302444 A7 B7 五、發明説明（/ ) 〔産業上的利用領域〕 本發明像鼷於包含在廢棄氣龌内之氣態《之處理•回 收裝置及其方法，尤指一種渉及光化學煙塵原因物質之 氣態烴的濃度使之在1V0L%以下而將其釋放在大氣中所 餺之工業上裝置及方法，並有關於包含在廢棄氣鱧之氣 態烴處理·回收裝置及其方法。 〔既有之技術〕 防染大氣層原因之一種光化學煙塵像由NO X與氣態烴 之反應所生成，綦此乃為以往所習知。 據此，過去以日本、美國、歃洲為首之先進國家，最 近即在台薄、墨西哥、中國、韓國等，以法律規範《格 限制形成防染源原因之NOx以及包含在大氣中揮發性烴 的排放濃度標準，為使此等規範數值透明化起見，在各 地大董設置有工業上規棋之處理•回收裝置。 其中，所以特別重視做為氣態烴發生源的問題，乃由 於貯藏揮發性烴類之際，在起货或存貨時從貯存樯或油 槽船所發生之廢棄氣釀，同時儲存在油雄槽時從油罐車 所發生之廢棄氣黼》 經濟部中央棣準局負工消費合作社印製 (請先閲讀背面之注$項再填寫本頁) 此種含有氣態烴廢棄氣驩之處理以及回收方法，以往 所廣泛使用之方法，即包括有 (1) 在特公昭54-8632號公報，待公昭54-5789號公報， 待公昭58-022503號公報等所掲載方式所示之吸收法。 (2) 使用氣醱分雄膜之方法（氣鼸分離膜法） (3) 強冷卻至-60〜70°C使之液化之方法， 本紙張尺度適用中國國家標準（CNS ) A4规格（210X：297公釐） 經濟部中央樣準局員工消费合作社印製 309444 A7 __B7_ 五、發明説明（> ) (4)使用活性硪或合成沸右之吸附方法等。 t 在以上（1)〜（4)之方法當中，由（1)之圾收法所示之 含有氣態烴醆棄氣臞之處理及回收法，在日本朗最為被 廣泛採用之方法。 玆針對此吸收法之處理及回收方法，詳加說明之，此 方法像包含， ♦將含有氣態《廢楽氣龌導入於吸收塔，以向流進行廢 棄氣體與有機液鼸吸收液的氣液鼸接»，以吸收液吸 收廢棄氣鼸中之氣態烴步爨。 •將吸收後之氣鼸從吸收塔的頂部排放於大氣中之步驟， •將吸收氣態烴之吸收液在真空容器中逬流蒸發，從該 吸收液分離及回收氣態《之步骤， •將分離及回收後之吸收液再度循回至吸收塔，予以循 瓌使用之步班方法（參照前所掲示之待公昭58-022503 號公報）。 〔發明所欲解決之課題〕 上述第（1)項吸收法所掲示之”含有氣觼《廢窠氣龌之 處理及回收法乃係從吸收塔之頂部釋放在大氣中之氣態 «濃度，即由真空容器之真空度而決定。 亦即，從吸牧塔頂部釋放在大氣中之氣戆«鼸度，例 如基於在日本之各都府縣所制定之防止公害條例像在5 V0L%以下，如此即有必要將真空度保持在30··Ηβ以下。 其中，除日本外，在歃美先進國家、台鼸、墨西哥等 國家，即刻意將排放鼸度訂定在美國環塊保護局（ΕΡΑ) 本紙張尺度適用中國國家梂準（CNS ) Α4規格（210Χ297公釐） ------Τ--i 裝------訂------Z: (請先閲讀背面之注意事項再填寫本頁) 經濟部中央揉準局負工消費合作社印裝 A7 __B7 _ 五、發明説明（今） 所規定之1V0L%以下（38Bg/L以下）。 t 欲使該規範數值播致明確起見，採取以上π)項吸收 法為例子，即有必要將真空容器的真空度限定在7*mHg 以下，尤其如考盧及配管中流動吸收液的阻抗損失時則 有必要將其限定在及以下。 然而，在此種真空度操作時，吸收液本身有一部分蒸 發，故不耐於循琛使用。一方面，迄今尚未見及有在2 muHg之高真空可處理 1〇〇〜2000b3 / Hr大置釋放氣醴 的真空泵。 是以，就以上（1)項之吸收法而言，頗難使釋放氣饑中 之烀澳度維持在1V0L%以下，迄今為上尚未實現過。 又，對於使用以上（2)項之氣讎分離膜之方法（氣鼸分 離膜法）亦具有相同之情形，使廢棄氣龌中之烴濃度處理 成1V0L%以下之技術，則尚未完成。 一方面，_於以上（3)項之強冷至-60〜-701C使之液化 之方法，在到逢露黏（de* point)時氣態《並不會被液 化。 玆針對此方法詳細說明之，廢棄氣鼸中之氣態熳濃度 為5 0〜1 0 0 V 0 L %之高»度時，如有少悬之甲烷，乙烷， 丙烷等成分，則，將其深度冷卻至-70 t：以下並去除 甲烷，乙烷而速到露黏.如此則有可能保持在1V0L%。 然而，廢棄氣臞中之熳濃度•如在貯藏及卸装石油等 «時，通常為5〜50V0L%之低囊度。 是以，玆針對石油之情況而言，如將其深度冷卻至 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） ------Υ---4 裝------訂------C冰 (請先閱讀背面之注意事項再填寫本頁) 經濟部中央橾準局員工消費合作社印製 S0Q444 A7 __B7_ 五、發明説明（4 ) -100TC附近時並無法將其保持在1V0L%以下。又，在約 -70t：刖可使用二«甲烷做為冷媒，惟此種冷媒，最近 刖因其毒性而有使用上問題，同時迄今尚未見及有在經 濟上可堪使用之可冷卻至- loot：的冷媒。 因此，將廢窠氣鼸中之烴嫌度保持在1V0L%以下之方 法，依現狀而言，雖有使用以上（4)項之活性硪或令成 沸石的吸附法，惟鬭於此種方法，則有如以下一般之問 題。 亦即，使用活性硪以吸附氣態《時以吸附熱，如以汽 油蒸汽為例，則為10〜15KCAL/奠耳，氣鼸Λ (汽油量） 愈多時則所發生之吸附熱愈為大量。如此，使活性磺吸 附塔的溫度上升，致常常發生火災事故。 防止此事故所用之手段，可考*(Α)在導入於吸收塔 之廢棄氣龌混合以空氣，減少毎單位時間之吸附熱，保 持該吸附塔的上升溫度在約6010以内。 然而，於廢棄氣饑故意输入空氣使之變為稀薄，則頗 為不經濟，同時因空氣之混合致被處理氣鼸依其比例增 加，如此則需加大吸附塔及附屬裝置，在經濟上亦不能 成立。 又，雖曾考慮及（Β)用水冷卻吸附塔並加以除熱，惟 縱然使用冷卻水亦僅能利用水的顯熱而已，尚無法期待 具有某種程度的冷卻效果。 至於，加大冷卻面稹，則基於單鈍之冷部效果為理由 而擴充吸附塔為必要以上措置，殊非有經濟上之效益。 本紙張尺度適用中國國家樑準（CNS ) Α4規格（210Χ297公釐） ----Ρ--.J---4 裝------訂-----丄 | (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局負工消費合作社印製 A7 B7 五、發明説明（r ) 更且，雖考嫌及以（C)如四氰化磺一般低沸黏而不燃性 f 冷媒的除熱方法，但採用此種方法時，無法將因奪取吸 附熱而使蒸發之四氯化磺釋放在大氣中，故有必要再度 予以冷卻使四氯化磺蒸汽維持在沸點以下而循回至原先 之液髏四氯化硪，此方法亦不具有經濟上效果。 一方面，做為活性硪吸附塔之除熱手段，即己鬭發有 使用蒸發潛熱大之液態烴（例如液髅石油）做為冷媒之方 法，且此種方法，在國外亦曾被廣泛採用。 此方法為，在吸附塔的内外部配設以液態烴的通路· 其中通過以液態烴，並利用其蒸發潛熱而進行除熱，並 將蒸發之烴氣讎以同種之液鼸《洗淨而予以回收之方法。 以上方法，雖使用冷卻水比較有優異的冷卻效果，但 如果液體烴的通路破損時，則有建帶發生火災事故之盧 ，因此，需將其設置在逋離居家，故仍有其缺失在。 至於，吸附塔的操作方法，一般换採用交互切換吸附 步驟以及解附步驟之邇轉方式，此方法為， • PSA(Pressure Swing Adsorption)循琢方式， • PTSA (Pressure and Teaperature Swing Adsorption) 循琛方式，而以上方式則為既知之技術。 關於PSA循琛方式，其中之解附步期乃為使用出口氣 黼的一部分做為清洗氣謹之方法，如此則因清洗最增大 而頗難以做囊繡後處理之缺點。 又PTSA循瓖方式，乃為使用霣熱加熱等做為解附手段 之加熱方法，此方法，偽由加熱進行解附，將吸附塔金 -7 - 本紙張尺度適用中國國家橾準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局貝工消费合作社印製 A7 __B7_ 五、發明説明（b ) 面施予加溫，冷卻，結果導致大Λ之熱損失，故在傅熱 時刖有耗費畏時間之缺點。 其中，_於氣態烴的濃度形成為1V0L%以下之稀薄廢 棄氣氣黼的處理法而言，以使用習知之活性磺或合成沸 石的吸附法最具有效，此種低囊度廢索氣鼸的處理法， 則以此種吸附法最具替遍。 然而，依現況而言，尚未存在有包含嫌厚之氣態烴， 處理100·3 /Hr以上大量廢棄氣饑，從該醆棄氣讎以良 好效率回收烴，並將排放在大氣中氣鼸之殘存濃度在1 VOL%以下之經濟上處理及回收装置或處理及回收方法。 本發明因鑑於以上之缺失，其目的偽在於提供一種處 理含有氣態®廢棄氣髑，補集及回收氣態烴之裝置及其 方法，同時從該廢棄氣鼸以高效率回收烴之外，並將排 放於大氣中氣釀之殘存濃度減少至1V0L%以下，以及在 廢窠氣驩中所含氣態《之處理·回收裝置及其方法。 又，本發明之另一目的在於提供一種將引起光化學》 塵原因物質之氣態烴之濃度減少至IV 0L%以下而予以釋 放之工業上裝置及其方法。 〔解決問題所需之手段〕 本發明旨在於達成以上之目的，而使用單塔式乃至多 塔式的吸附装置，其待擻為， ♦装《在該吸附装置之吸附劑，愾使用孔徑為4〜100埃 (augstroa)之合成沸石及/或疏水性砂隳，因此， •以該吸附爾做為吸附曆，由混合不同孔徑之上述吸附 本紙張尺度適用中國困家揉準（CNS ) A4规格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 裝------訂------(------- 經濟部中央標準局貝工消費合作社印製 A7 __B7_ 五、發明説明（7 ) 薄I之混合層或不同孔徑之吸附劑彼此装缜成多曆而形 成為吸附劑暦。 是以，依照本發明可逕予處理廢棄氣豔中之氣臁®蠹 度變為稀薄，同時可將以往之吸附法無法處理之「含有 約30 VOL%以上濃度之氣態烴廢棄氣髓」變為可能，對 於如此高濃度慵況，亦得以容易地將排放於大氣中氣饑 的殘存烴濃度維持在1V0L90以下，而且，有關於本發明 所用之裝置，亦可以達成小型化，形成一種可資拥I邇之 手提式裝置者。 亦即，醑於本發明之装置，愾以 「使用單塔式乃至多塔式的吸附装置於包含在廢棄氣 黼之氣態烴施予處理及回收裝置中，採用孔徑為4〜100 埃之合成沸石及/或疏水性矽謬裝«在該吸附装置做為 吸附劑，且由該吸附劑所形成之吸附靥，混合以不同孔 徑之吸附劑形成為混合層或將不同孔徑之吸附阐各自裝 «成多曆成為吸附薄麕為其特揪之含有廢窠氣髓之氣態 烴的處理及回收装置。」（申謫專利範圃第1項） 為要者旨。 又，鬭於本發明之方法，即以 「使用單塔式乃至多塔式的吸附装置於包含在廢窠氣 鱧之氣態烴施予處理及回收方法中，採用孔徑為4〜100 埃之合成沸石及/或疏水性矽醪裝《在詼吸附装置做為 趿附劑，且由該吸附_所形成之圾附層，混合以不同孔 徑之吸附劑形成為混合層或將不同孔徑之吸附_各自裝 本紙張尺度適用中國國家梂準（CNS ) A4規格（210X297公釐〉 ----*--Γ---4 裝------訂------1 ) (請先閲讀背面之注意事項再填寫本頁) A7 B7 經濟部中央揉準局貝工消費合作社印製 五、發明説明（S ) 1 1 J* 成 多 靥 成 為 吸 附 劑 層 9 在 上 述 吸 附 靥 導 入 以 含 有 氣 態 t 1 1 烴 廢 棄 氣 觴 t 處 理 該 廢 棄 氣 嫌 * 在 解 附 時 • 01 以 從 上 述 1 1 吸附靥所排放之部分結果氣黼及/或空氣加以清 洗 > 並 請 ! 先 從 該 清 洗 氣 釀 回 收 氣 態 烴 為 特 擻 之 含 有 廢 棄 氣 鼸 之 氣 態 閲 讀 la 烴 之 處 理 及 回 收 方 法 〇 J (申誚專利範圍第3 ί項） 背 Λ 1 I 之 1 1 * 為 要 者 旨 〇 注 意 \ | 以 下 玆 針 對 有 鬭 於 本 發 明 装 置 及 其 方 法 詳 加 說 明 之 〇 事 項 再 1 1 本 發 明 者 等 • 即 針 對 使 用 Q9 塔 式 乃 至 多 塔 式 之 吸 附 裝 填 寫 本 裝 置 於 包 含 在 m 棄 氣 m 之 氣 態 烴 施 予 處 理 及 回 收 裝 置 及 其 頁 1 I 方 法 中 • 經 潛 心 研 究 結 果 » 發 現 装 填 在 該 吸 附 装 置 之 吸 1 1 附 剤 氣 孔 徑 對 於 氣 態 的 吸 附 量 深 具 有 影 m t 且 與 氣 態 1 I 烴 的 分 子 大 小 亦 有 鼷 像 • 而 以 厂 使 用 氣 孔 徑 在 所 鼸 定 範 1 訂 圍 内 的 不 燃 性 吸 附 m (孔徑為4 100埃之合成沸石及/ 1 或 疏水 性矽腰）為特徽」 遽而完成本發明。 1 | 亦 即 • 氣 態 α 之 分 子 大 小 一 定 時 > 可 使 用 具 有 一 定 孔 1 I 徑 之 吸 附 m 9 例 如 處 理 如 石 油 m 氣 一 般 之 異 鏈 院 烴 » 正 1 丄 鏈 院 黼 烴 * 烯 烴 9 瑷 院 颶 烴 9 芳 族 烴 等 分 子 大 小 彼 此 相 1 異 成 分 所 形 成 之 氣 匾 時 > 刖 有 必 要 與 吸 附 孔 各 白 之 大 小 1 j 相 應 一 致 〇 1 1 其 中 • 如 使 用 孔 徑 分 佈 範 園 m 廣 之 活 性 m 時 1 則 可 吸 1- 附 上 述 之 全 部 成 分 » 由 於 吸 附 量 遇 多 • 随 著 此 種 吸 附 而 1 1 發 生 大 量 之 吸 附 熱 » 結 果 9 致 吸 附 層 的 溫 度 急 激 上 升 • \ 1 而 有 引 發 火 警 的 危 險 性 〇 1 I 因 此 » 如 為 活 性 m 之 情 形 • 刖 如 前 述 雖 有 去 除 熱 手 段 1 1 -10- 1 1 1 1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 309444 A7 B7 經濟部中央樣準局員工消費合作社印製 五、發明説明 ( 9 ) 1 1 為 其 必 要 條 件 9 但 去 除 此 種 熱 能 殊 非 易 事 0 1 1 相 反 者 9 本 發 明 % 如 前 述 9 % 使 用 一 定 孔 徑 範 圃 (4 1 I 10 〇埃） 之 不 同 孔 徑 的 合 成 沸 石 及 / 或 疏 水 性 矽 驩 > 依 此 請 1 1 9 可 併 合 使 用 與 構 成 廢 棄 氣 龌 中 氣 態 烀 各 分 子 彼 此 大 小 先 閲 1 |« 相 應 一 致 孔 徑 之 合 成 沸 石 及 / 或 疏 水 性 矽 膠 〇 fK 背 1 1 態 烴 的 吸 之 1 是 以 » 依 照 本 發 明 可 以 控 制 廢 棄 氣 體 中 之 氣 注 意 \ 附 量 進 而 可 控 制 及 附 熱 > 此 結 果 » 可 將 趿 附 裝 置 金 面 事 項 1 I 再 1 之 吸 附 層 的 熱 佈 播 得 均 勻 防 止 因 吸 附 熱 而 使 溫 度 急 激 上 升 f 並 可 預 期 該 吸 附 装 置 達 成 萬 全 之 安 金 性 〇 寫 本 頁 裝 1 使 用 活 性 硪 之 既 有 方 法 » 像 提 議 在 該 吸 附 層 内 摻 混 細 1 1 砂 及 石 頭 或 不 燃 性 並 有 大 熱 容 量 的 粒 狀 無 機 物 質 等 > 並 1 I 依 此 在 吸 附 層 内 所 産 生 之 局 部 加 熱 予 以 分 散 之 方 法 〇 1 1 惟 關 於 章 圖 厂 將 所 使 用 吸 收 劑 的 吸 附 孔 徑 與 被 吸 附 分 訂 I 子 併 合 J 之 本 發 明 裝 置 及 其 方 法 而 言 > 如 以 實 際 裝 置 加 1 I 以 操 作 並 詳 細 調 査 吸 附 層 内 的 溫 度 分 佈 » 已 知 在 整 個 吸 1 1 附 層 形 成 有 均 勻 之 溫 度 〇 1 對 於 此 種 厂 整 傭 趿 附 溫 度 的 均 勻 化 J 而 言 > 如 參 照 1 以 下 有 關 於 本 發 明 方 法 的 資 施 例 做 更 進 — 步 之 説 明 » 即 1 1 在 吸 附 劑 層 (A) 〔孔徑 :由約5 埃之合天 K沸石所形成之 I 吸 附 劑 層 吸 附 氣 够 烴 時 所 發 生 的 熱 量 1 僅 能 吸 附 因 受 1 吸 附 孔 徑 限 制 而 所 決 定 之 氣 態 烴 分 子 〇 因 此 » 此 吸 附 爾 1 1 層 (A)所發生的熱悬， 其數*並不多。 往下的吸附劑層 • 1 1 (B), 吸附劑靥< C)亦 有 相 同 之 情 形 0 I 1 冊] ί 1 1 1 1 1 1 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 經濟部中央標準局貝工消费合作社印製 A7 B7 五、發明説明（、。） 亦即，依照本發明，偽企圃將吸附熱予以分散，使在 f 吸附曆内流動之氣流中混然形成為一鼸化，從吸附裝置 之上端至下端形成大致均勻之溫度。 本發明卽如前述，其偽可處理以往吸附法認為頗難實 施之約30V0L%以上高濃度的含有氣態烴廢棄氣鼸，關於 此種情況，非但可沿整餹吸附曆使溫度大致逹成均勻， 而且有颺於此種高濃度的被處理氣體（廢棄氣黼）情形， 亦可以使排放在大氣氣醱中之殘存烴灌度維持在IV 0L % 以下。 相反者，習知之吸附法或氣黼分離膜法，雖可適用於 含有濃厚氣態烴的釋放氣鼸之處理，但如前述.此項技 術尚無法完成釋放氣讎中的烴濃度保持在1V0L%以下。 又，依照此種吸收法或氣醱分離膜法，在處理後釋放 在大氣中氣醱之濃度，一般為2〜5V0L%。 至於，習知吸附法的優點為，對於處理發生少量吸熱 熱之含有稀薄氣態《的釋放氣鼸，極為有效，此時，通 常在入口之鼸度為1V0L%以下，而出口之蠹度則為PPM 之等级。 此吸附法的缺黏為，如前所述，在處理含有濃厚氣態 烴之釋放氣醱時，會發生大量的吸附熱。 雖然已開發有使用蒸發潛熱大的液鼸烴（例如液黼石 油）做為除去此種吸附熱冷媒之方法，惟如上述仍具有 ι>». 危險性。 再者，雖曾考嫌使用水或低沸黏不燃性的四氯化磺等 -12- 本紙張尺度逋用中國國家梂準（CNS ) A4規格（210X297公釐） (請先聞讀背面之注意事項再填寫本頁) 訂 丄 309444 B7 經濟部中央標準局貝工消费合作社印製 五、發明説明（ vl ) 1 1 做 為 冷 媒 » 惟 如 前 述 > 如 為 水 的 情 形 參 則 不 能 期 待 其 所 1 1 希 望 的 冷 卻 效 果 1 又 » 如 為 四 氯 化, 硪 的 情 形 » 則 因 奪 取 1 1 吸 附 熱 而 蒸 發 之 四 氱 化 m 等 無 法 將 其 釋 放 在 大 氣 中 » 故 /-V 請 1 符 先 1 需 將 其 冷 卻 至 沸 點 以 下 再 度 循 回 至 原 先 之 液 龌 仍 不 閲 讀 L 1 經 濟 上 效 益 〇 背 1 1 之 1 本 發 明 所 涉 及 之 使 用 單 塔 式 乃 至 多 塔 式 的 吸 附 裝 置 • 注 意 -1 1 將 包 含 在 廢 棄 氣 鼸 之 氣 態 % 處 理 • 回 收 裝 以 及 其 方 法 *事 項 再 1 i ♦ 如 前 所 述 為 使 用 發 生 吸 附 熱 而 導 致 吸 附 曆 急 激 溫 度 填 寫 本 裝 上 升 播 得 降 下 起 見 9 将以往所汎用之可燃性话性硪吸 頁 1 I 附 劑 換 成 為 厂 以 一 定 孔 徑 範 園 (4 100 埃） 而 有 不 同 孔 徑 1 1 的 不 燃 性 合 成 沸 石 及 或 疏 水 性 之 矽 醪 J 9 並 藉 由 控 制 由 1 1 合 成 沸 石 及 / 或 疏 水 性 矽 醪 所 形 成 吸 附 m 之 孔 徑 與 吸 1 訂 附 量 9 並 將 其 作 成 可 任 意 控 制 吸 附 層 的 通 度 〇 1 在 本 發 明 中 9 對 於 做 為 吸 附 劑 使 用 之 ”合成沸石” rcU, 雜 Anr m 1 I 特 別 之 限 定 9 惟 最 好 僳 使 用 含 有 豐 m 矽 石 之 合 成 沸 石 ( 1 I 待 別 是 活 性 矽 石 )〇 1 另 一 方 面 » 本 發 明 所 使 用 之 "疏水性矽膠’ 9 PI? 不 吸 附 I 水 分 之 疏 水 性 物 質 • 鼷 於 一 種 親 油 性 物 質 0 此 疏 水 性 矽 1 I 驪 之 孔 徑 » 通 常 為 無 規 形 » 除 不 燃 性 之 外 • 其 吸 附 孔 的 1 1 分 佈 • 大 致 與 活 性 m 相 似 其 吸 附 舉 動 亦 與 活 性 磧 類 似。 l· 是 以 » 就 本 發 明 而 言 » 如 將 不 同 孔 徑 吸 着 雨 做 多 段 裝 1 1 » 時 * 最 具 效 果 者 為 將 瑰 水 性 矽 醪 配 置 在 被 處 理 氣 龌 ( \ 1 廢 寨 氣 鼸 )吸附層的最終段 (01 排 放 之 一 段 ) ) 1 I 依 此 可 籣 化 吸 附 步 骤 且 有 可 能 m 裝 置 本 釅 予 以 小 1 1 -13- i 1 1 1 1 本紙張尺度適用中ll國家揉準（CNS ) A4規格（210X297公嫠） 經濟部中央橾準局貝工消費合作社印製 A7 _B7_ 五、發明説明（_> ) 型化，如此，對於以往難以實施之含有_厚氣態烴發窠 t 氣體，與稀薄之氣體一搛，容易將氣鼸殘存烴_度在1 VOL%以下使之排放於大氣中，並依極具經濟效益構成 一有利之条統。 持別是，醑於本發明之上述条統，像適合利用在現行 法規下所實行之「往返於加油站與鐮油場之油罐車在卸 油後成為空車後將石油蒸汽循回於儲油場之情形（回流 方式）」，或美國現況所訂定之排放規範「在城市加油 站對汽車加油之情況」以及「從汽車加油孔所發生之汽 油蒸汽之處理情況J 。 亦即，就加油站而言，由於所設置之監視鼸制無法用 手操動，故其安全性輿操作之簡便性最被重視。 要者，即使不經由監視，由按鈕自動啓閉，期望開發 出不佔場地且安全性極高之防止不害機器，本發明所涉 及之裝置及其方法，可完全符合此期望。 又，鼸於本發明之裝置及其方法，不但適用於習知之 PSA法或PTSA法，而且亦適用於其他之VSA法，VTSA法等 ，此等適用亦包括在本發明中。 再者，本發明愾適用於含有汽油蒸汽排放氣黼的處理 與回收，同時亦適用於其他之苯，丙酮，甲酵等低沸黏 含煜排放氣黼，此等適用均槪括在本發明之内。更且， 本發明傜使用單塔式乃至多塔式之吸附裝置，具醱上，係 最具適用者乃為以下實施例所記載之雙塔式建鑛吸附裝 置，惟本發明並不受此種雙塔式達鑛吸附装置之限制。 -1 4 - 本ϋ尺度適用中國國家梂準（CNS ) A4規格（210X297公釐） ' ----.---.---f 裝------訂-----丄.1 (請先閲讀背面之注意事項再填寫本頁) A7 B7 經濟部中央樣準局貝工消費合作社印製 五、發明説明（G ) 1 1 Γ 實 施 例〕 1 1 以 下 ,列 舉 有闢於 本發明之 装 置 及 其 方 法 的 實 施 例 1 1 1 詳 細 說 明本 發 明，惟 本發明並 不 受 以 下 實 施 例 之 限 制 〇 請 1 先 1 (有關左 >本發明裝置之霄施例） 閱 讀 I 第 1 團你 表 示本發 明一實施 例 之 氣 態 烴 之 處 理 與 回 收 背 A 1 | 之 處 理 的 流程 圖 〇 注 意 1 I 此 實 施例 装 置，如 第1圓所 示 $ 偽 由 吸 附 塔 1 及 吸 附 事 項 再 1 L 塔 3 所 形成 之 雙塔式 缠纊吸附 装 置 9 此 吸 附 塔 2 . 3 僳 填 寫 本 裝 採 用 不 同孔 徑 吸附劑 (孔徑：4 100埃之豐富矽石之合 頁 1 I 成 沸 石 )由3 靥之吸附劑層（A) > (B), (C) 所 構 成 〇 1 1 又 9 就第 1 圏而言 ,1為含 有 汽 油 蒸 汽 廢 棄 氣 體 發 生 1 I 源 $ 4 為吸 引 解附後 淸洗氣龌 之 真 空 泵 t 5 為 汽 油 回 收 1 訂 器 • 6 為將 解 附後的 清洗氣體 分 配 在 汽 油 回 收 器 所 用 之 1 分 配 管 ,7 為 液面計 〇 1 | 又 • 11 , 11 ’為廢棄氣讎送氣管， 12 , 1 2 . 為 排 放 Mm 営 9 1 I 1 3 , 13 '為淸洗用氣黼送氣管， 14 . 1 4 ' 為 解 附 後 之 淸 洗 1 氣 體 送 氣管 1 15為從 汽油回收 器 之 揉 放 氣 am ΒΛ 循 回 於 睡 棄 ，-| 氣 黼 送 氣管 之 回流管 〇 1 1 (有闌於本發明方法之實施例） 1 1 以 下 ,針 對 本發明 方法由實 施 例 逐 加 説 明 〇 又 1 此 實 \ 施 例 偽 使用 以 上第1 _所示装 置 • 處 理 含 有 5^ -30V0L% 1 1 汽 油 蒸 汽之 睡 _氣釅 成為1 VOL% 以 下 之 淸 淨 氣 讎 而 嫌 放 1 1 於 大 氣 * " 方 面，為 回收廢窠 氣 鼸 中 之 JJst Π» 油 蒸 汽 的 實 例。 1 I 本 * 施例 偽使用 不同孔徑 之 β 富 矽 石 之 合 成 沸 石 做 1 1 -15· i 1 1 1 1 本紙張尺度適用中國國家標準（CNS > A4規格（210X297公釐） 經濟部中央揉準局貝工消費合作社印製 A7 __B7_ 五、發明説明（4 ) 為吸附劑，如第1圈所示，使用由3曆吸附««(A), (B) ,(C)所構成之吸附塔2, 3。 具體而言.俱沿著含有汽油蒸汽廢窠氣驩的流向， ♦最初之吸附雨層（A)僳具有約5埃孔徑含有大量矽石 之合成沸石〔東蘇公司産製之” ZSM5(商品名）”：X型 沸石] ♦其次之吸附劑牖（B)僳具有約7埃孔徑含有大量矽石之 合成沸石〔栗蘇公司産製之Y型沸石〕 •最後之吸附劑層（C)愾具有約80埃孔徑之疏水性矽膠 〔寓士矽利矽亞化學公司産製之” Q-l〇(商品名）”〕所 形成。 在本實施例中，像從含有5〜30V0L%之汽油蒸汽廢棄 氣體發生源所排放之廢棄氣臁，以鼓風櫬（圈面無表示） 或自行之壓力，自廢棄氣匾送氣管11, 11'輪送至由以 上吸附薄I層（A), (B), (C)所構成之吸附塔2, 3。 又，吸附塔2, 3,則將吸附步驟與解附步«交互替換 蓮作，而該替換時間為3〜10分鐘。 終結吸附步驟而處理完畢後之醆窠氣龌，刖從吸附塔 2(在替換解附步驟後為吸附塔3)的頂部，介由排放管12 (或排放管12’），將含有1 V0L%以下汽油蒸汽並有溉度 之空氣（清淨氣钃)揉放於大氣中。 一方面，終止吸附步骤後之吸附塔2(替換為吸附步驟 後即為吸附塔3)邸介由淸洗用氣讎送氣管13’（或13)输入 清洗用氣體（空氣），由真空泵4吸引而使之解附。（此 -16- 本紙張尺度適用中國國家梯準（CNS ) A4規格（210X297公釐） --------J.--4 裝------訂------^ ^ (請先閱讀背面之注意事項再填寫本頁) 經濟部中央樣準局貝工消費合作社印製 302444 A7 B7 五、發明説明（β ) 真空泵4偽在約25Torr下蓮轉。） 解附後之含有汽油蒸汽清洗氣鼸，即介由送氣管14’（ 或14)輪至汽油回收器5 ,通過分配管6與液鼸汽油接 觸，回收淸洗氣鼸中之汽油蒸汽形成為液鼸（汽油回收 液）〇 從汽油回收器5之排放氣黼，尚殘存有微置之汽油蒸 汽，故介由回流管15而再度返回至廢棄氣鼸送氣管11, 與廢棄氣體一起進行吸附處理。 又，汽油回收器5,則装設有檢澜液讎汽油位置所禰 之液面計7。且，吸附劑層（A), (B), (C)之溫度，在蓮 轉中彼此像保持在約40¾。即，鬭於吸附劑曆（A) , (B) * ,(C),因有分散吸附熱的功能，故從吸附塔2(3)之上 绱至下端大致保持有均勻之溫度（約40t：)。 第2画傜表示本資施例之蓮轉數據圃示。由該第2圚顥 然可知，依照本實施例，廢棄氣黼中之汽油蒸汽濃度像 介於5〜20 Vol%之變化範園，但無論為何種情況排放 在大氣中之氣體的汽油蒸汽濃度，仍然為〇 %。 〔發明之效果〕 本發明像如上所詳述乃使用單塔式乃至多塔式的吸附 sus aa 裝置， •以孔徑為4〜100埃之*有矽石之合成沸石及/或疏水 性矽睡做為裝馆在該吸附裝置用之吸附爾，並由 •混合不同孔徑吸附_混合層或由不同孔徑吸附W彼此 装埔成為多靥之吸著劑層所構成者為其特微，依此， 本紙張尺度逍用中國國家梂準（CNS ) A4规格（210X297公釐） ---->--.----{裝------訂------f:·».- (請先閱讀背面之注意事項再填寫本頁) 經濟部中央樣準局貝工消費合作社印製 A7 B7五、發明説明（4 ) 不拘其濃度在處理含有氣態®廢窠氣鱧時，容易将排 放在大氣中氣體所殘存之烴維持在1 Vol%以下，産 生顯著之效果。 而且有關於本發明之裝置，可使其形成為搬動型的手 提式裝置，故其工業上的利用儸值極大。 又，依然本發明，醑於處理大氣污染物質之氣態烴， 不但可以達成習知方法所無法連成之「美囲琛塊保護局 (EPA)所一定之1V0L%以下之規範數值」使排放氣龌播 致清淨，而且對於所發表之EPA措施所騣格規範的減半 數值的要求，亦能充分對應而獲得蓮轉實績。 〔圖面之簡單説明〕 第1圖僳表示本發明一實施例之氣態烴之處理•回收 裝置之流程圖。 第2圖俱表示本發明實施例之蓮轉數據圃。 (請先閲讀背面之注意事項再填寫本頁) -1 8 * I 本紙張尺度適用中國國家梂準（CNS > A4規格（210X297公釐） .Jn Hi m —I— -n I In an. A7 B7 五、發明説明（) 〔符號説明〕 1 ____廢棄氣體發生源 2 , 3 ...吸附塔 4 ....真空泵 5 ____汽油回收器 6 ____分配管 7 ....液面計 11, 11'....廢棄氣黼送氣管 12,12’....排放管 13.13'____淸洗用氣龌送氣管 14,14’____解附後之淸洗氣鼸送氣管 15 ....回流管 (A), (B), (C)____使用不同孔徑吸附劑的吸附薄I靥。 Μ i 一 装 訂 (〕 (請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局負工消费合作社印製 -1 9 _ 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐）302444 A7 B7 V. Description of the invention (/) [Industrial application field] The present invention resembles the gaseous gas contained in the waste gas, "Treatment / Recycling Device and its method, especially a substance causing photochemical soot The gaseous hydrocarbon concentration is 1V0L% or less to release it in the atmosphere of industrial equipment and methods, and there are gaseous hydrocarbon treatment and recovery equipment and methods contained in waste gas snakes. [Existing Technology] A photochemical soot image that prevents atmospheric contamination is produced by the reaction of NOx with gaseous hydrocarbons, which is known in the past. According to this, in the past, advanced countries headed by Japan, the United States, and Pizhou, and recently in Taiwan, Mexico, China, and South Korea, etc., have adopted laws and regulations to restrict NOx and the volatile hydrocarbons contained in the atmosphere. In order to make these norms transparent, the emission concentration standards have been set up in various local governments to handle industrial processing and recycling devices. Among them, the problem of being a source of gaseous hydrocarbons is particularly important, because when storing volatile hydrocarbons, the waste gas produced from the storage tank or tanker at the time of loading or storage is stored in the oil tank. Waste gas produced by oil tank trucks "Printed by the Consumers Cooperative of the Central Bureau of Economics and Trade of the Ministry of Economic Affairs (please read the note $ item on the back and then fill in this page) The treatment and recovery method of this waste gas containing gaseous hydrocarbons In the past, the widely used methods include (1) the absorption method shown in Japanese Patent Publication No. 54-8632, Japanese Patent Publication No. 54-5789, Japanese Patent Publication No. 58-022503, etc. (2) The method of using gas to separate the male membrane (air-membrane separation membrane method) (3) The method of strong cooling to -60 ~ 70 ° C to liquefy it, the paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X : 297 mm) 309444 A7 __B7_ printed by the Employees ’Consumer Cooperative of the Central Bureau of Samples of the Ministry of Economic Affairs 5. Description of the invention (>) (4) Adsorption methods such as active activated or synthetic boiling right. t Among the above methods (1) to (4), the disposal and recovery method of waste gas containing gaseous hydrocarbons as shown in the waste collection method of (1) is the most widely used method in Japan. The treatment and recovery methods of this absorption method are described in detail. This method includes, ♦ Introducing the gaseous liquid containing waste gas into the absorption tower to carry out the gas-liquid of waste gas and organic liquid mule absorption liquid.鹸 接 », absorb gaseous hydrocarbons in waste gas mullet with absorbent. • The step of discharging the absorbed gas mule into the atmosphere from the top of the absorption tower, • The evaporation of the absorption liquid that absorbs gaseous hydrocarbons in a vacuum vessel, and the separation and recovery of the gaseous state from the absorption liquid. And the recovered absorption liquid is recycled to the absorption tower again, and it is used for the step-by-step method (refer to the publication No. 58-022503 published before). [Problems to be Solved by the Invention] The "indicated by the absorption method described in item (1) above" contains the gas corpus "the treatment and recovery method of waste gas traps" is the concentration of gaseous state released in the atmosphere from the top of the absorption tower, ie It is determined by the vacuum degree of the vacuum container. That is, the air pressure released from the top of the suction grazing tower in the atmosphere is based on, for example, the pollution prevention regulations established in various capitals and prefectures in Japan like 5 V0L% or less, In this way, it is necessary to keep the vacuum degree below 30 ·· Ηβ. Among them, in addition to Japan, in the advanced countries of the United States, Taiwan, Mexico, and other countries, the emission threshold is deliberately set at the United States Ring Protection Agency (ΕΡΑ ) This paper scale is applicable to China National Standards (CNS) Α4 specification (210Χ297mm) ------ Τ--i 装 ------ 定 ------ Z: (Please read the back side first Please pay attention to this page and then fill out this page) A7 __B7 _ Printed by the Ministry of Economy Central Bureau of Accreditation Consumer Cooperative Fifth, the invention description (today) is below 1V0L% (below 38Bg / L). For clarity, take the above π) absorption method as an example, that is, it is necessary to The vacuum degree is limited to 7 * mHg or less, especially when the resistance loss of the absorption fluid flowing in the Caulu and piping is necessary to limit it to or below. However, when this kind of vacuum operation, part of the absorption liquid itself evaporates, Therefore, it is not suitable for use by Xunchen. On the one hand, no vacuum pump that can handle 100 ～ 2000b3 / Hr large release gas at high pressure of 2 muHg has been seen so far. Therefore, the absorption of the above (1) As far as the method is concerned, it is quite difficult to maintain the oxygen level in the release of gas hunger below 1V0L%, which has not been achieved so far. For the method using the gas separation membrane of the above item (2) (air separation membrane method) ) It also has the same situation, and the technology of processing the hydrocarbon concentration in the waste gas into 1V0L% or less has not been completed. On the one hand, _ liquefaction in the strong cooling of the above (3) to -60 ~ -701C Method, when the de * point is reached, the gaseous state will not be liquefied. Here is a detailed description of this method. The concentration of the gaseous waste in the waste gas mule is 5 0 ~ 1 0 0 V 0 L% high »When the temperature is low, if there is less methane, ethane, propane and other components, then Deep cooling to -70 t: the following and remove methane, ethane and quickly reach stickiness. In this way, it may be maintained at 1V0L%. However, the concentration of waste gas in waste gas • such as when storing and unloading oil, etc., usually It is a low capsule of 5 ~ 50V0L%. Therefore, for the case of petroleum, if it is deeply cooled to this paper scale, the Chinese National Standard (CNS) Α4 specification (210Χ297 mm) is applied ------ Υ --- 4 Pack ------ Order ------ C Bing (please read the precautions on the back before filling in this page) Printed by S0Q444 A7 __B7_ of the Central Consumer ’s Bureau of the Ministry of Economic Affairs Employee Consumer Cooperative Description of the invention (4) When it is near -100TC, it cannot be kept below 1V0L%. In addition, at about -70t: Di-methane can be used as a refrigerant. However, this refrigerant has recently had problems with its toxicity due to its toxicity. At the same time, it has not been seen so far and there is no economically viable use that can be cooled to- loot: The refrigerant. Therefore, the method of keeping the susceptibility of hydrocarbons in the waste gas to less than 1V0L%, according to the current situation, although there is an adsorption method using the active sieve or zeolite of the above item (4), but only in this method , There are general problems like the following. That is to say, when using active adsorbent to adsorb gaseous state, the heat of adsorption is used. For example, in the case of gasoline steam, it is 10 ~ 15KCAL / ear. The more the amount of heat of adsorption, the greater the amount of adsorption heat. . In this way, the temperature of the active sulphur adsorption tower rises, causing frequent fire accidents. The means used to prevent this accident can be considered * (Α) The waste gas introduced into the absorption tower is mixed with air to reduce the heat of adsorption per unit time and keep the rising temperature of the absorption tower within about 6010. However, deliberately inputting air into the waste gas to make it thinner is quite uneconomical. At the same time, due to the mixing of air, the amount of gas to be treated increases according to its proportion. In this case, it is necessary to increase the adsorption tower and ancillary equipment. Nor can it be established. In addition, although (B) cooling the adsorption tower with water and removing heat has been considered, even if the cooling water is used, only the sensible heat of the water can be utilized, and a certain degree of cooling effect cannot be expected. As for increasing the cooling surface, it is necessary to expand the adsorption tower based on the reason of the cold part of the single blunt. It is not economically beneficial. The size of this paper is suitable for China National Standards (CNS) Α4 specification (210Χ297mm) ---- Ρ-. J --- 4 Packing ------ order ----- 丄 | (Please read first Note on the back and then fill out this page) A7 B7 printed by the Consumer Labor Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Invention description (r) Moreover, although it is suspected that (C) is generally low-boiling and sticky like tetracyanosulfur Non-combustible f Refrigerant heat removal method, but when this method is used, the evaporated sulfur tetrachloride cannot be released into the atmosphere due to the absorption of the heat of adsorption, so it is necessary to cool it again to keep the tetrachlorosulfur vapor at the boiling point Following back to the original liquid skull tetrachloride, this method also has no economic effect. On the one hand, as a means of removing heat from the active adsorption towers, that is, there has been a method of using liquid hydrocarbons with large latent heat of evaporation (such as liquid petroleum) as the refrigerant, and this method has also been widely used abroad use. This method is to arrange the passages with liquid hydrocarbons inside and outside the adsorption tower. Among them, the liquid hydrocarbons are used to remove heat by using the latent heat of evaporation, and the evaporated hydrocarbon gas is washed with the same kind of liquid The method of recycling. Although the above method has better cooling effect using cooling water, if the passage of liquid hydrocarbon is damaged, there will be a fire accident in the construction zone. Therefore, it needs to be installed in the home away from home, so there are still some missing . As for the operation method of the adsorption tower, the method of alternating the adsorption step and the de-attachment step is generally used. This method is: • PSA (Pressure Swing Adsorption) method, • PTSA (Pressure and Teaperature Swing Adsorption) Xun Chen Way, and the above way is known technology. Regarding the PSA Xunchen method, the solution step is to use a part of the export air blower as a cleaning method, so it is quite difficult to do post-embroidery treatment due to the largest cleaning. The PTSA follows the urn method, which is a heating method using decoupling as a means of desorption. This method is to desorption by heating, and the adsorption tower gold-7-this paper standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) (please read the notes on the back before filling in this page) Order A7 printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. V. Invention description (b) The surface is heated, cooled, and the result It leads to a large Λ heat loss, so it has the disadvantage of time consuming in Fu Reshi. Among them, for the treatment method of the thin waste gas sluice with the concentration of gaseous hydrocarbons below 1 VOL%, the adsorption method using the conventional activated sulfonate or synthetic zeolite is the most effective. The treatment method is the most substitute for this adsorption method. However, according to the current situation, there are no gaseous hydrocarbons containing too thick, and a large amount of waste gas above 100 · 3 / Hr is processed, and hydrocarbons are recovered from the waste gas with good efficiency, and will be discharged into the atmosphere. Economical treatment and recovery device or treatment and recovery method with residual concentration below 1 VOL%. In view of the above deficiencies, the purpose of the present invention is to provide an apparatus and method for processing waste gas containing waste gas, supplementing and recovering gaseous hydrocarbons, and recovering hydrocarbons from the waste gas ram with high efficiency, and The residual concentration of gas brewing discharged into the atmosphere is reduced to less than 1V0L%, as well as the treatment and recovery device and method of the gaseous state contained in the waste gas. In addition, another object of the present invention is to provide an industrial device and method for reducing the concentration of gaseous hydrocarbons that cause photochemical dust-causing substances to be lower than IV 0 L%. [Means needed to solve the problem] The present invention aims to achieve the above objectives, and the use of single-tower or multi-tower-type adsorption device, which will be completed, ♦ Install the "adsorbent in the adsorption device, if the pore size is used 4 ~ 100 Angstrom (augstroa) synthetic zeolite and / or hydrophobic sand frog, therefore, • using this adsorption as the adsorption calendar, by mixing the above adsorption with different pore diameters, this paper scale is suitable for China's Sleeping Home (CNS) A4 Specifications (210X297mm) (Please read the precautions on the back before filling in this page) Packing ------ Ordered ---- (------- Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Printed A7 __B7_ V. Description of the invention (7) The thin I mixed layer or the adsorbents with different pore diameters are packed into each other to form an adsorbent. So, according to the present invention, waste gas can be treated Gasoline® becomes thinner, and at the same time, it is possible to "waste gas pulp containing gaseous hydrocarbons with a concentration of about 30 VOL% or more" which cannot be handled by the conventional adsorption method. It is also easy to change such a high concentration The concentration of residual hydrocarbons emitted into the atmosphere is maintained at 1V0L90 to In addition, the device used in the present invention can also be miniaturized to form a portable device that can be supported by the I. That is, the device of the present invention can be used to "use a single tower or more The tower-type adsorption device adopts synthetic zeolite and / or hydrophobic silica with a pore size of 4 to 100 Angstroms in the treatment and recovery device of the gaseous hydrocarbons contained in the waste gas falcon «In this adsorption device as an adsorbent, And the adsorbent formed by the adsorbent is mixed with adsorbents of different pore diameters to form a mixed layer or the adsorption of different pore diameters is separately installed Gaseous hydrocarbon processing and recovery device. "(Sentence 1 of the patent application) is the main purpose. In addition, the method of the present invention is to include" using a single tower type or even multi-tower type adsorption device in In the method of treating and recovering gaseous hydrocarbons from waste gas snakes, synthetic zeolites with a pore size of 4 to 100 Angstroms and / or hydrophobic silica mash are installed in the "Zhei adsorption device as an adhesive agent, and the adsorption The attached layer of rubbish is mixed with The pore size of the adsorbent is formed as a mixed layer or the adsorption of different pore sizes_The paper size of each package is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm> ---- *-Γ --- 4 package-- ---- Subscribe ------ 1) (Please read the precautions on the back before filling out this page) A7 B7 Printed by the Central Bureau of Economic Affairs of the Ministry of Economic Affairs Beigong Consumer Cooperative V. Invention Instructions (S) 1 1 J * Chengduoyu becomes the adsorbent layer 9. The waste gas is treated by introducing waste gas containing gaseous t 1 1 into the above-mentioned adsorbed tungsten. * At the time of desorption • 01 is part of the resulting gas discharged from the above 1 1 adsorbed tungsten Rinse and / or air to be cleaned> Please! First, recover gaseous hydrocarbons from the cleaning gas for the special gas containing waste gaseous gas. Read the treatment and recovery methods of hydrocarbons. 〇J (Patent Scope 3) ) 1 of 1 of the back Λ 1 I * is the main purpose. Note \ | The following is for the device and device of the present invention The method is described in detail. Item 1 1 The inventors, etc. • That is, for the adsorption equipment using Q9 tower type or even multi-tower type, fill in this device in the treatment and recovery device and its page of gaseous hydrocarbons contained in m waste gas m 1 I method • The results of painstaking research »It was found that the suction 1 packed in the adsorption device 1 1 The attached gas pore size has a deep influence on the adsorption amount of the gaseous state mt and also has the image of the molecular size of the gaseous 1 I hydrocarbon. The present invention was completed using a non-combustible adsorption m with a pore size within the range defined by the Naim range 1 (synthetic zeolite with a pore size of 4 100 Angstroms and / or a hydrophobic silicon waist) as a special emblem. 1 | That is, when the molecular size of gaseous α is constant > Adsorption m 9 with a certain pore diameter 1 I can be used, for example, to deal with heterogeneous chain hydrocarbons such as petroleum m gas »normal 1 chain chain hydrocarbons * olefin 9 瑷Hurricane 9 Aromatic hydrocarbons and other molecules of mutually different size 1 The gas plaque formed by different components > It is necessary to correspond to the size of each of the adsorption pores 1 j corresponding 〇1 1 Where • If using pore size distribution Fanyuan m wide When the activity is m, 1 can absorb 1- with all of the above components »Due to the large amount of adsorption • With this adsorption, 1 1 generates a large amount of heat of adsorption» Result 9 The temperature of the adsorption layer rises sharply Danger of fire alarm 〇1 I Therefore, if it is the case of active m • As mentioned above, although there is a means to remove heat 1 1 -10- 1 1 1 1 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 ) 309444 A7 B7 Printed by the Employee Consumer Cooperative of the Central Prototype Bureau of the Ministry of Economic Affairs 5. Description of the invention (9) 1 1 is a necessary condition 9 but it is not easy to remove such heat energy 0 1 1 Opposite 9 The invention% As mentioned above 9% Synthetic zeolites and / or hydrophobic silicas with different pore sizes (4 1 I 10 〇Angstroms) with different pore sizes> 1 1 9 can be used in combination with each other to form gaseous molecules in the waste gas compartment Size first reading 1 | «Synthetic zeolite and / or hydrophobic silica with corresponding uniform pore size 〇fK back 1 The absorption of 1 1 state hydrocarbon is yes» According to the present invention, the gas in the waste gas can be controlled. Attached heat> This result »The heat distribution of the adsorption layer of the fuze device gold surface 1 I and 1 can be evenly distributed to prevent the temperature from rising sharply due to the heat of adsorption f and the adsorption can be expected Set up a perfect security. Write this page. 1 The existing method of using active sacred »Like proposed to mix fine 1 1 sand and stone or non-combustible granular inorganic substance with large heat capacity in the adsorption layer > And 1 I. The method of dispersing the local heating generated in the adsorption layer according to this method. However, the device according to the invention of the Zhangtu Factory which combines the adsorption pore size of the absorbent used with the adsorbed sub-I and J In terms of methods > if the actual device is added with 1 I to operate and investigate the temperature distribution in the adsorption layer in detail »It is known that a uniform temperature is formed throughout the adsorption layer 1 1. For such a factory, the temperature of the entire attachment is increased. In terms of homogenization J> If you refer to the following, there are more examples of the method of the present invention to make further progress-a step-by-step explanation »ie 1 1 in the adsorbent layer (A) [pore size: from about 5 Angstroms of Hetian K zeolite Formed by I The heat generated when the adsorbent layer adsorbs enough gas for hydrocarbons 1 It can only adsorb gaseous hydrocarbon molecules determined by the limitation of 1 adsorption pore size. Therefore »This adsorption is 1 1 The thermal suspension that occurs in layer (A), the number of * Not much. The lower adsorbent layer • 1 1 (B), the adsorbent T &C; the same situation 0 I 1 volume] ί 1 1 1 1 1 1 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification ( 210X 297 mm) A7 B7 printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (.) That is, in accordance with the present invention, the pseudo-enterprise disperses the heat of adsorption to flow within the f adsorption history The airflow is mixed to form a smelt, forming a substantially uniform temperature from the upper end to the lower end of the adsorption device. The present invention is as good as the foregoing, and it can pseudo-process high-concentration waste gas containing gaseous hydrocarbons with a high concentration of about 30V0L% or more, which is considered difficult to be carried out by conventional adsorption methods. In addition, the high concentration of the gas to be treated (abandoned gas) can also maintain the residual hydrocarbons discharged in the atmosphere to be below IV 0L%. On the contrary, the conventional adsorption method or gaseous separation membrane method can be applied to the treatment of released gaseous monks containing thick gaseous hydrocarbons, but as mentioned above. the following. In addition, according to this absorption method or gas separation membrane method, the concentration of gas released in the atmosphere after the treatment is generally 2 to 5 vol%. As for the advantages of the conventional adsorption method, it is extremely effective for the treatment of released gas mules containing a small amount of endothermic heat containing a thin gaseous state. At this time, the inlet multitude is usually less than 1V0L%, and the outlet worm is PPM level. The lack of viscosity in this adsorption method is that, as described above, a large amount of heat of adsorption will occur when dealing with the release gas containing thick gaseous hydrocarbons. Although liquid olean hydrocarbons (such as liquid tar oil) with a large latent heat of evaporation have been developed as a method for removing such adsorbed heat refrigerants, they still have ι > ». Danger as described above. In addition, although it has been suspected of using water or low-boiling non-combustible sulphur tetrachloride, etc. -12- This paper uses the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the back page first Matters needing attention and then fill out this page) Order 309444 B7 Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of Invention (vl) 1 1 As a refrigerant »Only as mentioned above > So 1 1 The desired cooling effect 1 In addition »In the case of tetrachloride, saccharine», the vaporization of tetrahydrom due to the capture of 1 1 adsorption heat cannot release it into the atmosphere »Therefore, -V please sign 1 First, it needs to be cooled to below the boiling point and then recirculated to the original liquid sump. Don't read L 1 Economically beneficial. Back 1 1 of 1 The invention relates to the use of single-tower or multi-tower-type adsorption devices. Note- 1 1 will be included in the gaseous% of waste gas Management • Recycling equipment and its methods * Matters 1 i ♦ As mentioned above, for the use of adsorption heat, the adsorption temperature will cause abrupt temperature. Fill in this equipment, as it rises, broadcasts, and lowers. 9 Use the flammability words that have been used in the past. 1 I attached the agent to a factory with a certain pore size (4 100 Angstroms) and a non-combustible synthetic zeolite with a different pore size 1 1 and hydrophobic silica mash J 9 and by controlling the synthesis of 1 1 zeolite and / or hydrophobic The pore size of the adsorption m formed by the silica mash and the adsorption 1 are set to 9 and made to be able to control the passivity of the adsorption layer arbitrarily. 1 In the present invention 9 for the “synthetic zeolite” rcU used as an adsorbent, hetero Anr m 1 I is specifically limited to 9 but it is best to use synthetic zeolites containing abundant m silica (1 I to be activated silica). On the other hand »" Hydrophobic Silicone "9 PI? Not suck I Water-repellent substance • Repellent to an oleophilic substance 0 This hydrophobic silicon 1 I Pore size of pores »Usually random» In addition to non-combustibility • Distribution of its adsorption pores 1 1 • It is roughly similar to the activity m The adsorption behavior is also similar to active moraine. l · Is »As far as the present invention is concerned» For example, if different apertures are used to absorb rain and do multiple installations 1 1 »When * The most effective one is to arrange the rose water-based silicon mash in the treated air nipple (\ 1 鮮 寨 气 鼸) for adsorption The final section of the layer (the first section of the 01 emission)) 1 I The adsorption step can be based on this and it is possible that the device will be smaller 1 1 -13- i 1 1 1 1 This paper size is applicable to ll national standards (CNS ) A4 specification (210X297 gong) The A7 _B7_ printed by the Beigong Consumer Cooperative of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs V. Description of the invention (_ >) Type, so that for the gas that contains _thick gaseous hydrocarbons which is difficult to implement in the past, At the same time as the thin gas, it is easy to discharge the residual hydrocarbons of the gas mule below 1 VOL% so that it can be discharged into the atmosphere, and constitute a favorable rule according to the extremely economic benefits. The difference is that, based on the above-mentioned principles of the present invention, it is suitable to use the “cargo tanker between the gas station and the sickle oil field that becomes empty after unloading the oil and recycles the oil vapor to the storage system, which is implemented under the current regulations. The situation of the oil field (reflow method) ", or the emission regulations stipulated in the current state of the United States" the situation of refueling cars at urban gas stations "and" the treatment of gasoline vapors that occur from the car refueling hole J. That is, for refueling For the station, since the monitoring system can not be operated by hand, the safety and simplicity of operation are the most important. The key, even without monitoring, is automatically opened and closed by the button, and it is expected that the development will not occupy the site. And the safety is extremely high to prevent harm to the machine. The device and method of the present invention can fully meet this expectation. The device and method of the present invention are not only applicable to the conventional PSA method or PTSA method, Moreover, it is also applicable to other VSA methods, VTSA methods, etc. These applications are also included in the present invention. Furthermore, the present invention is applicable to the treatment and recovery of exhaust gas containing gasoline vapor emissions, and also applicable For other benzene, acetone, formazan and other low-boiling viscous gas-containing exhaust fumes, these applications are all included in the present invention. Moreover, the present invention uses single-tower or multi-tower-type adsorption devices. On the top, the most applicable is the double-tower ore-building adsorption device described in the following examples, but the invention is not limited by this double-tower ore-absorbing device. -1 4-This ϋ scale applies China National Standard (CNS) A4 Specification (210X297mm) '----.---.--- f Pack ------ order ----- 丄 .1 (Please read the back of the first (Notes and then fill out this page) A7 B7 Printed by the Central Sample Bureau of the Ministry of Economic Affairs Beigong Consumer Cooperative V. Description of the invention (G) 1 1 Γ Example] 1 1 The following lists the devices and methods pioneered in the invention Example 1 1 1 The present invention is described in detail, but the present invention is not limited by the following examples. Please 1 first 1 (relevant to the left> Example of the device of the present invention) Read I Group 1 You indicate an implementation of the present invention Examples of the treatment of gaseous hydrocarbons Flowchart of processing with recovery back A 1 | Note 1 I The device of this embodiment, as shown in the first circle, is a double-tower entangled adsorption device formed by the adsorption tower 1 and the adsorption items and then the L tower 3 9 This adsorption tower 2. 3 Li filled with different pore size adsorbent (pore size: 4 100 Angstrom rich silica hinge 1 I into zeolite) consists of 3 sorbent layer (A) > (B), (C) Composition 〇1 1 and 9 As far as the first ring is concerned, 1 is a waste gas containing gasoline vapor generation 1 I source $ 4 is a vacuum pump t 5 for attracting and degassing the gas after washing and degassing. 5 is a gasoline recovery unit. 6 is a distribution pipe for distributing the decontaminated cleaning gas to the gasoline recovery unit, 7 is a liquid level gauge 〇1 | and • 11, 11 'is a waste gas supply pipe, 12, 1 2. For the emission of Mm 営9 1 I 1 3, 13 'is the air supply pipe for air wash, 14. 1 4' is the air wash pipe after decoupling 1 gas supply pipe 1 15 is for steam The rubbing and degassing of the recycler am ΒΛ returns to sleep,-| the return pipe of the air supply pipe 〇1 1 (there is a stop in the embodiment of the method of the present invention) 1 1 The following, for the method of the present invention is added step by step Description 〇1. This example uses the device shown in the first 1 _ as shown in the example above. The treatment contains 5 ^ -30V0L% 1 1 Gasoline steam sleep _ 酽 becomes 1 VOL% less than the clean gas and is suspected to be released 1 1 In terms of the atmosphere * ", it is an example of recovering JJst Π »oil vapor in waste gas. 1 I This example uses pseudo-silica-rich synthetic zeolites with different pore sizes to make 1 1 -15 · i 1 1 1 1 The paper size is applicable to China National Standards (CNS & A4 specifications (210X297mm) Central Ministry of Economic Affairs Printed A7 __B7_ by the Beigong Consumer Cooperative Society of the Standardization Bureau. V. Description of the invention (4) is an adsorbent, as shown in the first circle, it is composed of 3 calendar adsorption «« (A), (B), (C) Adsorption towers 2. 3. Specifically. All along the flow direction of the waste gas containing gasoline steam. ♦ The original adsorption rain layer (A) has a pore size of about 5 angstroms and a synthetic zeolite containing a large amount of silica (produced by Dongsu Company) "ZSM5 (trade name)": X-type zeolite] ♦ Secondly, the adsorbent (B) has a synthetic zeolite with a pore size of about 7 Angstrom and contains a large amount of silica [Y-type zeolite manufactured by Lisu Corporation] • Last The adsorbent layer (C) is formed of a hydrophobic silicone gel with a pore size of about 80 angstroms ("Ql〇 (trade name)" manufactured by Yushi Silicia Chemical Co.] In this embodiment, the image contains 5 ~ 30V0L% of the waste gas emitted from the source of gasoline steam waste gas is blown (The circle surface is not shown) or its own pressure, from the waste gas plaque supply pipe 11, 11 'round to the adsorption tower 2, 3 composed of the above adsorption thin I layer (A), (B), (C). In addition, for adsorption towers 2 and 3, the adsorption step and the de-attachment step «replace the lotus, and the replacement time is 3 to 10 minutes. After the adsorption step is completed and the treatment is completed, the air is swollen, from the adsorption tower 2 (At the top of the adsorption tower 3 after the replacement and de-attachment step), through the discharge pipe 12 (or discharge pipe 12 '), knead the air (clean gas) containing 1 V0L% of gasoline vapor and having an irrigation degree in In the atmosphere, on the one hand, the adsorption tower 2 (after the adsorption step is replaced with the adsorption tower 3) after the adsorption step is fed with the cleaning gas (air) through the air supply pipe 13 '(or 13) for the cleaning gas, It is attracted by the vacuum pump 4 to make it unattached. (This -16- This paper scale is applicable to China National Standards (CNS) A4 specification (210X297mm) -------- J .-- 4 装 --- --- Subscribe ------ ^ ^ (Please read the precautions on the back before filling in this page) Printed by 302444 A7 B7, Beigong Consumer Cooperative of the Central Bureau of Samples of the Ministry of Economic Affairs V. Description of Invention (β) True The pump 4 turns around at about 25 Torr.) After desorption, it contains gasoline vapor to clean the gas mule, that is, it passes through the air supply pipe 14 '(or 14) to the gasoline recycler 5, and comes into contact with the liquid mule gasoline through the distribution pipe 6. Gasoline steam recovered from the scrubbing gas is formed into liquid naphtha (gasoline recovery liquid). From the exhaust gas of the gasoline recovery unit 5, there is still a slight amount of gasoline vapor remaining, so it is returned to the waste gas again through the return pipe 15 The eluent gas pipe 11 performs adsorption treatment together with waste gas. In addition, the gasoline recovery unit 5 is equipped with a liquid level gauge 7 for detecting the position of the gasoline. Moreover, the temperature of the adsorbent layers (A), (B), (C) is maintained at about 40¾ during lotus rotation. That is, because of the adsorbent calendar (A), (B) *, (C), because of the function of dispersing the heat of adsorption, the temperature from the top of the adsorption tower 2 (3) to the lower end is maintained at a substantially uniform temperature (about 40t :). The second painting shows the lotus transfer data garden of this example. It can be seen from the second part that according to this embodiment, the concentration of gasoline vapor in the waste gas tank varies from 5 to 20 Vol%, but the concentration of gasoline vapor of the gas emitted in the atmosphere no matter what the situation is , Still 0%. [Effects of the invention] As detailed above, the present invention uses a single-tower or multi-tower type adsorption sus aa device, with a pore size of 4 ~ 100 Angstroms * Synthetic zeolite with silica and / or hydrophobic silica As the adsorbent used by the installation in the adsorption device, it is composed of • mixed different pore diameter adsorption_mixed layers or different pore diameters adsorbed to each other to become a sorbent layer of Tatra. , The paper size is free to use China National Standards (CNS) A4 specification (210X297mm) ---- > --.---- {装 ------ 定 ------ f: · ».- (please read the precautions on the back before filling in this page) A7 B7 printed by Beigong Consumer Cooperative of the Central Bureau of Samples of the Ministry of Economic Affairs V. Description of invention (4) Regardless of its concentration in the treatment of gaseous waste At this time, it is easy to maintain the residual hydrocarbons emitted by the gas in the atmosphere below 1 Vol%, which has a significant effect. In addition, the device of the present invention can be formed as a carrying-type hand-held device, so its industrial utilization value is extremely large. In addition, according to the present invention, the treatment of gaseous hydrocarbons of atmospheric pollutants can not only achieve the “standard value below 1V0L% specified by the Meiyuchen Block Protection Agency (EPA)” that cannot be achieved by conventional methods. It is clean and broadcast, and the requirements for halving the numerical value of the published EPA measures can also fully respond to the results of lotus conversion. [Brief Description of Drawings] Figure 1 shows a flow chart of a gaseous hydrocarbon processing and recovery device according to an embodiment of the present invention. Figure 2 shows the lotus data garden in the embodiment of the present invention. (Please read the precautions on the back before filling this page) -1 8 * I This paper size is applicable to China National Standard (CNS & A4 specifications (210X297 mm). Jn Hi m —I— -n I In an. A7 B7 V. Description of invention () [Symbol description] 1 ____ Waste gas generation source 2, 3 ... Adsorption tower 4 .... Vacuum pump 5 ____ Gasoline recycler 6 ____ Distribution pipe 7 .... Liquid Count 11, 11, '... Waste air supply pipe 12,12' ...... Discharge pipe 13.13 '____ Washing air scoop supply pipe 14,14' ____ After de-bonding, wash the gas Air supply pipe 15 .... Reflux pipes (A), (B), (C) ____ Adsorption thin I with different pore size adsorbents. Μ i One binding () (Please read the precautions on the back before filling in This page) Printed by the National Bureau of Standards, Ministry of Economic Affairs, Negative Labor Consumer Cooperative -1 9 _ This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm)