200401663 玖、發明說明： 發明所屬之技術領域 本發明涉及含氮氟化物氣體的淨化劑及淨化方法。更詳 細地說是涉及有效地淨化從半導體製造程序排出的、含有 氮氟化物氣體的淨化劑及淨化方法，其淨化劑在空氣中比 較穩定且容易保存、使用，在淨化中或淨化後的後處理中 不伴有危險，另外不排出NOx。 先前技術 在半導體製造工業中，作爲矽、矽氧化物等的乾腐蝕氣 體和CVD裝置的室式淸淨氣體係使用三氟化氮。已知三氟 化氮對於水的溶解度小，與酸或鹼幾乎都不反應，在室溫 下相當穩定，對於地球溫室化效應的影響較大，除此之外 有報告其容許濃度達到1 Oppm，當其毒性較高，直接排放 到大氣中時，對於人體及環境有害，因此在半導體製造程 序使用後必需進行淨化。 另外，雖然三氟化氮在常溫、常壓下穩定，但在乾腐蝕 和淸淨程序中，通過熱、放電等生成四氟化二氮、二氟化 二氮、六氟化二氮等的氮氟化物。由於這些氣體比三氟化 氮的毒性還強，所以與三氟化氮必須同樣進行淨化。 以往，作爲氮氟化物的淨化劑，開發了將鈣和/或鎂作 爲有效成份的淨化劑（日本第9 9 0 3 3 / 1 9 9 4號發明專利申請 公開公報）、將金屬鋅、金屬鋁或兩者的混合物作爲主成份 的淨化劑（日本第1 3425 6/1 994號發明專利申請公開公報）、 由锆或锆系合金構成的淨化劑（日本第238128/1994號發明 專利申請公開公報）、將氧化亞錫作爲有效成份的淨化劑 200401663 (曰本第5 0 1 8 / 1 9 9 9號發明專利申請公開公報）等。由於氮氟 化物在常溫下穩定，所以即使在使用任何淨化劑時都要進 行加熱、淨化處理。 另外，作爲其他的淨化方法’有將含有氮氟化物的氣體 導入到使用氫氣、甲烷、丙烷的燃燒爐的火焰中燃燒的方 法、在加熱下與金屬氧化物接觸淨化的方法等。200401663 (ii) Description of the invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a purifying agent and a purifying method for a nitrogen-containing fluoride gas. More specifically, it relates to a purifying agent and a purifying method for efficiently purifying nitrogen fluoride gas discharged from a semiconductor manufacturing process. The purifying agent is relatively stable in the air and is easy to store and use. During or after purification, There is no danger involved in the process, and NOx is not emitted. Prior art In the semiconductor manufacturing industry, nitrogen trifluoride is used as a chamber-type purge gas system for dry etching gases such as silicon, silicon oxide, and CVD devices. It is known that nitrogen trifluoride has low solubility in water, almost does not react with acids or alkalis, is quite stable at room temperature, and has a large impact on the global warming effect. In addition, it has been reported that its allowable concentration reaches 1 Oppm When it is highly toxic and directly discharged into the atmosphere, it is harmful to the human body and the environment, so it must be purified after the semiconductor manufacturing process is used. In addition, although nitrogen trifluoride is stable at normal temperature and pressure, in dry etching and cleaning processes, heat, discharge, etc. are used to generate dinitrogen tetrafluoride, dinitrogen difluoride, and dinitrogen hexafluoride. Nitrogen fluoride. Since these gases are more toxic than nitrogen trifluoride, they must be purified in the same way as nitrogen trifluoride. Conventionally, as a purifying agent for nitrogen fluoride, a purifying agent using calcium and / or magnesium as an active ingredient has been developed (Japanese Patent Publication No. 9 0 3 3/1 9 9 4), metal zinc, metal A purifying agent containing aluminum or a mixture of both as a main component (Japanese Patent Publication No. 1 3425 6/1 994), a purifying agent composed of zirconium or a zirconium alloy (Japanese Patent No. 238128/1994) Gazette), a purifying agent using stannous oxide as an effective ingredient (200401663) (Invention Publication of Patent Application No. 5018/1999) and the like. Since the nitrogen fluoride is stable at normal temperature, it is necessary to heat and purify it even when using any purifying agent. In addition, other purification methods' include a method of introducing a nitrogen fluoride-containing gas into a flame of a combustion furnace using hydrogen, methane, and propane, and a method of contacting and purifying with a metal oxide under heating.
可是，將鈣和/或鎂作爲有效成份的淨化劑或者將金屬 鋅、金屬鋁或兩者的混合物作爲主成份的淨化劑’由於有 效成份、主成份容易與氧或者水反應，所以除了保存、使 用上困難之外，對於淨化後的未反應淨化劑的後處理時， 有急劇放熱、產生有害氣體等的危險。另外’由锆或鍩系 合金構成的淨化劑，雖然在常溫的空氣中穩定，但在淨化 溫度附近的高溫下與氧劇烈反應。進而，由於，三氟化氮的 濃度高等引起高溫時，則與通常作爲三氟化氮的稀釋氣體 使用的氮也進行劇烈反應，有引起熱失控的危險。However, purifiers containing calcium and / or magnesium as active ingredients or purifiers containing metallic zinc, metallic aluminum, or a mixture of both as the main ingredients, are effective because the active ingredients and the main ingredients easily react with oxygen or water. In addition to difficulties in use, there is a danger of rapid heat generation and generation of harmful gases during the post-treatment of purified unreacted cleaning agents. In addition, a purifying agent composed of a zirconium or hafnium-based alloy is stable in air at normal temperature, but reacts violently with oxygen at a high temperature near the purifying temperature. Furthermore, when a high temperature is caused by a high concentration of nitrogen trifluoride, the reaction with nitrogen, which is generally used as a diluent gas of nitrogen trifluoride, also violently reacts, which may cause thermal runaway.
另外，將氧化亞錫作爲有效成份的淨化劑，從常溫到高 溫的空氣中是比較穩定的，但由於含有三氟化氮的氣體淨 化而生成的SnF2的密度比作爲有效成份的Sn〇小，所以淨 化劑在淨化反應結束的部分產生膨脹，引起淨化筒內的壓 力損失的增加或者閉塞，儘管還殘留有淨化能力，但是也 必需更換成新的淨化劑繼續淨化。 進而，將含有氮氟化物的氣體導入到燃燒爐的火焰中燃 燒的方法、在加熱下與金屬氧化物接觸淨化的方法，都有 排出N0X的不良現象。 因此，本發明要解決的課題在於提供淨化劑及使用它的 200401663 淨化方法，其淨化劑在含有三氟化氮等的氮氟化物的氣體 淨化中，可在空氣中比較穩定且容易保存、使用，在淨化 中不發生由於稀釋氣體的種類引起熱失控，或者在淨化後 的後處理中的急劇放熱和產生有害氣體等的危險，另外， 在淨化中不會引起淨化筒內的壓力損失增加或者閉塞，並 且不排出NOx，可高效地淨化含有氮氟化物的氣體。 發明內容 本發明者們爲了解決這些課題進行銳意地硏究的結 果，發現了含有氧化亞錫及由鹼土族金屬的氧化物、氫氧 化物、碳酸鹽、鑭的氧化物、氫氧化物、碳酸鹽組成選出 的1種以上的化合物作爲有效成份的淨化劑，在空氣中比 較穩定，容易保存、使用。另外，本發明者們發現通過將 含有氮氟化物作爲有害成份的氣體在加熱下與上述淨化劑 接觸，在淨化中不會發生由於稀釋氣體的種類引起熱失 控，或者在淨化後的後處理中引起急劇的放熱和發生有害 氣體等，另外，在淨化中不會引起淨化筒內的壓力損失增 加或者引起閉塞，進而不排出NOx，可高效地淨化含有氮 氟化物的氣體，從而完成了本發明的含有氮氟化物氣體之 淨化劑及淨化方法。 即，本發明是含有氮氟化物氣體之淨化劑，其中作爲有 效成份含有氧化亞錫，以及從鹼土族金屬的氧化物、氫氧 化物、碳酸鹽、鑭系元素的氧化物、氫氧化物、碳酸鹽中 選出的1種以上的化合物。 另外，本發明也是含有氮化物的氣體的淨化方法，其 中將含有氮氟化物作爲有害成份的氣體，在加熱下，與淨 200401663 化劑接觸，進行淨化’作爲淨化劑的有效成份含有氧化亞 錫，以及鹼土族金屬的氧化物、氫氧化物、碳酸鹽、鑭系 元素的氧化物、氫氧化物、碳酸鹽中選出的1種以上的化 合物。 本發明的含有氮氟化物氣體之淨化劑可容易地進行其 保存、使用等。另外’本發明的含有氮氟化物的氣體的淨 化方法，在淨化中不發生由於稀釋氣體的種類引起熱失 控、或者在淨化後的後處理中不引起劇烈的放熱和有害氣 體的發生等，另外，在淨化中，在淨化筒內不會發生壓力 損失的增加或者閉塞，進而，不排出NOx，可高效地淨化 含有氮氟化物的氣體。 實施方式 本發明的含有氮氟化物氣體之淨化劑及淨化方法，適用 於淨化含在氮、氬、氨等的氣體中的三氟化氮、四氟化二 氮 '二氟化二氮、六氟化二氮等的氮氟化物的淨化劑及淨 化方法。 本發明的含有氮氟化物氣體之淨化劑是作爲有效成份 含有氧化亞錫及從鹼土族金屬的氧化物、氫氧化物、碳酸 鹽 '鑭系元素的氧化物、氫氧化物、碳酸鹽中選出的1種 以上的化合物的淨化劑。 另外’本發明的含有氮氟化物的氣體的淨化方法，是將 含有氮氟化物的氣體，在加熱下，與上述淨化劑接觸、淨 化的淨化方法。 以下’對於本發明的含有氮氟化物氣體之淨化劑進行詳 細的說明。 200401663 在本發明的淨化劑中，作爲有效成份之一使用的氧化亞 錫（S η 0 )，是市售的粉末等狀態、純度9 8 %以上的，所以通 常可使用這些的市售品。 另外，上述以外的作爲有效成份的鹼土族金屬的氧化 物、氫氧化物、碳酸鹽、鑭系元素的氧化物、氫氧化物、 碳酸鹽，可舉出鈹、鎂、鈣、緦、鋇、鑭、鈽、鐯、銨、 釤、銪等的氧化物、氫氧化物、碳酸鹽，但從價廉且容易 得到的點上看，較佳爲使用鎂、鈣、緦或鑭的氧化物、氫 氧化物、碳酸鹽。另外，這些的鹼土族金屬化合物、鑭系 元素化合物可單獨使用也可2種以上並用。 本發明的淨化劑，配製時將含在淨化劑中的錫的原子數 和、鹼土族金屬的原子數及鑭系元素的原子數的合計原子 數的比作成1 . 0 . 1〜2.0，較佳爲〇 . 3〜1 .0。鹼土族金屬的原 子數及鑭系元素的合計原子數，不足錫的原子數1 0 %時， 在含有三氟化氮的氣體的淨化中，會引起將主成份的Sn〇 變換成S n F 2的反應。S n F 2的密度是4.5 7 g / c m3，與作爲主成 份的SnO(密度是6.95g/cm3)相比是小的，所以淨化劑的淨 化反應終了的部分膨脹，引起淨化筒內的壓力損失增加或 者閉塞的不良現象。另外，鹼土族金屬的原子數及鑭系元 素的原子數的合計原子數，在超過錫的原子數的2.0倍時， 產生排出NOx的不良現象。 另外，本發明的淨化劑，爲了提高造粒時的成型性和成 型強度，除了有效成份之外可添加成型助劑。作爲這樣的 成型助劑，可使用氟化鋰、氟化鈉、氟化鉀、氟化鎂、氟 化鈣、氟化鑭等的金屬氟化物，但是其中，在提高成型強 200401663 度的效果優良的點上，特別較佳爲使用氟化鉀。 單獨或者混合2種以上使用。這些成型助劑的加 配製淨化劑時添加 '混煉到有效成份中。成型助 量，根據成型條件而不同，不能一槪地特定，過 不到作爲成型助劑的效果，若過多時，淨化能力 以通常對於淨化劑總重量是〇. 1〜1 〇 w t %、較佳爲 5 w t % 〇 另外，本發明的淨化劑也可以含有對於氮氟化 不給予壞影響的雜質、惰性物質等。進而，使用 劑也可以含有水分，但較佳爲不含水的，通常淨 水分配製成2 w t %以下。另外，即使含有這些成型 質、惰性物質、水分等時，但是淨化劑中的有效 量，通常也需在70wt%以上、較佳爲90wt%以上 本發明的淨化劑的成型方法沒有特別限制，例 化劑成份中加入水作成漿液或餅狀後，擠出成型 當的長度、乾燥的方法或者用壓片成型將淨化劑 的方法。 另外’本發明的淨化劑可以通過將氧化亞錫等 的鹼土族金屬化合物及鑭的化合物選出的1種以 物等混合、成型進行配製，也可將氧化亞錫等成型 將從鹼土族金屬化合物及鑭系元素的化合物選出 上的化合物等也成型後，混合這些而進行配製。 在本發明的淨化劑中，在任何一種配製方法与 要成型成直徑1〜1 〇 m m左右的球狀或者直徑〇. 5 右而長度2〜20mm左右的圓柱狀或者類似它的形 這些可以 入，可在 劑的添加 少時，得 降低，所 f 0.5 〜 :物的淨化 前的淨化 化劑中的 !助劑、雜 成份的含 〇 如可在淨 、切成適 成份造粒 和由上述 上的化合 的同時， 的1種以 3，通常需 〜5 m m左 狀或相當 -10- 200401663 它的大小及形狀後，再配製。 以下’對於本發明的含有氮氟化物的氣體的淨化方法進 行詳細的說明。 本發明的淨化方法，是在加熱下將含有氮氟化物的氣體 與上述的淨化劑接觸來淨化的方法。但是作爲淨化劑的有 效成份的一部分，使用鹼土族金屬的氫氧化物、碳酸鹽、 鑭系元素的氫氧化物、碳酸鹽時，上述中的一些的化合物 在加熱時成爲氧化物，發揮鹼土族金屬的氧化物、鑭系元 素的氧化物的效果。 用本發明的淨化方法，將含有三氟化氮的氣體，與作爲 有效成份含有氧化亞錫及氧化鈣物的淨化劑接觸而淨化 時’可推測發生以下的（式1)(式2)或（式3)的反應。在本發 明的淨化方法中，從這些的反應式中明顯知道生成 CaSnF6、Sn02、CaF2，但由於這些反應生成物的合計體積 和反應前的淨化劑的有效成份的體積的差很小，所以不用 擔心引起淨化筒的塡充材料（淨化劑及反應生成物）膨脹 後’在淨化筒內壓力損失的增加或者閉塞。例如，在（式3) 的反應時，作爲淨化劑的有效成份的Sn〇、Ca〇的密度分 別是6.95g/cm3、3.37g/cm3’作爲反應生成物的Sn〇2、CaF2 的密度分別是7.0g/cm3、3.08g/cm3，由於這些是等莫耳比 的，兩者的平均密度的差小，體積的差也小。 [化1] 3Sn〇+ Ca〇+ 2NF3—> 2Sn〇2 + CaSnF6 + N2 (式 1) 6SnO + 4CaO + 4NF3-> 5Sn02 + 3CaF2 + CaSnF6 + 2N2 (式2) -11 - 200401663 3Sn〇+ 3Ca〇+ 2NF3— 3Sn〇2 + 3CaF2 + N2 (式 3) 另外，在上述反應中，在使用La 2 0 3等的鑭系元素化合 物代替Ca〇等的鹼土族金屬化合物時，按照上述反應式’ 可淨化含有氮氟化物的氣體。 在本發明的淨化方法中，使含有氮氟化物的氣體與淨化 劑接觸的溫度，通常是200〜800°C、較佳爲250〜600°C ° 在溫度比20CTC低時，氮氟化物的淨化能力下降。另外溫度 高於800°C時，不能使用不銹鋼作淨化筒，而必須使用耐熱 性更高的材質。 另外，進行淨化時的淨化筒內的壓力，通常是常壓，但 例如也可從lKPa的減壓到0.2MPa(絕對壓力）的加壓下進 行。 在本發明的淨化方法中，用於塡充淨化劑的淨化筒，通 常是圓筒狀，大小通常是內徑10〜500mm、長度20〜2000mm 左右。塡充於淨化筒的淨化劑的塡充長度，通常是1 〇〜 1000mm左右、較佳爲50〜500mm左右。淨化劑的塡充長度 是10mm以下時，含有氮氟化物的氣體的淨化不充分，在 1 000mm以上時，壓力損失變大。另外，作爲用於加熱淨化 筒的手段，通常是在淨化筒的外側設置加熱器，通過外部 的控制裝置控制溫度。另外，在本發明的淨化方法中，除 了將淨化劑作爲固定床使用外，也可作爲移動床、流動床 使用。 對於使用本發明的淨化方法時的含有氮氟化物的氣體 流速沒有特別限制，但一般較佳爲含在氣體中的氮氟化物 的濃度越高將流速變得越小。氮氟化物的濃度通常在1 %以 200401663 下，但流量小時，可以進行含有更高濃度的氮氟化物的氣 體的淨化處理。 淨化筒是根據氮氟化物的濃度、流量等進行設計的，但 較佳爲在氮氟化物的濃度是〇. 1 %以下的比較低濃度時，空 筒線速度（LV)是0.5〜50cm/sec、氮氟化物的濃度是01%〜 1%左右時，LV是0.05〜20cm/sec、氮氟化物的濃度是1% 以上的高濃度時，是1 0 c m / s e c以下的範圍內設計的。 實施例 以下，用實施例對於本發明的含有氮氟化物氣體的淨化 劑及淨化方法進行具體地說明。 實施例1 (淨化劑的配製） 將市售的氧化亞錫（純度99%)及氧化鈣（純度99%)粉碎 到ΙΟΟμιη以下’使原子數的比（sn:Ca)達到1 :0.5地進行混 合。將混合物裝入內徑20mm、高度5mm的模具內後，使 用油壓頂用1 5 0〜1 6 0 k g / c m2的壓力加壓1 〇秒鐘成型後，破 碎得到的劑，進而用篩將通過3 · 3 6mm的篩孔、通不過 2.00mm的篩孔的劑作爲淨化劑。 (淨化試驗） 將上述的淨化劑塡充到內徑2 3.9 m m、長度2 0 0 m m的 SUS316L制的淨化筒的內部，使塡充長度成爲i〇〇mm。將 淨化筒的淨化劑的溫度加熱到4 0 〇 t：後，將含有N F 3 (流量 1 3 · 4 6 m 1 / m i η)的氣（合g十流量1 3 4 6 m 1 / m i η)導入到淨化筒中淨 化含有NF3的氣體。 此時’每1 0分鐘採取從淨化筒的排出口排出的淨化氣 -13- 200401663 體的一部分’用氣相色譜法（檢測下限1〇ppm)進行分析，測 疋直到fe測N F3的時間，求出對於每1 L (升）淨化劑的n f 3 的淨化處理量（L)(淨化處理能力）的同時，用檢測管（（株）瓦 斯特科製）檢查有無NOx的排出。其結果如表1所示。 實施例2、3 除了將實施例1的淨化劑的氧化亞錫和氧化鈣的混合 比按原子數的比（S n : C a)分別達到1 : 〇 . 3、1: 〇. 7 5進行混合 外’其他與實施例1相同地配製淨化劑。使用這些淨化劑， 與實施例1相同地進行N F 3的淨化試驗。其結果如表1所 7\\ 0 實施例4、5 除了將實施例1的淨化試驗的NF3的濃度分別變成 0.2%、2.0%之外，其他、與實施例1相同地進行NF3的淨化 試驗。其結果如表1所示。 實施例6、7 除了將實施例1的配製淨化劑的氧化鈣分別替換成氫 氧化鈣、碳酸鈣之外，其他與實施例1相同地配製淨化劑。 使用這些淨化劑，與實施例1相同地進行NF3的淨化試驗。 其結果如表1所示。 實施例8、9 除了將實施例1的配製淨化劑的氧化鈣分別替換成氧 化鎂、氧化鋸之外，其他與實施例1相同地配製淨化劑。 使用這些淨化劑，與實施例1相同地進行NF3的淨化試驗。 其結果如表1所示。 實施例1 0 -14- 200401663 (淨化劑的配製） 將市售的氧化亞錫（純度9 9 %)及氧化鑭（純度9 9 %)粉碎 到100 // m以下，使原子數的比（Sn:La)達到1 :〇.5地進行混 合。通過將混合物裝入內徑20mm、高度5mm的模具後， 使用油壓頂用150〜160kg/cm2的壓力加壓1〇秒鐘成型後， 粉碎得到的劑，進而用篩將通過3.3 6mm的篩孔、通不過 2.0 0 m m的篩孔的劑作爲淨化劑。 (淨化試驗） 將上述的淨化劑塡充到內徑23.9mm、長度200mm的 SUS3 16L制的淨化筒的內部使塡充長度成爲100mm。將淨 化筒的淨化劑的溫度加熱到400°C後，將含有NF3(流量 13.4 6]111/1^11)的氮（合計流量1 3461111/111丨11)導入到淨化筒中淨 化含有NF3的氣體。 此時，每1 0分鐘採取從淨化筒的排出口排出的淨化氣 體的一部分，用氣相色譜法（檢測下限l〇ppm)進行分析，測 定直到檢測NF3的時間，求出對於每il(升）淨化劑的NF3 的淨化處理量（L)(淨化處理能力）的同時，用檢測管（（株）瓦 斯特科制）檢查有無NOx的排出。其結果如表1所示。 實施例1 1、12 除了將配製實施例1 0的淨化劑的氧化亞錫和氧化鑭的 混合比按原子數的比（S n : L a)分別達到1 : 〇 · 3、1 : 0 · 7 5進行混 合外，其他與實施例1 0相同地配製淨化劑。使用這些淨化 劑，與實施例1 〇相同地進行NF3的淨化試驗。其結果如表 1所示。 實施例1 3、1 4 -15- 200401663 除了將實施例1 〇的淨化試驗的NF3的濃度分別變成 0 · 2 %、2 · 0 %之外，其他與實施例1 0相同地進行N F 3的淨化 試驗。其結果如表1所示。 實施例1 5、1 6 除了將實施例1 〇的配製淨化劑的氧化鑭分別替換成氫 氧化鑭、碳酸鑭之外，其他與實施例1 0相同地配製淨化 劑。使用這些淨化劑，與實施例1 〇相同地進行NF3的淨化 試驗。其結果如表1所示。 實施例1 7 · (淨化劑的配製） 將市售的氧化亞錫（純度99%)及氧化鈣（純度99%)及氧 化鑭（純度99%)粉碎到ΙΟΟμιη以下，使原子數的比（Sn:Ca:La) 達到1 : 0.3 : 0.2地進行混合。通過將混合物裝入到內徑 20mm、高度5mm的模具後，使用油壓頂用150〜160kg/cm2 的壓力加壓1 0秒鐘成型後，粉碎得到的劑，進而用篩將通 過3.3 6mm的篩孔、通不過2.00mm的篩孔的劑作爲淨化劑。 (淨化試驗） · 將上述的淨化劑塡充到內徑23.9mm、長度200mm的 SUS3 16L制的淨化筒的內部，使塡充長度成爲100mm。將 淨化筒的淨化劑的溫度加熱到40(TC後，將含有NF3(流量 1 3.4 6 ηι 1 / m i η)的氮（合計流量1 3 4 6 m 1 / m i η)導入到淨化筒中淨 化含有NF3的氣體。 此時，每1 0分鐘採取從淨化筒的排出口排出的淨化氣 體的一部分，用氣相色譜法（檢測下限lOppm)進行分析，測 定直到檢測NF3的時間，求出對於每1L(升）淨化劑的NF3 -16 - 200401663 白勺淨化處理量（L)(淨化處理能力）的同時，用檢測管（（株）瓦 斯特科制）檢查有無Ν Ο x的排出。其結果如表1所示。 實施例1 8 除了將實施例丨7配製的淨化劑的氧化亞錫、氧化鈣、 氧化鑭的混合比達到原子數的比（Sn:Ca:La)爲1:〇2:〇3進 行混合之外’其他與實施例1 7相同地配製淨化劑，使用這 些淨化劑’與實施例1 7相同地進行NF3的淨化試驗。其結 果如表1所示。 比較例1 (淨化劑的配製） 在市售的氧化亞錫（純度99%) 1 000g中，加入將氟化鉀 (KF、關東化學（株）制、試藥特級）50g溶解到65g水中的水 溶液進行混合。用擠出成型機將得到的餅狀物從直徑 1.6mm的噴嘴板擠出，切斷得到的成型物，作成長度3〜5rnm 左右的顆粒’在氮氣氛圍下邊加熱到1 20 °C邊乾燥約1 2小 時配製淨化劑。 (淨化試驗） 除了使用上述的淨化劑之外，與實施例1相同地進行 NF3的淨化試驗。可是，由於在檢測NF3之前淨化筒的壓力 損失變大’所以終止了淨化試驗。將有無Ν 0 x的排出情況， 和從終止了淨化試驗的時間求出對於每1L(升）淨化劑的 NF3的淨化處理量（L)(淨化處理能力）的結果如表1所示。 比較例2 將市售的氧化鈣（純度99%)粉碎到100 μιη以下，裝入到 內徑2 0 m m、高度5 m m的模具後，使用油壓頂用1 5〇〜 -17- 200401663 16 0kg/cm2的壓力加壓l〇秒鐘成型後，粉碎得到的劑，進 而用篩將通過3.36mm的篩孔、通不過2.00mm的篩孔的劑 作爲淨化劑。 除了使用上述的淨化劑之外’與實施例1相同地進行 NF3的淨化試驗。可是，由於在淨化試驗開始後立即確認排 出數千ρ ρ πι的N 0 ’所以終止了淨化試驗。 比較例3 將市售的氧化鑭（純度99%)粉碎到ΙΟΟμιη以下，裝入到 內徑20mm、高度5mm的模具後，使用油壓頂用150〜 馨 160kg/cm2的壓力加壓1〇秒鐘成型後，粉碎得到的劑，進 而用篩將通過3.36mm的篩孔、通不過2.00mm的篩孔的劑 作爲淨化劑。 除了使用上述的淨化劑之外，與實施例1相同地進行 NF3的淨化試驗。可是，由於在淨化試驗開始後立即確認排 出數千ρ p m的N〇，所以終止了淨化試驗。 發明的效果 本發明提供含有氮氟化物的氣體的淨化劑及淨化方 肇 法，在淨化劑中，作 有效成份含有氧化亞錫，以及從鹼 土類金屬的氧化物、氫氧化物、碳酸鹽、鑭系元素的氧化 物、氫氧化物、碳酸鹽中選出的1種以上的化合物，在淨 化方法中，使含有氮氟化物的氣體在加熱下與上述淨化劑 接觸而進行淨化。該淨化劑可容易地進行其保存、使用， 在淨化中不發生由于稀釋氣體的種類引起熱擊穿、或者在 淨化後的後處理中的劇烈的放熱和有害氣體的生成等，另 外，在淨化中，在淨化筒內不會發生壓力損失的增加或者 ‘18- 200401663 閉塞，進而，不排出NOx，可高效地淨化含有氮氟化物的 氣體。 圖式簡單說明：無In addition, the purification agent using stannous oxide as an active ingredient is relatively stable in air from normal temperature to high temperature, but the density of SnF2 generated by purifying a gas containing nitrogen trifluoride is smaller than that of Sn0 as an active ingredient. Therefore, the purifying agent swells at the end of the purifying reaction, causing an increase or occlusion of the pressure loss in the purifying cylinder. Although the purifying ability still remains, it must be replaced with a new purifying agent to continue purifying. Furthermore, both the method of introducing a nitrogen fluoride-containing gas into a flame of a combustion furnace and burning it, and the method of contacting and purifying with a metal oxide under heating have the disadvantages of exhausting NOx. Therefore, the problem to be solved by the present invention is to provide a purifying agent and a 200401663 purifying method using the purifying agent. The purifying agent can be relatively stable in air and is easy to store and use in purifying a gas containing nitrogen fluoride such as nitrogen trifluoride. In the purification, there is no danger of thermal runaway due to the type of diluent gas, or the rapid release of heat and the generation of harmful gases in the post-purification treatment. In addition, the pressure loss in the purification cylinder does not increase during the purification or It is occluded and does not emit NOx, and can efficiently purify nitrogen fluoride-containing gas. SUMMARY OF THE INVENTION As a result of earnest research to solve these problems, the present inventors have found that stannous oxide and oxides, hydroxides, carbonates, lanthanum oxides, hydroxides, and carbonates containing stannous oxide and alkaline earth metals are included. One or more compounds selected from the salt composition as active ingredient purifying agents are relatively stable in the air and are easy to store and use. In addition, the inventors have found that by contacting a gas containing nitrogen fluoride as a harmful component with the above-mentioned purifying agent under heating, thermal runaway due to the type of the diluent gas does not occur during purification, or in post-treatment after purification Causes rapid heat generation, generation of harmful gases, etc. In addition, during purification, it does not cause an increase in pressure loss in the purification cylinder or cause occlusion, and thus does not discharge NOx, and can efficiently purify nitrogen-containing fluoride gas, thereby completing the present invention. Purifying agent and purifying method containing nitrogen fluoride gas. That is, the present invention is a purifying agent containing nitrogen fluoride gas, which contains stannous oxide as an active ingredient, and oxides, hydroxides, carbonates, lanthanide oxides, hydroxides, One or more compounds selected from carbonates. In addition, the present invention is also a method for purifying a nitride-containing gas, in which a gas containing nitrogen fluoride as a harmful component is contacted with a net 200401663 chemical agent under heating to perform purification. As an effective component of the cleaning agent, stannous oxide is contained. And one or more compounds selected from oxides, hydroxides, carbonates, oxides, hydroxides, and carbonates of alkaline earth metals. The nitrogen fluoride gas-containing purifying agent of the present invention can be easily stored and used. In addition, the method for purifying a nitrogen fluoride-containing gas according to the present invention does not cause thermal runaway due to the type of diluent gas during purification, or does not cause severe exothermic heat and harmful gas generation in the post-purification aftertreatment. During purification, no increase in pressure loss or occlusion occurs in the purification cylinder, and further, NOx is not discharged, and the nitrogen fluoride-containing gas can be efficiently purified. Embodiments The purifying agent and purifying method containing nitrogen fluoride gas according to the present invention are suitable for purifying nitrogen trifluoride, dinitrogen tetrafluoride, dinitrogen difluoride, and hexafluoride contained in nitrogen, argon, ammonia and the like. Purifying agent and purifying method for nitrogen fluoride such as dinitrogen fluoride. The nitrogen fluoride gas-containing purifying agent of the present invention contains stannous oxide as an effective ingredient and is selected from oxides, hydroxides, carbonates, and oxides, hydroxides, and carbonates of alkaline earth metals. A purifying agent for more than one compound. The method of purifying a nitrogen fluoride-containing gas according to the present invention is a method of purifying a nitrogen fluoride-containing gas by heating and purifying the nitrogen fluoride-containing gas. Hereinafter, the purifying agent containing nitrogen fluoride gas according to the present invention will be described in detail. 200401663 In the purifying agent of the present invention, stannous oxide (S η 0) used as one of the active ingredients is in the state of a commercially available powder and has a purity of 98% or more. Therefore, these commercially available products can be generally used. Examples of oxides, hydroxides, carbonates, oxides, hydroxides, and carbonates of alkaline earth metals other than the above as effective ingredients include beryllium, magnesium, calcium, scandium, barium, Oxides, hydroxides, and carbonates of lanthanum, osmium, osmium, ammonium, osmium, osmium and the like, but from the viewpoint of being inexpensive and easily available, it is preferable to use oxides of magnesium, calcium, osmium or lanthanum, Hydroxide, carbonate. These alkaline earth metal compounds and lanthanoid compounds may be used alone or in combination of two or more. The purification agent of the present invention is formulated to have a ratio of the number of atoms of tin contained in the purification agent to the total number of atoms of the number of atoms of the alkaline earth metals and the number of atoms of the lanthanoids to 1.0. 1 to 2.0, more Preferably, it is 0.3 to 1.0. When the number of atoms of alkaline earth metals and the total number of atoms of lanthanides is less than 10% of the number of atoms of tin, the purification of a nitrogen trifluoride-containing gas may cause the conversion of Sn 0 into Sn F 2 response. The density of Sn F 2 is 4.5 7 g / c m3, which is smaller than that of SnO (density 6.95 g / cm3) as the main component, so the part of the purification reaction of the purifying agent swells, causing the Bad pressure loss or occlusion. In addition, when the total atomic number of the number of atoms of the alkaline earth group metal and the number of atoms of the lanthanoid element exceeds 2.0 times the atomic number of tin, a defective phenomenon of NOx emission occurs. In addition, in the purifying agent of the present invention, a molding aid may be added in addition to the effective ingredients in order to improve the moldability and molding strength during granulation. As such a molding aid, metal fluorides such as lithium fluoride, sodium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, and lanthanum fluoride can be used, but among them, the effect of improving the molding strength by 200,401,663 is excellent. From this point, it is particularly preferable to use potassium fluoride. Use alone or as a mixture of two or more. The addition of these forming auxiliaries is added to the active ingredients when formulated as a scavenger. The amount of molding aid depends on the molding conditions, and cannot be specified overnight. The effect as a molding aid is too small. If it is too large, the purification capacity is usually 0.1 to 1 〇wt%, relatively It is preferably 5 wt%. In addition, the purifying agent of the present invention may contain impurities, inert substances, and the like that do not adversely affect nitrogen fluorination. Furthermore, the agent may contain water, but it is preferably water-free, and the purified water distribution is usually 2 wt% or less. In addition, even when these molding substances, inert substances, moisture, etc. are contained, the effective amount of the cleaning agent usually needs to be 70% by weight or more, preferably 90% by weight or more. The method of forming the cleaning agent of the present invention is not particularly limited. After adding water to the chemical agent component to form a slurry or a cake, the length of the extrusion molding method, the drying method, or the method of pressing the tablet to form a scavenger. In addition, the purifying agent of the present invention can be prepared by mixing and molding one kind of alkaline earth metal compound such as stannous oxide and a compound of lanthanum, etc., or molding of stannous oxide or the like from an alkaline earth metal compound Compounds selected from compounds of lanthanoids and lanthanoids are also formed, and these are mixed and prepared. In the purifying agent of the present invention, in any one of the preparation methods and a spherical shape having a diameter of about 1 to 10 mm or a diameter of about 0.5 to the right and a cylindrical shape having a length of about 2 to 20 mm or the like, these can be inserted into , Can be reduced when the addition of the agent is small, so f 0.5 ~: in the purification agent before the purification of the material! Auxiliaries, miscellaneous ingredients containing 〇 such as can be cleaned, cut into the appropriate ingredients granulation and from the above At the same time as the combination of 1 and 3, it usually takes ~ 5 mm left or equivalent -10- 200401663 to prepare it after its size and shape. Hereinafter, a method for purifying a nitrogen fluoride-containing gas according to the present invention will be described in detail. The purifying method of the present invention is a method in which a nitrogen fluoride-containing gas is brought into contact with the purifying agent described above under heating. However, as a part of the active ingredient of the purifying agent, when an alkaline earth metal hydroxide, a carbonate, a lanthanide hydroxide, or a carbonate is used, some of the above compounds become oxides when heated, exerting an alkaline earth group. Effects of metal oxides and lanthanide oxides. In the purification method of the present invention, when a gas containing nitrogen trifluoride is contacted with a cleaning agent containing stannous oxide and calcium oxide as an effective component to purify, it is estimated that the following (formula 1) (formula 2) or (Equation 3). In the purification method of the present invention, it is apparent from these reaction formulas that CaSnF6, Sn02, and CaF2 are produced. However, since the difference between the total volume of these reaction products and the volume of the active ingredient of the purification agent before the reaction is small, it is not necessary It is feared that after the filling material (purifying agent and reaction product) of the purification cylinder is expanded, the pressure loss in the purification cylinder increases or occludes. For example, in the reaction of (Formula 3), the density of Sn0 and Ca0 as the effective components of the scavenger are 6.95g / cm3 and 3.37g / cm3 ', respectively. The density of Sn02 and CaF2 as the reaction product are respectively It is 7.0g / cm3, 3.08g / cm3, because these are equal molar ratios, the difference between the average density of the two is small, and the difference between the volumes is also small. 3Sn〇 + Ca〇 + 2NF3— > 2Sn〇2 + CaSnF6 + N2 (Formula 1) 6SnO + 4CaO + 4NF3- > 5Sn02 + 3CaF2 + CaSnF6 + 2N2 (Formula 2) -11-200401663 3Sn〇 + 3Ca〇 + 2NF3— 3Sn〇2 + 3CaF2 + N2 (Formula 3) In the above reaction, when a lanthanide compound such as La 2 0 3 is used instead of an alkaline earth metal compound such as Ca 0, the above reaction is followed. Formula 'can purify the gas containing nitrogen fluoride. In the purification method of the present invention, the temperature at which the nitrogen fluoride-containing gas is brought into contact with the purifying agent is usually 200 to 800 ° C, preferably 250 to 600 ° C. When the temperature is lower than 20CTC, the nitrogen fluoride Purification capacity is reduced. In addition, when the temperature is higher than 800 ° C, stainless steel cannot be used as the purifying cylinder, but a material with higher heat resistance must be used. The pressure in the purification cylinder during the purification is usually normal pressure. For example, the pressure may be reduced from a pressure of 1 KPa to a pressure of 0.2 MPa (absolute pressure). In the purifying method of the present invention, the purifying cylinder used for filling the purifying agent is generally cylindrical, and the size is usually about 10 to 500 mm in inner diameter and about 20 to 2000 mm in length. The filling length of the cleaning agent filled in the purification cylinder is usually about 10 to 1000 mm, preferably about 50 to 500 mm. When the filling length of the cleaning agent is 10 mm or less, the purification of the nitrogen fluoride-containing gas is insufficient, and when it is 1,000 mm or more, the pressure loss becomes large. In addition, as a means for heating the purification cylinder, a heater is usually provided outside the purification cylinder, and the temperature is controlled by an external control device. In addition, in the purification method of the present invention, in addition to using the purification agent as a fixed bed, it can also be used as a moving bed or a fluidized bed. The flow rate of the nitrogen fluoride-containing gas when using the purification method of the present invention is not particularly limited, but it is generally preferred that the higher the concentration of the nitrogen fluoride contained in the gas, the smaller the flow rate. The concentration of nitrogen fluoride is usually 1% to 200401663, but when the flow rate is small, the purification process of the gas containing a higher concentration of nitrogen fluoride can be performed. The purifying cylinder is designed according to the concentration, flow rate, etc. of the nitrogen fluoride, but it is preferable that the linear velocity (LV) of the empty cylinder is 0.5 ~ 50cm / at a relatively low concentration of the nitrogen fluoride concentration of 0.1% or less. When sec, the concentration of nitrogen fluoride is about 01% to 1%, LV is 0.05 to 20cm / sec, and when the concentration of nitrogen fluoride is 1% or more, it is designed to be within 10 cm / sec. . Examples Hereinafter, the purifying agent and purifying method for a nitrogen fluoride gas-containing gas according to the present invention will be specifically described using examples. Example 1 (Preparation of Scavenger) The commercially available stannous oxide (99% purity) and calcium oxide (99% purity) were pulverized to 100 μm or less, so that the atomic ratio (sn: Ca) was 1: 0.5. mixing. The mixture was charged into a mold having an inner diameter of 20 mm and a height of 5 mm. The mixture was pressurized with a hydraulic jack at a pressure of 150 to 160 kg / cm2 for 10 seconds, and then the obtained agent was crushed, and then sieved. The agent that passed through a sieve opening of 3.36 mm but did not pass through a sieve opening of 2.00 mm was used as a purifying agent. (Purification test) The above-mentioned purifying agent was filled into a purifying cylinder made of SUS316L having an inner diameter of 23.9 mm and a length of 200 m, so that the filling length was 100 mm. After the temperature of the purifying agent of the purifying cylinder is heated to 400 ° t, the gas containing NF 3 (flow rate 1 3 · 4 6 m 1 / mi η) (g 10 flow rate 1 3 4 6 m 1 / mi η) is heated. ) It is introduced into the purification cylinder to purify the gas containing NF3. At this time, 'a part of the purified gas discharged from the exhaust port of the purification cartridge-13-200401663 is taken every 10 minutes' and analyzed by gas chromatography (lower detection limit 10 ppm). To determine the purification treatment amount (L) (purification treatment capacity) of nf 3 per 1 L (liter) of the cleaning agent, check the presence or absence of NOx emission using a test tube (manufactured by Vasco). The results are shown in Table 1. Examples 2 and 3 Except that the mixing ratio of stannous oxide and calcium oxide of the purifying agent of Example 1 was reached by the ratio of the number of atoms (S n: C a) to 1: 0.3, 1: 0.75, respectively. Except for the mixture, the cleaning agent was prepared in the same manner as in Example 1. Using these purifying agents, a purifying test of N F 3 was performed in the same manner as in Example 1. The results are shown in Table 1. 7 \\ 0 Examples 4 and 5 The NF3 purification test was performed in the same manner as in Example 1 except that the concentration of NF3 in the purification test in Example 1 was changed to 0.2% and 2.0%, respectively. . The results are shown in Table 1. Examples 6 and 7 A scavenger was prepared in the same manner as in Example 1 except that the calcium oxide prepared in the scavenger of Example 1 was replaced with calcium hydroxide and calcium carbonate, respectively. Using these purifying agents, a purifying test of NF3 was performed in the same manner as in Example 1. The results are shown in Table 1. Examples 8 and 9 A scavenger was prepared in the same manner as in Example 1 except that the calcium oxide prepared in the scavenger of Example 1 was replaced with magnesium oxide and an oxide saw, respectively. Using these purifying agents, a purifying test of NF3 was performed in the same manner as in Example 1. The results are shown in Table 1. Example 1 0 -14- 200401663 (preparation of purifying agent) A commercially available stannous oxide (purity: 99%) and lanthanum oxide (purity: 99%) were pulverized to 100 // m or less, so that the atomic ratio ( Sn: La) was mixed to 1: 0.5. After the mixture was charged into a mold having an inner diameter of 20 mm and a height of 5 mm, the mixture was press-molded with a pressure of 150 to 160 kg / cm2 for 10 seconds using a hydraulic jack, and then the obtained agent was pulverized, and then passed through a sieve of 3.3 6 mm with a sieve. Agents that do not pass through a sieve opening of 2.0 mm are used as purifying agents. (Purification test) The above-mentioned purifying agent was filled into a purifying cylinder made of SUS3 16L having an inner diameter of 23.9 mm and a length of 200 mm so that the filling length was 100 mm. After the temperature of the purifying agent of the purifying cylinder is 400 ° C, nitrogen (total flow rate 1 3461111/111 丨 11) containing NF3 (flow rate 13.4 6) 111/1 ^ 11) is introduced into the purifying cylinder to purify the gas containing NF3. . At this time, a part of the purified gas discharged from the exhaust port of the purification cartridge was taken every 10 minutes, and analyzed by gas chromatography (lower detection limit 10 ppm), and the time until detection of NF3 was measured. ) Purify the amount of purification treatment (L) (purification treatment capacity) of NF3 of the cleaning agent, and check the presence or absence of NOx emission with a test tube (manufactured by Vasco). The results are shown in Table 1. Examples 1 and 12 Except that the mixing ratio of stannous oxide and lanthanum oxide in the cleaning agent of Example 10 was prepared according to the atomic ratio (S n: L a) to reach 1: 0 · 3, 1: 0 A scavenger was prepared in the same manner as in Example 10 except that the mixing was performed in 75. Using these purifying agents, a purifying test of NF3 was performed in the same manner as in Example 10. The results are shown in Table 1. Example 1 3, 1 4 -15- 200401663 Except that the concentration of NF3 in the purification test of Example 10 was changed to 0.2% and 2.0%, respectively, other NF3 was performed in the same manner as in Example 10. Purification test. The results are shown in Table 1. Example 1 5 and 16 A scavenger was prepared in the same manner as in Example 10 except that the lanthanum oxide prepared as the scavenger in Example 10 was replaced with lanthanum hydroxide and lanthanum carbonate, respectively. Using these purifying agents, a purifying test of NF3 was performed in the same manner as in Example 10. The results are shown in Table 1. Example 17 7 (Preparation of Purifying Agent) Commercially available stannous oxide (purity: 99%), calcium oxide (purity: 99%), and lanthanum oxide (purity: 99%) were pulverized to 100 μm or less, and the atomic ratio ( Sn: Ca: La) was mixed so as to have a ratio of 1: 0.3: 0.2. After filling the mixture into a mold having an inner diameter of 20 mm and a height of 5 mm, the mixture was press-molded with a pressure of 150 to 160 kg / cm2 for 10 seconds using a hydraulic jack, and the obtained agent was pulverized, and then passed through a sieve to pass a 3.3 6 mm Agents with sieve openings that do not pass through 2.00mm sieve openings are used as purifying agents. (Purification test) · The above-mentioned purifying agent was filled into a purifying cylinder made of SUS3 16L having an inner diameter of 23.9 mm and a length of 200 mm, so that the filling length was 100 mm. The temperature of the purifying agent in the purifying cylinder is heated to 40 (TC), and nitrogen containing NF3 (flow rate 1 3.4 6 η 1 / mi η) (total flow rate 1 3 4 6 m 1 / mi η) is introduced into the purifying cylinder to purify the NF3 gas. At this time, a part of the purified gas exhausted from the exhaust port of the purification cylinder was taken every 10 minutes, and analyzed by gas chromatography (lower detection limit 10 ppm), and the time until the detection of NF3 was measured. (Liter) of NF3 -16-200401663 of the purifying agent, while checking the purifying treatment amount (L) (purifying treating capacity), check the presence or absence of ΝΟ × discharge with a test tube (manufactured by Vasco). The results are as follows: Shown in Table 1. Example 18 Except that the mixing ratio of stannous oxide, calcium oxide, and lanthanum oxide of the purifying agent prepared in Example 7 to the atomic ratio (Sn: Ca: La) was 1:02: 〇3 Except for mixing, “Surfactants were prepared in the same manner as in Example 17 and these detergents were used.” The NF3 purification test was performed in the same manner as in Example 17. The results are shown in Table 1. Comparative Example 1 (Purification Formulation of the agent) To 1 000 g of commercially available stannous oxide (purity 99%), add An aqueous solution of 50 g of potassium fluoride (KF, manufactured by Kanto Chemical Co., Ltd.) and dissolved in 65 g of water was mixed. The obtained cake was extruded from a nozzle plate having a diameter of 1.6 mm with an extrusion molding machine and cut. The obtained molded article was made into particles having a length of about 3 to 5 nm. 'Dried for about 12 hours while heating to 1 20 ° C under a nitrogen atmosphere. (Purification test) Except using the above-mentioned cleaning agent, the same as in the examples 1 The NF3 purification test was performed in the same way. However, the pressure loss of the purification cylinder was increased before the detection of NF3. Therefore, the purification test was terminated. The presence or absence of N 0 x was discharged, and the time for which the purification test was terminated was calculated. The results of the purification treatment amount (L) (purification treatment capacity) of NF3 per 1 L (liter) of the purification agent are shown in Table 1. Comparative Example 2 A commercially available calcium oxide (purity: 99%) was pulverized to 100 μm or less, and charged with After inserting it into a mold with an inner diameter of 20 mm and a height of 5 mm, use a hydraulic jack to press and mold with a pressure of 150 to -17-200401663 16 0 kg / cm2 for 10 seconds, and then pulverize the obtained agent. The sieve will pass through a 3.36mm sieve and will not pass 2.00 A sieve with a diameter of mm was used as a purifying agent. A purifying test of NF3 was performed in the same manner as in Example 1 except that the purifying agent described above was used. However, it was confirmed that thousands of ρ ρ ππ of N 0 were discharged immediately after the purification test was started. 'So the cleanup test was terminated. Comparative Example 3 A commercially available lanthanum oxide (99% purity) was pulverized to a size of 100 μm or less, and it was loaded into a mold with an inner diameter of 20 mm and a height of 5 mm. The oil pressure was 150 to 160 kg / cm2. After forming under pressure for 10 seconds, the obtained agent was pulverized, and the agent passing through a sieve hole of 3.36 mm but not passing through a sieve hole of 2.00 mm was used as a sieving agent with a sieve. A purification test of NF3 was performed in the same manner as in Example 1 except that the above-mentioned purifying agent was used. However, it was confirmed immediately after the start of the purification test that thousands of ρ p m of NO was discharged, so the purification test was terminated. Effects of the Invention The present invention provides a purifying agent and a purifying method for a nitrogen fluoride-containing gas. The purifying agent contains stannous oxide as an active ingredient, and oxides, hydroxides, carbonates, and lanthanides of alkaline earth metals. One or more compounds selected from the oxides, hydroxides, and carbonates of the elements are purified by contacting the nitrogen fluoride-containing gas with the above-mentioned purifying agent in a purification method. The purifying agent can be easily stored and used, and does not cause thermal breakdown due to the type of diluent gas during purification, or severe heat generation and harmful gas generation in the post-purification post-treatment. In the purification cartridge, no increase in pressure loss or occlusion of '18 -200401663 occurred, and further, NOx was not discharged, and nitrogen-fluoride-containing gas could be efficiently purified. Schematic description: None
-]9- 200401663 表1 淨化劑成份 (原子數比） 有害 成份 濃度 (%) 淨化溫度 (°C) 淨化處理 能力 吨的 排出 實施例1 SnO, CaO (1:0.5) nf3 1.0 400 124 ^frrr 寸 lit: 實施例2 SnO, CaO (1:0.3) nf3 1.0 400 132 Μ j\\\ 實施例3 SnO, CaO (1:0.75) nf3 1.0 400 115 >fnr ^Ttr j\\\ 實施例4 SnO, CaO (1:0.5) nf3 0.2 400 129 4m. iMl J \ \N 實施例5 SnO, CaO (1:0.5) nf3 2.0 400 102 4rni l it I j\\\ 實施例6 SnO, Ca(0H)2 (1:0.5) nf3 1.0 400 102 M j\\\ 實施例7 Sn〇，Ca(C〇3)2 (1:0.5) nf3 1.0 400 88 4rrr II IT 實施例8 Sn〇,Mg〇（1:0.5) nf3 1.0 400 130 4txT- ntll： 實施例9 SnO, SrO (1:0.5) nf3 1.0 400 89 >fnr 寸111 實施例10 SnO, La203 (1:0.5) nf3 1.0 400 128 >fnr. jitr y\\\ 實施例11 SnO, La203 (1:0.3) nf3 1.0 400 120 Ατττ ΤΠΤΤ j\\\ 實施例12 SnO, La203 (1:0.75) nf3 1.0 400 101 Titr 實施例13 SnO, La203 (1:0.5) nf3 0.2 400 131 4rrt Tlln 實施例14 Sn〇，La2〇3 (1:0.5) nf3 2.0 400 99 4nr. ΊΙΙ l J \ 實施例15 Sn〇，La(〇H)3 (1:0.5) nf3 1.0 400 81 >fnT in Γ J\ \N 實施例16 SnO, La2(C03)3 (1:0.5) nf3 1.0 400 76 1Ι1Γ 實施例17 Sn〇，CaO, La2〇3 (1:0.3:0.2) nf3 1.0 400 122 4nx till J \\\ 實施例18 Sn〇，Ca〇，La2〇3 (1:0.2:0.3) nf3 1.0 400 118 4rrr. ΤΠΤ 比較例1 SnO, KF nf3 1.0 400 62 4m： ΤΤΤΠ j\ \\ 比較例2 CaO nf3 1.0 400 — 有 比較例3 L3,2〇^ nf3 1.0 400 — 有-] 9- 200401663 Table 1 Purifier composition (atomic ratio) Hazardous component concentration (%) Purification temperature (° C) Purification treatment capacity Tons of discharge Example 1 SnO, CaO (1: 0.5) nf3 1.0 400 124 ^ frrr Lit: Example 2 SnO, CaO (1: 0.3) nf3 1.0 400 132 Μ j \\\ Example 3 SnO, CaO (1: 0.75) nf3 1.0 400 115 > fnr ^ Ttr j \\\ Example 4 SnO, CaO (1: 0.5) nf3 0.2 400 129 4m.iMl J \ \ N Example 5 SnO, CaO (1: 0.5) nf3 2.0 400 102 4rni l it I j \\\ Example 6 SnO, Ca (0H ) 2 (1: 0.5) nf3 1.0 400 102 M j \\\ Example 7 Sn0, Ca (C〇3) 2 (1: 0.5) nf3 1.0 400 88 4rrr II IT Example 8 Sn0, Mg〇 ( 1: 0.5) nf3 1.0 400 130 4txT-ntll: Example 9 SnO, SrO (1: 0.5) nf3 1.0 400 89 > fnr inch 111 Example 10 SnO, La203 (1: 0.5) nf3 1.0 400 128 > fnr jitr y \\\ Example 11 SnO, La203 (1: 0.3) nf3 1.0 400 120 Ατττ ΤΠΤΤ j \\\ Example 12 SnO, La203 (1: 0.75) nf3 1.0 400 101 Titr Example 13 SnO, La203 ( 1: 0.5) nf3 0.2 400 131 4rrt Tlln Example 14 Sn0, La2 03 (1: 0.5) nf3 2.0 400 99 4nr. ΊΙΙ l J \ real Example 15 Sn〇, La (〇H) 3 (1: 0.5) nf3 1.0 400 81 > fnT in Γ J \ \ N Example 16 SnO, La2 (C03) 3 (1: 0.5) nf3 1.0 400 76 1Ι1Γ Example 17 Sn0, CaO, La2 03 (1: 0.3: 0.2) nf3 1.0 400 122 4nx till J \\\ Example 18 Sn0, Ca0, La2 03 (1: 0.2: 0.3) nf3 1.0 400 118 4rrr. ΤΠΤ Comparative Example 1 SnO, KF nf3 1.0 400 62 4m: ΤΤΤΠ j \ \\ Comparative Example 2 CaO nf3 1.0 400 — Yes Comparative Example 3 L3, 2〇 ^ nf3 1.0 400 — Yes