1 ^-· 523491 it Α7 _Β7_ V. Description of the Invention (i) (Comparative Example 2) The same as Example 11 except that the commercially available soda lime 4 0 0 cc instead of the fluorine component reaction treatment agent was filled in the treatment cylinder, Measure the concentration of the aerosol ions and fluoride ions in the gas at the outlet of the processing cylinder, and measure the maximum p-degree of each temperature sensor. After measuring the pressure at the inlet of the processing cylinder, the fluorine component and gas contained in the gas before processing The ratio (%) of the components is shown in FIG. 7. As shown in Fig. 7, although the chlorine component and the fluorine component of nitrogen trifluoride were simultaneously processed from the beginning to a certain time, the chloride ion was detected earlier than the fluoride ion at the outlet of the processing cylinder. The gaseous ion concentration in the outlet gas of the processing cylinder until 1PPB! Was exceeded, the amount of chlorine trifluoride treated was 60 grams, and the fluoride ion concentration until the amount of trifluoride gas before 1ppm was 110 grams. See also each temperature sensor as shown in Figure 8. The maximum temperature that can be reached is 200 ° C. The pressure at the inlet of the processing vessel was as shown in Fig. 9, and it increased to 0.02 kg / cm2 at the same time as the confirmation and reaction processes proceeded. [Effects of the Invention] According to the method for treating the exhaust gas containing halogen fluoride according to the present invention, the treating agent (please read the precautions on the back before filling this page) ------- order -------- -• ^ Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the People ’s Republic of China, the manufacturing system may be leaky and plugged when it is in danger of being manufactured. A row of raw films made of crystal dry halogen gas and electrified are placed in a thin film with fluorine fif '. There are 0-chemical reasons for the formation of brine in the brine. The film formation gas has a -2 fluorine or thin body. The upper half contains the upper lead. The first half of the process can be used to make the halogen X, warm. The reason of being equalized, fluorine harm is included in the hot place: the paper size of the paper is subject to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 523491 A7 B7 V. Description of the invention ('?) The plain view of the plain sheet is placed on the surface of the cylinder and the structure of the cylinder B 〇 〇 The double cylinder of the cylinder is issued in this example. The actual diagram of the actual plan is shown in the vertical section of the pseudo-graph. Figure 1 Vertical 2 Figure 2nd Figure 2nd Figure 1st Example 1傺 傺 僳 僳 傺 傺 傺 傺 图 图 图 图 图 图 图 图 号 符 符 符 参 参 参 参 参 参 参 参 参 参 参 参 参 参 参 参 参 参 参 参 参 参 参 参 参 参 参 参 参 参 参 参 参 参 参 参 参 参 S double case implementation table C Table C chart diagram. Paintings ❶. The value of the table is set to the analysis chart. The analysis of the temperature is divided into the temperature of the body. The internal force of the body. The internal pressure of the cylinder. The pressure of the cylinder. The mouth of the mouth. The mouth of the mouth. (Please read the notes on the back and fill in this page again.) The Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs printed 8 internal and external heat pipes that can be rusted and rusted. _14 Net copper gas inlet mouthpiece test 0 degree Out-of-temperature cylinder type mu controller measuring 0 degrees temperature type «% electric heating This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) IP -------- Order ------ ---line'