經濟部智慧財產局員工消費合作钍印製 491814 A7 B7 五、發明說明（i) 技術領域 本發明係有關再利用含矽酸成分及鋁成分之無機廢棄 物，藉由將已調節過矽鋁比之上述無機廢棄物與鹼性水溶 液一同混合後，一邊施以超音波，一邊於耐壓反應容器內 加熱或加壓使其反應；或者是將已調節過矽鋁比之上述無 機廢棄物與鹼性水溶液一同混合後，一邊使其於加熱反應 管內連續流動，一邊施以加熱處理及超音波處理來製造人 工沸石之方法，以及製造裝置。 過去技術 自古以來，人工沸石大多以煤灰、特別是以在火力發 電場等中燃燒煤時所產生，被稱爲飛灰之微粉的燃燒灰作 爲原料，再添加2〜4N的鹼性水溶液於這些原料中，然後 藉由在大氣壓下加熱處理而製成。因而，生成的人工沸石 之品質與作爲原料之煤的組成相依存，於品質上亦受到限 制，雖其表面被沸石化，然而多孔質之孔的內部不一定被 沸石化，故所製造之人工沸石的品質未必令人滿足。 又，作爲製造人工沸石之方法而被熟知者，如使用煤 灰或垃圾焚化灰等之焚化灰，以分批式的反應裝置來進行 者，此方法已被揭示於特開平6 - 32 1 5 26號公報等中。又 ，作爲連續製造人工沸石之方法，如揭示於特開平一 3 245 1 8號公報中，使用循環流動反應槽之人工沸石的製造 裝置。此外，被稱爲合成沸石之觸媒用沸石，雖其構造皆 爲沸石，然而在其合成上，必須於1 〇〇 °C以上的高溫區域 ---------------^---------^ (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） -4- 經濟部智慧財產局員工消費合作社印制农 491814 A7 B7 五、發明說明（2 ) 進行反應，而且，因所使用的矽酸及鋁等原料若不爲高純 度之物，則將阻害沸石的生成，故不能使用純度低的原料 〇 又，存在於火山周邊之火山灰、浮石、火山玻璃等的 火山噴出物之降塵，既無法作爲工業用原料來利用，又不 能使用於農地，故從所謂土地的有效利用面看來，其利用 的方法將成爲問題。 又，於全國的各市、鎭、村中，在垃圾處理上，皆將 其分類爲數種類之垃圾後，收集之。例如，一般雖分類成 可燃垃圾、不可燃垃圾、大件的垃圾、有害垃圾等，然而 其分類方法將依市鎭村而有所不同。這些垃圾之中，可燃 垃圾一般雖可於焚化場中焚化，然而其焚化灰的處分卻成 爲另一問題。又，在不可燃垃圾方面’雖然玻璃、金屬以 及合成樹脂之一部分可被再利用，但是如瓶等的玻璃、罐 等的金屬、盒子、保特瓶等的合成樹脂成品之處理將形成 問題。 目前，全國的一般廢棄物排出量已超過5000萬噸， 而其中的大約85 %被施以焚化、壓碎、資源化等之處理 。然而，將被直接掩埋的垃圾與來自垃圾處理設施的焚化 灰等總合所得之掩埋量逐年增加。因而，在各市鎭村方面 ，雖時而將此逐年增加之焚化灰的大部分利用於掩埋地’ 時而將其固化成沸石等之形態後作爲廢棄物來處理’然而 卻因在處理地的確保上招致困難等而成爲嚴重的社會問題 --------訂--------.線 (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） -5- 遥齊Sr皆慧讨轰苟員11省費士净fi沪製 491814 A7 _____ B7 五、發明說明（3 ) 更者，在產業界方面，於利用矽藻土之工業上所產生 之廢砂藻土的處理；以及在冶煉IS業界方面，於冶煉或精 製時所發生之鋁渣滓的處理將成爲問題。此外，在製鋁業 界方面，鋁砂箱之鹼性廢洗淨液的處理問題、以及具稻殼 等之禾本科植物的廢棄物等之廢棄物處理，亦成爲問題。 因此，將上述的各種廢棄物作爲資源來活用之人工沸 石的製造方法已被考慮，然而在以往的分批式反應裝置中 ，不僅生產性無法提昇，在使用循環流動反應槽之製造裝 置時，反應溫度的確保亦相當困難。 發明的揭示 本發明係將含矽酸成分以及/或鋁成分之物質與矽酸富 集材或鋁富集材相以所定的矽鋁比相配合後，再與鹼性水 溶液混合’然後將此混合而得之原料混合物放入耐壓反應 容器，一邊施以超音波振動一邊加熱或加壓使其反應來合 成人工沸石者，此外作爲其他之方法者，即將含矽酸成分 以及/或鋁成分之物質與矽酸富集材或鋁富集材相以所定的 矽鋁比相配合後，再與鹼性水溶液混合，然後將此混合而 得之原料混合物設置於耐載熱體槽中，一邊施以超音波振 盪’一邊藉由以至少具有使原料混合物連續地流動於被加 熱的反應管內之人工沸石生成步驟爲特徵之加熱反應管接 觸來合成人工沸石者。藉前述的加熱反應管接觸來合成之 人工沸石的連續製造方法，其特徵爲將含砂酸成分以及/或 鋁成分之物質與矽酸富集材或鋁富集材相以所定的矽鋁比 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） --------^---------^ (請先閱讀背面之注意事項再填寫本頁) 491814 A7 ____B7 五、發明說明（4 ) 相配合後，再與鹼性水溶液混合，然後將此混合而得之原 料混合物設置於耐載熱體槽中，一邊施以超音波振盪，一 邊藉由以至少具有使原料混合物連續地流動於被加熱的反 應管內之人工沸石生成步驟者。 若依據此發明，將前述的原料混合物設置於載熱體槽 中’ 一邊施以超音波振盪，一邊藉由原料混合物通過被加 熱之反應管內部時所產生的亂流作用，充分且有效率地攪 拌此原料混合物。而上述原料混合物，係由將含矽酸成分 以及/或鋁成分之物質與矽酸富集材或鋁富集材相以所定的 矽鋁比相配合後，再與鹼性水溶液混合而得。此時，因反 應管的全長已依據所定的條件而被設定，故將前述的原料 混合物供給於被加熱的反應管後，反應立即開始。其結果 ，不J堇可促進人工沸石的生成反應，並且亦可達成縮短反 應時間與提昇製造效率之功效。 在作爲含有成爲合成人工沸石時之原料的鋁成分之物 質方面，能使用含有鋁酸之鹼性廢液，而在作爲含鋁酸之 鹼性廢液方面，則可使用製造鋁成品時之鋁砂箱的鹼性廢 洗淨液，或將製造耐酸鋁時所產生的鋁淤渣加鹼溶解者。 又，在作爲含有成爲合成人工沸石時之原料的矽酸成分之 物質方面，能使用由稻、麥等禾本科植物中加鹼抽出之矽 酸成分。 作爲矽酸富集材，能使用玻璃、矽藻土、或水玻璃， 而其中以廢玻璃的碎玻璃作爲前述之玻璃者爲佳。又，作 爲鋁富集材，能使用渣滓。 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) · ' 線 491814 A7 B7 五、發明說明（5 ) 在作爲含有成爲合成人工沸石時之原料的矽酸成分以 及鋁成分之物質方面，能使用火山噴出物之降塵，而作爲 該火山噴出物之降塵，能使用火山玻璃。 在作爲含矽酸成分以及鋁成分之物質方面，可使用焚 化灰，而作爲前述的焚化灰，能使用可燃性廢棄物的焚化 灰，而其中以使用都市垃圾、垃圾固體化燃料的焚化灰作 爲該可燃性廢棄物爲佳，此外，作爲前述的可燃性廢棄物 ，亦可使用污泥，而作爲該污泥者，以使用在古紙離解後 ，於回收纖維之工程上，藉由除塵操作所產生之污泥爲佳 。作爲前述的污泥者，亦可使用藉由廢水處理所產生之污 泥。 在作爲合成人工沸石時之加熱處理方面，大多於60〜 230/C的範圍內進行，而作爲前述的加熱處理者，可使用紅 外線放射來加熱耐壓反應容器或載熱體，又，亦可合倂使 用飽和蒸氣與紅外線放射來加熱前述的耐壓反應容器或載 熱體。 更者，作爲前述的加熱處理者，亦可使用微波加熱來 加熱耐壓反應容器或載熱體，或合倂使用飽和蒸氣與微波 加熱來加熱耐壓反應容器或載熱體。 更進一步地，作爲加熱處理者，亦可使用感應加熱來 加熱載熱體，或組合飽和蒸氣與感應加熱亦可。 . 在作爲於反應時的反應管上施以超音波時的振動數方 面，以18至500kHz的範圍內進行爲佳。 作爲反應時的鹼性水溶液者，以氫氧化鈉水溶液或氫 (請先閱讀背面之注意事項再填寫本頁) 訂----.----iw線- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -8- 491814 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（6) 氧化鉀水溶液爲佳，而作爲反應時之鹼性水溶液的濃度， 則以2至4N爲佳。 在藉由本發明之加熱反應管接觸來製造人工沸石之製 造方法上，於前述人工沸石生成步驟方面，設置了反應管 長變更操作。 若根據此發明，因設置有變更反應管長之操作，故即 使在人工沸石的生成速度會依人工沸石原料及鹼性水溶液 各個的種類或濃度、料漿（slurry )的流速、以及反應管的 設定條件等之改變而變更之情況下，亦可輕易地控制以其 生成速度爲基準之反應時間。 在藉由本發明之加熱反應管接觸來製造人工沸石的製 造方法上，具有如下的特徵，即將含矽酸成分以及/或鋁成 分之物質與矽酸富集材或鋁富集材相以所定的矽鋁比相配 合後，再與鹼性水溶液混合，然後在此混合而得之原料混 合物中配合所定量的人工沸石。 若根據此發明，由於在供給於反應管的原料混合物中 ，預先配合了所定量的人工沸石，而其人工沸石將成爲種 結晶而使人工沸石的生成極易發生，故能謀求縮短反應時 間與提昇製造效率。 在藉由本發明之加熱反應管接觸來製造人工沸石的製 造方法上，具有如下的特徵，即擁有前述之人工沸石的生 成步驟，與更進一步地由含有生成之人工沸石的料漿中分 離出人工沸石的分離步驟，以及置換人工沸石之類型的步 驟，和脫去人工沸石之水的脫水步驟。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -g - --------^----^----.線 (請先閱讀背面之注意事項再填寫本頁) 491814 A7 B7 五、發明說明（7 ) 若根據此發明，由於在上述之人工沸石的生成步驟中 ，加入人工沸石的分離步驟，人工沸石之類型的置換步驟 ，以及人工沸石的脫水步驟，故能藉由連續步驟有效率地 製造人工沸石。 前述的各步驟，即人工沸石的生成步驟、人工沸石的 分離步驟、人工沸石之類型的置換步驟、以及人工沸石的 脫水步驟具有如下的特徵，即其相互間因具有壓力差，故 可壓送前記原料混合物及人工沸石。 若根據此發明，因使上述各步驟之相互間產生有壓力 差，故能輕易地壓送原料混合物及人工沸石。其結果，能 容易且有效率地進行人工沸石的製造。 在藉由本發明之加熱反應管接觸來製造人工沸石的製 造方法上，具有如下的特徵，即前述人工沸石的脫水步驟 係藉由吸取脫水槽內的空氣及水蒸氣使其減壓，再加壓· 加熱吸取後之空氣及水蒸氣使其再度回到存在有人工沸石 的脫水槽中之旋管內，然後在蒸發人工沸石中之水分的同 時，使水蒸氣於旋管內凝結濃縮後排出來進行脫水，其後 繼續重覆這些動作。 若根據此發明，利用於加壓•加熱吸取後之空氣及水 蒸氣時所產生之熱，則可有效率地進行脫水。 在藉由本發明之加熱反應管接觸來製造人工沸石的製 造方法上，具有如下的特徵，即至少具有將含矽酸成分以 及/或鋁成分之物質與矽酸富集林或鋁富集材相以所定的砂 鋁比相配合後，再與鹼性水溶液混合，然後使此混合而得 --------------------訂---------線 IAW. (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） -10 - 491814 A7 ___B7__ 五、發明說明（8 ) 之原料混合物連續地流動於依所定條件被設定且被加熱的 反應管內之人工沸石生成裝置。此時，最好在前述反應管 內設置隔板。 在藉由本發明之加熱反應管接觸來製造人工沸石的製 造方法上，具有如下的特徵，即於前述的反應管中設置有 變更反應管長之操作。 在藉由本發明之加熱反應管接觸來製造人工沸石的製 造方法上’具有如下的特徵，即在由前述料漿的混合槽至 前述反應管的入口處之任一地方，設置一個爲了添加人工 沸石於原料混合物之人工沸石的投入口或者是含有人工沸 石之鹼性水溶液的投入口。而上述原料混合物，係由將含 矽酸成分以及/或鋁成分之物質與矽酸富集材或鋁富集材相 以所定的矽鋁比相配合後，再與鹼性水溶液混合而得。 在藉由本發明之加熱反應管接觸來製造人工沸石的製 造裝置上，具有如下的特徵，即擁有前述人工沸石的生成 裝置、人工沸石的分離裝置、人工沸石之類型的置換裝置 、以及人工沸石的脫水裝置。 在藉由本發明之加熱反應管接觸來製造人工沸石的製 造裝置上，具有如下的特徵，即於前述的各裝置上，設置 壓力檢定操作，與基於該壓力檢定操作而使各裝置的相互 間有壓力差產生之壓力調整操作。 . 若根據此發明，因於各裝置上，設置壓力檢定操作， 與基於其壓力檢定操作而使各裝置的相互間有壓力差產生 之壓力調整操作，故藉由那些操作，能使各步驟的相互間 -11 - (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） 491814 A7 _ B7 五、發明說明（9 ) 有壓力差產生。其結果，不僅能夠容易地壓送原料混合物 及人工沸石，亦能夠容易且有效率地進行人工沸石的製造 〇 圖式之簡單說明 第1圖係顯示藉由本發明之加熱反應管接觸來製造人 工沸石的製造方法之一例的流程圖，第2圖係顯示藉由本 發明之加熱反應管接觸來製造人工沸石的製造方法之一例 的系統圖，第3圖、第4圖係顯示人工沸石的生成裝置之結 構圖，第5圖係顯示反應管內之亂流的狀態之說明圖，第6 圖係顯示於反應管內設置隔板之一例的結構圖’第7圖係 顯示人工沸石的分離裝置之一例的結構圖，第8圖係顯示 人工沸石的脫水裝置之一例的結構圖。 1爲人工沸石的連續製造裝置 2爲原料混合物準備裝置 3原料貯藏槽 4鹼性水溶液槽 5原料混合槽 5a矽酸富集槽 5b鋁富集槽 · 6原料混合物供給槽 B人工沸石的生成裝置 7反應管 -12- (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） 491814 A7 _B7 五、發明說明（1〇) 7a超音波振動器 8載熱體槽 9載熱體油 1 0加熱器 1 1，27,33,38,43 回轉泵 P投入口 20冷卻器 20a導管 C人工沸石分離裝置 21人工沸石分離裝置 22,29分隔壁 23分離槽 24Λ1,36,41 排出部 25,25a，25b，40a 空氣口 26,26b，37,42 移送部 5 1壓力調節系統 D，F人工沸石的洗淨裝置 . 28, 39人工沸石洗淨裝置 ί 30,40洗淨槽 ί 31a，50洗淨水供給槽 ； 34人工沸石的類型置換裝置 : 35類型置換槽 ) ； 34a溶液槽 ； 44脫水裝置 •13- (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） 491814 經濟部智慧財產局員工消費合作社印製 A7 ______B7__ 五、發明說明（H) 45成品槽 46脫水槽 47壓縮機 E人工沸石的類型置換裝置 G人工沸石的脫水裝置 R泵 欲實施發明的最佳形態 本發明所述之人工沸石的製造方法，係將含矽酸成分 以及/或鋁成分之物質與矽酸富集材或鋁富集材相以所定的 矽鋁比相配合後，再與鹼性水溶液混合，然後將此混合而 得之原料混合物放入耐壓反應容器，一邊施以超音波振動 一邊加熱或加壓使其反應來合成人工沸石之法，此外作爲 其他之方法者，即將含矽酸成分以及/或鋁成分之物質與砂 酸富集材或鋁富集材相以所定的矽鋁比相配合後，再與鹼 性水溶液混合，然後將此混合而得之原料混合物設置於耐 載熱體槽中，一邊施以超音波振盪，一邊藉由以至少具有 使原料混合物連續地流動於被加熱的反應管內之人工沸石 生成步驟爲特徵之加熱反應管接觸來合成人工沸石之法。 所得人工沸石的主要成分爲鈣十字沸石、絲光沸石、 八面沸石、沸石A、羥基方鈉石等，亦含有少量的其他成 分。又，沸石以外的部分，即作爲非沸石成分者，如有機 物、鐵分、其他的不純物，以及與在形成沸石途中所產生 的中間生成物共存之物。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） _ 14 - --------------------訂---------線 (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 491814 A7 B7 五、發明說明（12) 在本發明中所述之含鋁成分的物質，就是所謂含有鋁 酸之鋁廢液，或者是稱爲鋁砂箱的鹼性廢洗淨液，或者是 將製造耐酸鋁時所產生的鋁淤渣加鹼溶解者。此外，作爲 鋁砂箱的鹼性廢洗淨液而能舉出者，如在以鹼洗淨於製造 鋁窗框、軸承、閥、精密工具、球管、線材、板材等的鋁 成品時之砂箱時所產生的廢液。 此外，所謂將製造耐酸鋁時所產生的鋁淤渣加鹼溶解 者，係指陽極氧化鋁後，使用鹼中和藉實施耐腐蝕性氧化 膜程序所生成的鋁酸性廢液，再分離此水溶性成分後所得 之氫氧化鋁的沉澱凝膠，或者是以鹼中和後，藉由添加鹼 於分離後所得之沉澱物或蛋糕狀物質中，而溶解析出含有 鋁酸鹽之廢液。 ，在本發明中所述之含矽酸成分的物質，就是所謂以鹼 性水溶液由含.有矽酸成分之廢棄物中溶解萃取出矽酸成分 之物，而作爲含有矽酸成分之廢棄物者，可舉出稻、麥等 之禾本科植物的稻殼、植物體。 前述的禾本科植物係所謂單子葉植物的一科，若除去 竹類則全爲草本。稻、麥、玉米、栗子、稗子、燕麥等穀 物皆屬此科，爲農業上之重要群體。此外，如芒、白茅等 一般，以雜草的形態廣泛地分布於世界上，而存在有600 屬1萬種以上的種類。 在禾本科植物的種子殼或植物體中含有非晶質的二氧 化矽，特別是在種子方面，其含有比例較多。該當非晶質 的二氧化矽，反應活性高，藉由與強鹼性水溶液混合加熱 --------訂---------線-4/^. (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） -15- 491814 A7 ____B7____ 五、發明說明（13) ，可在鹼性水溶液中溶解析出矽酸鹽成分。又，使用禾本 科植物的焚化灰，雖可合成人工沸石，但是爲了顯示製造 不含有焚化灰中之未燃燒碳素的白色人工沸石之例子，在 本發明中使用使矽酸成分由禾本科植物中加鹼溶解析出之 物質來進行人工沸石的合成。 在本發明中所謂火山噴出物之降塵，係藉由火山活動 噴出後，降落下來之物質，即所謂的浮石、火山灰等，然 而對照本發明的實施，爲了使熔融狀態的熔岩於空氣中急 速冷卻，最好使用於結晶化進行之前已凝固聚結起來，呈 粒子狀之微小非結晶狀態的自然玻璃之火山玻璃。 在本發明中所謂的焚化灰，係指含有以矽酸及鋁作爲 非結晶性之矽酸鋁鹽的焚化灰，可舉例出如可燃性廢棄物 之焚/化灰，以垃圾固體化燃料爲熱源使其燃燒所產生之焚 化灰以及煤灰.。在此，所謂可燃性廢棄物，係指由人間的 各種活動所產生的棄物中之可燃性物質，無論其爲一般廢 棄物以及產業廢棄物。所謂產業廢棄物，可舉例出如伴隨 著土木•建築工事等所產生之木材、紙等的可燃性之廢棄 物等。又，在本發明中所謂的都市垃圾，係指於可燃性廢 棄物中，作爲一般廢棄物而由家庭中所排出之生垃圾以外 的其他可燃性垃圾。 更者，在本發明中所謂的污泥，係指離解古紙後，在 回收纖維之步驟上因除塵操作所產生，被稱爲紙漿之污泥 ，以及因食品工場、地下水處理場等之廢水處理而產生之 活性污泥。在所謂紙漿的污泥方面，亦包含有經由過氧化 -16- (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） 491814 A7 ___ B7____ 五、發明說明（14) 氫、高氯酸、高溴酸等水溶液之處理’而除去污泥中之有 機物質者。又，所謂垃圾固體化燃料（Rdf : MmmmD FUEL )，係指由人間的各種活動所產生的棄物中’挑選出可 燃性之物質，將其破碎成一定的大小後，乾燥至含水率爲 10%左右，再依據情況混合石灰’使其固體化者’通常於 lkg中含有約2000〜3OOOkcal的熱量’其主要作爲發電用 的燃料來使用。 在本發明中所謂的矽酸富集材，係指大量含有玻璃、 矽藻土、水玻璃等之矽酸物質者。所謂前述的玻璃’係指 矽酸鹽玻璃，可舉例出如矽酸玻璃、鹼石灰玻璃、鉀鹼石 灰玻璃、鉛玻璃、鋇玻璃、硼矽酸玻璃等。又，作爲鹼石 灰玻璃而可舉出者，例如板玻璃、瓶玻璃、無鉛玻璃等。 從而，在本發明中，能使用作爲板玻璃、瓶玻璃、餐桌用 品玻璃、家庭用品玻璃、電氣用玻璃、照明用玻璃、理化 學用玻璃、醫療用玻璃、光學玻璃等玻璃使用後所產生的 廢棄物之碎玻璃。更進一步，亦包含爲了回收作爲廢棄物 的玻璃，於粉碎時所生成之玻璃的粉末者。爲了實施本發 i 明，在火山噴出物之降塵及焚化灰中所添加混合之玻璃， I 以使用顆粒小之粉末狀的玻璃爲佳。 σ 3 | 又，所謂前述的矽藻土，其大部分係指爲單細胞藻類 I 之矽藻的遺骸，就是由矽藻殼所形成之矽質的堆積物，其 1 ^ 通常混合有黏土、火山灰、有機物質等，而其本質爲含水 f > 非晶質二氧化矽。矽藻土的用途廣，被利用於吸附材料、 P 助濾材料、保溫材料、保冷材料、塡充材料、硏磨材料等 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -17- ------------------------------ (請先閱讀背面之注咅？事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 491814 A7 B7 五、發明說明（15) ，一般可依據其用途，粉碎矽藻土原土，並使其能適用於 目的用途般地精製之。然而’在本發明中，雖以被使用於 各種用途之矽藻土爲主，但是亦可使用使用後之廢矽藻土 。例如能舉出在水處理上，或在食品工業中精製砂糖、麥 芽糖、醬油、酒、啤酒、糖漿、植物油等之步驟上，在化 學工業中被使用之溶劑、機械油、石油等之精製步驟上， 在纖維工業中被使用之天然纖維、人造纖維之精製步驟上 ，作爲助濾材而已被使用過的廢矽藻土。 所謂前述的水玻璃，係指被表爲一般式Na2〇 · nSi〇2 • mH2〇的矽酸鈉之中的液狀者，在市場販賣品中以η = 2 〜4者爲主體，在本發明中，雖使用Si〇2/Na2〇的莫耳比（ η )爲2.1的水玻璃1號，但是亦可使用其他品味之物。 在本發明中所謂的鋁富集材，係指鋁渣滓或鋁酸蘇打 水溶液等之鋁含有量多的物質。所謂前述的鋁渣滓，係指 在鋁熔融步驟中所生成的氧化鋁與金屬鋁纏結，成爲渣滓 ，而覆蓋熔融鋁的表面之物，在鋁的軋製業及合金業等方 面，雖發生於溶融鋁步驟中，但是其組成將隨發生的狀況 而不同，雖然由熔解爐中剛掏出之鋁渣滓組成的大部分爲 金屬鋁，氧化鋁僅佔1 5〜40 % ，然而於渣滓處理業中所生 成之鋁渣滓的組成中，氧化鋁的含量超過50 % 。但是，在 本發明的鋁渣滓組成，並沒有被特別地限定。以往，鋁渣 滓基本上被視爲產業廢棄物，雖然努力於減少其生成量及 其金屬鋁的回收，然而在其有效利用上，幾乎不受重視。 此外，關於鋁酸蘇打水方面，能使用市場販賣之物。本發 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -18 - " --------^----.----.1^ Γ請先閱讀背面之注意事項再填寫本頁) 491814 A7 B7 五、發明說明（16) (請先閱讀背面之注意事項再填寫本頁) 明中所使用之玻璃、矽藻土或鋁渣滓的添加量，與使用原 料的矽鋁比，即（Si〇2和Al2〇3的重量組成比）X 1.7、以 及應當製造之人工沸石的種類相依存。即，火山噴出物之 降麈的矽鋁比大致上爲3〜4，而僅以火山噴出物之降塵爲 原料，進行鹼之加熱處理所得的人工沸石，係鈣十字沸石 及絲光沸石之混合物，其孔徑於鈣十字沸石方面爲0.4〜 0.5nm，於絲光沸石方面爲0.6〜0.7nm，陽離子交換容量 於鈣十字沸石方面大約爲380cmol ( + ) kg — 1，於絲光沸 石方面大約爲300cmol ( + ) kg— ^且具有脫臭作用。又 ，僅以焚化灰爲原料，進行鹼之加熱處理所得的人工沸石 ，係羥基方鈉石，雖其孔徑小，陽離子交換容量大，但是 髁無脫臭作用。雖藉由添加玻璃或矽藻土於火山噴出物之 降塵或焚化灰中，可使矽鋁比變高，但是若添加鋁渣滓於 火山噴出物之降塵或焚化灰中，將使矽鋁比變低。例如， 經齊邹智慧財轰局員工消費合作社印製 相對焚化灰之固體部分，藉由添加玻璃或矽藻土 20重量％ 以上，使矽鋁比變爲2以上，則所得的人工沸石中之鈣十 字沸石的比例將漸增。又，相對焚化灰之固體部分，若添 加玻璃或矽藻土 40至50重量％ ，使矽鋁比變爲2.5以上， 則人工沸石的成分幾乎全爲鈣十字沸石。更者，若藉由提 高玻璃或矽藻土的添加量至60重量％以上，使矽鋁比變爲 4以上，則於人工沸石中八面沸石的比例將漸增。另一方面 ，藉由添加鋁渣滓於焚化灰中，使矽鋁比變低，則進行鹼 之加熱處理所得的人工沸石中，羥基方鈉石的生成將變多 -19· 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 491814 A7 _B7 _ 五、發明說明（17) 在本發明中所謂的鹼性水溶液，係指溶解於水之鹼金 屬的氫氧化物，例如氫氧化鈉、氫氧化鉀、氫氧化鈣、氫 氧化鋇、氫氧化鋰等之水溶液，其中以使用氫氧化鈉水溶 液或氫氧化鉀水溶液爲佳。作爲反應時之鹼濃度，雖於0.5 〜4.5N間亦可引起反應，但是在本發明的實施上，則以2 至4 N的氫氧化鈉水溶液爲佳。 在本發明中所謂的原料混合物，係指將含矽酸成分以 及/或鋁成分之物質與矽酸富集材或鋁富集材相，以所定的 矽鋁比相配合後，再與鹼性水溶液混合而得之混合物。如 顯不於第2圖的系統圖中其調製方法的一例般’藉由將所 定量的飛灰等之人工沸石原料，與所定量之預先被調製爲 所定濃度的鹼性水溶液投入原料混合槽中，並於所定的時 間下混合之法來準備前述的原料混合物。例如，在使用氫 氧化鈉水溶液的情況下，最好以相對於人工沸石原料1之2 〜12 (更好爲3〜8 )的比例，混合稀釋成2〜3.5N之氫 氧化鈉水溶液。此外，鹼性水溶液的濃度與其配合比，將 參考人工沸石原料之種類、反應條件、反應時間、所期望 的生產量等來作適宜的設定。 I 雖然前述的原料混合物與鹼性水溶液的混合方法並無 | 特別地限定，但是，例如可藉由螺旋槳型之一般的攪拌混 ) 合器等來進行。以此法準備之原料混合物，藉由供給泵供 : 給於人工沸石生成步驟的裝置。此時，最好於其途中加溫 > (例如，80〜100 °C左右）供給。 c " 此外，因藉由本發明之加熱反應管接觸來製造人工沸Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs for employee cooperation printing 491814 A7 B7 V. Description of the invention (i) TECHNICAL FIELD The present invention relates to the reuse of inorganic waste containing silicic acid and aluminum components. After the above-mentioned inorganic waste is mixed with an alkaline aqueous solution, it is heated or pressurized in a pressure-resistant reaction vessel to react while applying an ultrasonic wave; or the above-mentioned inorganic waste and alkali having adjusted the silicon-aluminum ratio are reacted. A method for manufacturing artificial zeolite and a device for applying a heat treatment and an ultrasonic treatment while continuously flowing the alkaline aqueous solution together in a heating reaction tube. In the past, since ancient times, artificial zeolites mostly used coal ash, especially combustion ash called fly ash, which is generated when coal is burned in thermal power plants, etc., and added 2 ~ 4N alkaline aqueous solution to These raw materials are then prepared by heat treatment under atmospheric pressure. Therefore, the quality of the artificial zeolite produced depends on the composition of the coal as a raw material, and the quality is also limited. Although the surface is zeolized, the interior of the porous pores is not necessarily zeolized. Therefore, the artificial The quality of zeolite is not necessarily satisfactory. Also, as a method for producing artificial zeolite, such as using incineration ash such as coal ash or waste incineration ash and performing it in a batch type reaction device, this method has been disclosed in JP 6-32 1 5 No. 26 and the like. Further, as a method for continuously producing artificial zeolite, as disclosed in Japanese Patent Application Laid-Open No. 3 245 18, an apparatus for producing artificial zeolite using a circulating flow reaction tank. In addition, the catalyst zeolite called synthetic zeolite, although its structure is all zeolite, but in its synthesis, it must be in a high temperature region above 1000 ° C ------------- -^ --------- ^ (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -4- Ministry of Economic Affairs Intellectual Property Bureau employee consumer cooperative printed agriculture 491814 A7 B7 V. Description of the invention (2) Reaction, and because the raw materials such as silicic acid and aluminum used are not high-purity substances, it will hinder the generation of zeolite, so Low-purity raw materials must not be used. Also, the dustfall of volcanic ash, volcanic ash, pumice, volcanic glass, etc. that exists around the volcano cannot be used as industrial raw materials or agricultural land. Therefore, the so-called effective use of land On the face of it, the method of its use will become a problem. In cities, towns, and villages across the country, they are sorted into several types of garbage and collected. For example, although it is generally classified as combustible garbage, non-combustible garbage, oversized garbage, hazardous garbage, etc., the classification method will vary depending on the city's village. Among these refuses, although combustible refuse can generally be incinerated in incinerators, the disposal of incineration ash becomes another problem. In terms of non-combustible garbage, although glass, metal, and some synthetic resin can be reused, processing of synthetic resin products such as glass such as bottles, metal such as cans, boxes, and special bottles will cause problems. At present, the general waste discharge of the country has exceeded 50 million tons, and about 85% of them have been treated by incineration, crushing and recycling. However, the combined landfill volume of directly buried waste and incineration ash from waste treatment facilities has increased year by year. Therefore, in the villages and villages of each city, although most of this year-to-year increase in incineration ash is used in landfills, it is cured into zeolite and other forms of waste and treated as waste. However, Ensuring difficulties and other serious social problems -------- Order --------. Line (please read the precautions on the back before filling this page) This paper size applies Chinese national standards (CNS) A4 specification (210 X 297 mm) -5- Yao Qi Sr Jihui discusses staff members 11 provinces Fischer net fi Shanghai system 491814 A7 _____ B7 5. Invention description (3) In addition, in the industry The treatment of waste diatomaceous earth produced in the industry using diatomaceous earth; and in the smelting IS industry, the treatment of aluminum dross that occurs during smelting or refining will become a problem. In addition, in the aluminum industry, the disposal of alkaline waste cleaning liquids in aluminum sand boxes and the disposal of wastes such as gramineous plants with rice husks have become problems. Therefore, a manufacturing method of artificial zeolite that utilizes the various wastes described above as a resource has been considered. However, in the conventional batch type reaction device, not only the productivity cannot be improved, but also when a manufacturing device of a circulating flow reaction tank is used, It is also quite difficult to ensure the reaction temperature. DISCLOSURE OF THE INVENTION The present invention is to mix a substance containing a silicic acid component and / or an aluminum component with a silicic acid-rich material or an aluminum-rich material at a predetermined silicon-aluminum ratio, and then mix it with an alkaline aqueous solution. The raw material mixture obtained by mixing is put into a pressure-resistant reaction container, and heated or pressurized while subjecting it to ultrasonic reaction to synthesize artificial zeolite. In addition, as another method, it contains a silicic acid component and / or an aluminum component. After the substance is mixed with the silicic acid-rich material or the aluminum-rich material at a predetermined ratio of silicon to aluminum, it is then mixed with an alkaline aqueous solution, and the raw material mixture obtained by mixing this is set in a heat-resistant body tank. A person who synthesizes artificial zeolite by applying ultrasonic oscillation while contacting a heated reaction tube characterized by at least an artificial zeolite generation step of continuously flowing a raw material mixture into a heated reaction tube. The continuous production method of artificial zeolite synthesized by contacting the heating reaction tube described above, characterized in that the substance containing oxalic acid component and / or aluminum component is mixed with a silicic acid-rich material or an aluminum-rich material at a predetermined ratio of silicon to aluminum. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 public love) -------- ^ --------- ^ (Please read the precautions on the back before filling this page ) 491814 A7 ____B7 V. Description of the invention (4) After mixing, mix it with an alkaline aqueous solution, and then set the mixed raw material mixture in a heat-resistant body tank, while applying ultrasonic vibration, while using Those having at least an artificial zeolite generation step for continuously flowing the raw material mixture into the heated reaction tube. According to this invention, the aforementioned raw material mixture is set in a heating medium tank. 'While ultrasonic oscillation is applied, the turbulent flow generated when the raw material mixture passes through the interior of the heated reaction tube is sufficient and efficient. This raw material mixture was stirred. The above raw material mixture is obtained by mixing a material containing a silicic acid component and / or an aluminum component with a silicic acid-rich material or an aluminum-rich material at a predetermined ratio of silicon to aluminum, and then mixing it with an alkaline aqueous solution. At this time, since the full length of the reaction tube has been set according to predetermined conditions, the reaction is started immediately after the aforementioned raw material mixture is supplied to the heated reaction tube. As a result, it is possible to promote the formation reaction of artificial zeolite, and also achieve the effect of shortening the reaction time and improving the manufacturing efficiency. As the material containing the aluminum component as a raw material for synthetic artificial zeolite, an alkaline waste liquid containing aluminate can be used, and as the alkaline waste liquid containing aluminate, aluminum used in the manufacture of aluminum products can be used. Alkaline waste washing liquid in the sand box, or the aluminum sludge produced during the manufacture of acid-resistant aluminum is dissolved by adding alkali. In addition, as a substance containing a silicic acid component as a raw material when synthesizing artificial zeolite, a silicic acid component extracted from a gramineous plant such as rice or wheat can be used. As the silicic acid-enriched material, glass, diatomaceous earth, or water glass can be used, and among them, broken glass of waste glass is preferred as the aforementioned glass. As an aluminum-rich material, slag can be used. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) · 'Line 491814 A7 B7 V. Description of the invention (5) In terms of the silicic acid component and the aluminum component of the raw material in the case of artificial zeolite, volcanic ejection dust can be used, and as the volcanic ejection dust, volcanic glass can be used. As a material containing a silicic acid component and an aluminum component, incineration ash can be used, and as the aforementioned incineration ash, incineration ash of combustible waste can be used, and among them, incineration ash using municipal garbage and solid waste fuel is used as the incineration ash. The combustible waste is preferred. In addition, as the aforementioned combustible waste, sludge can also be used. As the sludge, it can be used in the process of recycling fibers after disintegration of ancient paper. The resulting sludge is preferred. As the aforementioned sludge, sludge produced by wastewater treatment can also be used. In the case of synthetic artificial zeolite, the heat treatment is mostly performed in the range of 60 to 230 / C. As the aforementioned heat treatment, infrared radiation can be used to heat the pressure-resistant reaction container or the heating medium. A combination of saturated steam and infrared radiation is used to heat the pressure-resistant reaction vessel or heating medium. Further, as the aforementioned heat treatment person, microwave heating may be used to heat the pressure-resistant reaction container or the heating medium, or a combination of saturated steam and microwave heating may be used to heat the pressure-resistant reaction container or the heating medium. Furthermore, as a heat treatment person, induction heating may be used to heat the heating medium, or saturated vapor and induction heating may be combined. The number of vibrations when an ultrasonic wave is applied to the reaction tube during the reaction is preferably performed in a range of 18 to 500 kHz. As the alkaline aqueous solution at the time of the reaction, use sodium hydroxide aqueous solution or hydrogen (please read the precautions on the back before filling this page) Order ----.---- iw line-This paper size applies to Chinese national standards ( CNS) A4 specification (210 X 297 mm) -8- 491814 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (6) The potassium oxide aqueous solution is better, and it is used as the concentration of alkaline aqueous solution during the reaction , Preferably from 2 to 4N. In the method for manufacturing artificial zeolite by contacting the heated reaction tube of the present invention, in the aforementioned artificial zeolite generation step, a change operation length of the reaction tube is provided. According to this invention, since the operation for changing the length of the reaction tube is provided, the rate of production of artificial zeolite depends on the type or concentration of the artificial zeolite raw material and the alkaline aqueous solution, the flow rate of the slurry, and the setting of the reaction tube. In the case of changes in conditions, etc., it is also possible to easily control the reaction time based on its generation rate. The method for manufacturing artificial zeolite by contacting the heated reaction tube of the present invention has the following characteristics, that is, a substance containing a silicic acid component and / or an aluminum component is phased with a silicic acid-rich material or an aluminum-rich material in a predetermined manner. After the silicon-aluminum ratio is mixed, it is mixed with an alkaline aqueous solution, and then a predetermined amount of artificial zeolite is added to the raw material mixture obtained by mixing. According to this invention, since a predetermined amount of artificial zeolite is blended in the raw material mixture supplied to the reaction tube, the artificial zeolite will become a kind of crystal and the production of artificial zeolite will easily occur. Therefore, it is possible to shorten the reaction time and Improve manufacturing efficiency. The method for producing artificial zeolite by contacting the heated reaction tube of the present invention has the following characteristics: it has the aforementioned artificial zeolite generation step, and further separates artificial from the slurry containing the artificial zeolite produced. A zeolite separation step, a step of replacing the type of artificial zeolite, and a dehydration step of removing water from the artificial zeolite. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -g--------- ^ ---- ^ ----. Line (please read the precautions on the back first) (Fill in this page again) 491814 A7 B7 V. Description of the invention (7) According to this invention, because in the above-mentioned artificial zeolite generation step, an artificial zeolite separation step, an artificial zeolite type replacement step, and an artificial zeolite are added. The dehydration step makes it possible to efficiently produce artificial zeolite through continuous steps. Each of the foregoing steps, that is, the artificial zeolite generation step, the artificial zeolite separation step, the artificial zeolite type replacement step, and the artificial zeolite dehydration step have the following characteristics: they can be pressure-fed due to the pressure difference between them. The raw material mixture and artificial zeolite described above. According to this invention, since a pressure difference is generated between the above steps, the raw material mixture and the artificial zeolite can be easily pressure-fed. As a result, it is possible to easily and efficiently manufacture artificial zeolite. The method for manufacturing artificial zeolite by contacting the heated reaction tube of the present invention has the following characteristics. The dehydration step of the artificial zeolite is performed by sucking air and water vapor in the dehydration tank to reduce the pressure, and then pressurizing. · After heating and sucking the air and water vapor, return it to the spiral tube in the dewatering tank with artificial zeolite, and then evaporate the water in the artificial zeolite while condensing and condensing the water vapor in the spiral tube. Dehydration is performed, and then these actions are repeated. According to this invention, it is possible to efficiently perform dehydration by using the heat generated when the air and water vapor are extracted after being pressurized and heated. The method for producing an artificial zeolite by contacting the heated reaction tube of the present invention has the following characteristics: it has at least a phase containing a silicic acid component and / or an aluminum component and a silicic acid-rich forest or an aluminum-rich material. After mixing with the specified sand-aluminum ratio, it is mixed with an alkaline aqueous solution, and then mixed to obtain -------------------- Order -------- --- Line IAW. (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -10-491814 A7 ___B7__ V. Description of the invention (8 ) The raw material mixture continuously flows in an artificial zeolite generating device in a reaction tube that is set and heated under predetermined conditions. In this case, it is preferable to provide a partition in the reaction tube. The method for producing artificial zeolite by contacting the heated reaction tube of the present invention has the feature that an operation for changing the length of the reaction tube is provided in the aforementioned reaction tube. The method for producing artificial zeolite by contacting the heated reaction tube according to the present invention has the feature that an artificial zeolite is provided for adding the artificial zeolite from the mixing tank of the slurry to the entrance of the reaction tube. The inlet of the artificial zeolite in the raw material mixture or the inlet of the alkaline aqueous solution containing artificial zeolite. The above-mentioned raw material mixture is obtained by mixing a material containing a silicic acid component and / or an aluminum component with a silicic acid-rich material or an aluminum-rich material at a predetermined silicon-aluminum ratio, and then mixing it with an alkaline aqueous solution. The manufacturing device for manufacturing artificial zeolite by contacting the heated reaction tube of the present invention has the following characteristics: it has the aforementioned artificial zeolite generation device, artificial zeolite separation device, artificial zeolite type replacement device, and artificial zeolite. Dewatering device. The manufacturing apparatus for manufacturing artificial zeolite by contacting the heated reaction tube of the present invention has the feature that a pressure test operation is provided on each of the aforementioned devices, and the devices are mutually connected based on the pressure test operation. Pressure adjustment operation caused by pressure difference. According to this invention, since each device is provided with a pressure verification operation and a pressure adjustment operation that causes a pressure difference between each device based on the pressure verification operation, the operations of each step can be performed by those operations. Mutual-11-(Please read the notes on the back before filling this page) This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) 491814 A7 _ B7 V. Description of the invention (9) Pressure Poorly produced. As a result, not only the raw material mixture and the artificial zeolite can be easily pressed and fed, but also the production of artificial zeolite can be easily and efficiently. Brief Description of the Drawings Figure 1 shows the production of artificial zeolite by contacting the heating reaction tube of the present invention. A flowchart of an example of a manufacturing method is shown in FIG. 2. FIG. 2 is a system diagram showing an example of a method for manufacturing artificial zeolite by contacting the heating reaction tube of the present invention, and FIGS. 3 and 4 are diagrams showing a device for generating artificial zeolite. Structure diagram, FIG. 5 is an explanatory diagram showing a state of turbulent flow in a reaction tube, and FIG. 6 is a structure diagram showing an example of a partition plate provided in the reaction tube. FIG. 7 is an example of a separation device of artificial zeolite. FIG. 8 is a structural diagram showing an example of a dehydration device for artificial zeolite. 1 is a continuous manufacturing device for artificial zeolite 2 is a raw material mixture preparation device 3 raw material storage tank 4 alkaline aqueous solution tank 5 raw material mixing tank 5a silicic acid enrichment tank 5b aluminum enrichment tank 6 raw material mixture supply tank B artificial zeolite generation device 7Reaction tube-12- (Please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 491814 A7 _B7 V. Description of the invention (1〇) 7a Ultrasonic vibrator 8 heat carrier tank 9 heat carrier oil 1 0 heater 1 1, 27, 33, 38, 43 rotary pump P input port 20 cooler 20a conduit C artificial zeolite separation device 21 artificial zeolite separation device 22, 29 partition wall 23 separation tank 24Λ1, 36, 41 discharge section 25, 25a, 25b, 40a air port 26, 26b, 37, 42 transfer section 5 1 pressure regulating system D, F artificial zeolite cleaning device. 28, 39 artificial Zeolite washing device ί 30,40 washing tank ί 31a, 50 washing water supply tank; 34 artificial zeolite type replacement device: 35 type replacement tank); 34a solution tank; 44 dewatering device • 13- (Please read the back first (Please note before filling out this page) This paper size applies to China Standard (CNS) A4 (210 X 297 mm) 491814 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ______B7__ V. Description of the invention (H) 45 finished product tank 46 dehydration tank 47 compressor E type of artificial zeolite replacement device G Desirable device for artificial zeolite R pump The best form of the invention to be implemented The method for producing artificial zeolite according to the present invention is to combine a material containing a silicic acid component and / or an aluminum component with a silicic acid-rich material or an aluminum-rich material After the phase is matched with the predetermined silicon-aluminum ratio, it is mixed with an alkaline aqueous solution, and then the raw material mixture obtained by mixing is put into a pressure-resistant reaction container, and heated or pressurized to react while applying ultrasonic vibration to synthesize. The method of artificial zeolite, in addition to other methods, is to mix the material containing silicic acid component and / or aluminum component with oxalic acid-rich material or aluminum-rich material in a predetermined ratio of silicon and aluminum, and then mix with alkaline. The aqueous solution is mixed, and the mixed raw material mixture is set in a heat-resistant medium tank. While applying ultrasonic oscillation, at least the raw material mixture is continuously flowed through the substrate. Artificial zeolite within the reaction tube heat generating step of heating the reaction tube characterized by contacting the zeolite synthesis method of doing so. The main components of the obtained artificial zeolite are phillipsite, mordenite, faujasite, zeolite A, hydroxysodalite, etc., and also contains a small amount of other components. The parts other than zeolite are those that are not zeolite components, such as organic matter, iron, and other impurities, as well as those that coexist with intermediate products generated during the formation of zeolite. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) _ 14--------------------- Order ------- --Line (please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 491814 A7 B7 V. Description of the invention (12) The substance containing aluminum in the present invention is The so-called aluminum waste liquid containing aluminate is either an alkaline waste cleaning solution called an aluminum sand box, or an aluminum sludge produced during the manufacture of acid-resistant aluminum is dissolved by adding alkali. In addition, as an alkaline waste cleaning solution for an aluminum sand box, for example, when alkaline cleaning is used to produce aluminum finished products such as aluminum window frames, bearings, valves, precision tools, bulbs, wires, and plates, etc. Waste liquid from the flask. In addition, the person who dissolves the aluminum sludge generated during the manufacture of acid-resistant aluminum and dissolves it with alkali refers to the use of anodized aluminum to neutralize the aluminum acid waste liquid generated by the implementation of the corrosion-resistant oxide film procedure, and then separate the water-soluble The precipitated gel of aluminum hydroxide obtained after the sexual component is neutralized with alkali, and the waste liquid containing aluminate is dissolved and dissolved by adding alkali to the precipitate or cake-like substance obtained after separation. In the present invention, the substance containing a silicic acid component is a so-called alkaline aqueous solution which dissolves and extracts a silicic acid component from a waste containing a silicic acid component, and uses it as a waste containing a silicic acid component. Examples include rice husks and plant bodies of grasses such as rice and wheat. The aforementioned family of gramineous plants is a family of so-called monocotyledons, which are all herbs except for bamboo. Grains such as rice, wheat, corn, chestnuts, gardenia, and oats belong to this family and are important groups in agriculture. In addition, such as awn, white grass, etc., they are widely distributed in the world in the form of weeds, and there are more than 600 genera and 10,000 species. The seed shell or plant body of the gramineous plant contains amorphous silicon dioxide, especially in the case of seeds, which contains a large proportion. The amorphous silicon dioxide has high reactivity, and is heated by mixing with a strong alkaline aqueous solution .-------- Order --------- Line-4 / ^. (Please read first Note on the back, please fill in this page again) This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) -15- 491814 A7 ____B7____ 5. Description of the invention (13), which can be dissolved in alkaline aqueous solution Silicate composition. In addition, although incinerated ash using a gramineous plant can synthesize artificial zeolite, in order to show an example of producing a white artificial zeolite that does not contain unburned carbon in the incinerated ash, the present invention uses a silicic acid component from a gramineous plant. Alkali is used to dissolve the eluted substances to synthesize artificial zeolite. In the present invention, the so-called dustfall of volcanic eruption material refers to the material that falls after volcanic activity, namely, so-called pumice, volcanic ash, etc. However, in contrast to the implementation of the present invention, in order to rapidly cool molten lava in the air, It is best to use volcanic glass, which has been solidified and agglomerated before the crystallization is carried out, and is in the form of particles in a small amorphous state. In the present invention, the so-called incineration ash refers to incineration ash containing silicic acid and aluminum as non-crystalline aluminum silicate salts, and examples thereof include incineration / ash of combustible waste, and solid waste fuel is used as The incineration ash and coal ash produced by the combustion of heat source. Here, the so-called flammable waste refers to flammable substances in wastes generated by various human activities, regardless of whether they are general wastes or industrial wastes. Examples of industrial waste include flammable wastes such as wood and paper that are produced by civil engineering and construction works. The term "municipal garbage" as used in the present invention refers to flammable garbage other than raw garbage discharged from households as a general waste in a combustible waste. Furthermore, in the present invention, the so-called sludge refers to the sludge produced by the dust removal operation during the fiber recovery step after dissolving the ancient paper, and the sludge called pulp, and the waste water treatment of food factories, groundwater treatment plants, etc. The resulting activated sludge. The so-called pulp sludge also includes peroxidation-16- (please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 491814 A7 ___ B7____ 5. Description of the invention (14) Treatment of aqueous solutions such as hydrogen, perchloric acid, perbromic acid, etc. to remove organic substances in sludge. In addition, the so-called solid waste fuel (Rdf: MmmmD FUEL) refers to 'selecting combustible materials from wastes produced by various human activities, crushing them into a certain size, and drying them to a moisture content of 10 %, And depending on the situation, the lime is 'solidified' and usually contains about 2,000 to 3,000 kcal of heat in 1 kg. It is mainly used as a fuel for power generation. The so-called silicic acid-rich material in the present invention refers to those containing a large amount of silicic acid substances such as glass, diatomaceous earth, and water glass. The aforementioned glass' means silicate glass, and examples thereof include silicate glass, soda lime glass, potassium soda lime glass, lead glass, barium glass, and borosilicate glass. Examples of the soda lime ash glass include plate glass, bottle glass, and lead-free glass. Therefore, in the present invention, it is possible to use glass produced by using glass such as plate glass, bottle glass, tableware glass, houseware glass, electrical glass, lighting glass, physical and chemical glass, medical glass, and optical glass. Broken glass of waste. Furthermore, it also includes powders of glass produced during crushing in order to recover glass as waste. In order to implement the present invention, it is preferable to use powdered glass having a small particle size as a mixed glass added to the dustfall and incineration ash of the volcanic eruption. σ 3 | Also, most of the so-called diatomaceous earth refers to the remains of diatoms that are unicellular algae I, which are siliceous deposits formed by diatom shells. 1 ^ is usually mixed with clay, Volcanic ash, organic matter, etc., and its essence is water-containing f > amorphous silicon dioxide. Diatomite has a wide range of uses, and is used in adsorption materials, P filter aids, heat insulation materials, cold insulation materials, filling materials, honing materials, etc. This paper applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) ) -17- ------------------------------ (Please read the note on the back? Matters before filling out this page) Economy Printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau 491814 A7 B7 V. Invention Description (15) Generally, the diatomite raw soil can be crushed according to its use and made suitable for the purpose. However, in the present invention, although diatomaceous earth mainly used in various applications is used, it is also possible to use waste diatomaceous earth after use. For example, in the process of water treatment or in the process of refining sugar, maltose, soy sauce, wine, beer, syrup, vegetable oil, etc. in the food industry, the steps of refining solvents, machine oils, petroleum, etc. used in the chemical industry The waste diatomite has been used as a filter aid in the purification steps of natural fibers and rayon used in the fiber industry. The aforementioned water glass refers to a liquid state among sodium silicates expressed as the general formula Na2〇 · nSi〇2 · mH2〇. In the marketed products, η = 2 to 4 is the main body. In the invention, although water glass No. 1 having a molar ratio (η) of Si02 / Na2O of 2.1 is used, other tastes may be used. The aluminum-rich material used in the present invention refers to a substance having a large amount of aluminum, such as aluminum dross or an aqueous solution of aluminate soda. The aforementioned aluminum dross refers to the alumina produced in the aluminum melting step entangles with metallic aluminum to become dross, and covers the surface of the molten aluminum. Although it occurs in the aluminum rolling industry and alloy industry, In the step of melting aluminum, its composition will be different according to the situation. Although most of the aluminum dross just taken out of the melting furnace is metal aluminum, alumina only accounts for 15 ~ 40%. In the composition of the aluminum dross produced in the industry, the content of alumina exceeds 50%. However, the aluminum dross composition in the present invention is not particularly limited. In the past, aluminum slag was basically regarded as industrial waste. Although efforts were made to reduce the amount of aluminum slag produced and the recovery of its metal aluminum, it has received little attention for its effective use. In addition, as for the aluminate soda, it is possible to use what is marketed. The paper size of this issue applies to China National Standard (CNS) A4 (210 X 297 mm) -18-" -------- ^ ----.----. 1 ^ Γ Read the notes on the back and fill in this page) 491814 A7 B7 V. Description of the invention (16) (Please read the notes on the back before filling in this page) The amount of glass, diatomaceous earth or aluminum slag used in the instructions, It depends on the silicon-aluminum ratio of the raw materials, namely (the weight composition ratio of SiO2 and Al203) X 1.7, and the type of artificial zeolite to be manufactured. That is, the silica-to-aluminum ratio of the volcanic eruption is approximately 3 to 4, and the artificial zeolite obtained by performing alkali heat treatment using the volcanic eruption as the raw material is a mixture of calcined zeolite and mordenite. Its pore diameter is 0.4 to 0.5 nm for phillipsite, 0.6 to 0.7 nm for mordenite, and the cation exchange capacity is about 380 cmol (+) kg — 1 for mordenite, and about 300 cmol (+ for mordenite) ) kg— ^ and has a deodorizing effect. In addition, artificial zeolite obtained by incineration ash as a raw material and subjected to alkali heating treatment is a hydroxy sodalite. Although it has a small pore size and a large cation exchange capacity, it has no deodorizing effect. Although the silica-aluminum ratio can be increased by adding glass or diatomaceous earth to the dust-fall or incineration ash of the volcanic ejection, the addition of aluminum slag to the dust-fall or incineration ash of the volcanic ejection will change the silica-aluminum ratio. low. For example, if the solid portion of the incinerated ash is printed by the employee cooperative of the Qi Zou Zhicai Bureau, and the glass-diatomite is added by 20% by weight or more, the silicon-aluminum ratio becomes 2 or more. The proportion of phillipsite will gradually increase. In addition, if glass or diatomaceous earth is added in an amount of 40 to 50% by weight relative to the solid portion of the incineration ash, and the silica-alumina ratio becomes 2.5 or more, the composition of artificial zeolite is almost all zeolite. Furthermore, if the amount of glass or diatomaceous earth is increased to 60% by weight or more, and the silica-alumina ratio is changed to 4 or more, the proportion of faujasite in artificial zeolite will gradually increase. On the other hand, by adding aluminum slag to the incineration ash to reduce the silicon-aluminum ratio, the artificial zeolite obtained by the alkali heating treatment will increase the production of hydroxy sodalite-19. This paper is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 491814 A7 _B7 _ V. Description of the invention (17) The so-called alkaline aqueous solution in the present invention refers to the hydroxide of an alkali metal dissolved in water, such as hydrogen As the aqueous solution of sodium oxide, potassium hydroxide, calcium hydroxide, barium hydroxide, lithium hydroxide, etc., it is preferable to use an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide. Although the alkali concentration at the time of the reaction may cause the reaction between 0.5 and 4.5 N, in the practice of the present invention, a 2 to 4 N sodium hydroxide aqueous solution is preferred. The so-called raw material mixture in the present invention refers to a material containing a silicic acid component and / or an aluminum component and a silicic acid-enriched material or an aluminum-enriched material, mixed with a predetermined silicon-aluminum ratio, and then alkaline. A mixture obtained by mixing aqueous solutions. As an example of the preparation method shown in the system diagram of FIG. 2, 'by putting a predetermined amount of artificial zeolite material such as fly ash and a predetermined amount of an alkaline aqueous solution prepared to a predetermined concentration into a raw material mixing tank, And mixing at a predetermined time to prepare the aforementioned raw material mixture. For example, when using an aqueous sodium hydroxide solution, it is preferable to mix and dilute the aqueous solution of sodium hydroxide to 2 to 3.5N at a ratio of 2 to 12 (more preferably 3 to 8) relative to the artificial zeolite raw material 1. In addition, the concentration of the alkaline aqueous solution and its compounding ratio are appropriately set with reference to the kind of artificial zeolite raw material, reaction conditions, reaction time, desired production amount, and the like. I Although the method of mixing the aforementioned raw material mixture and the alkaline aqueous solution is not particularly limited, it can be performed, for example, by using a propeller-type general stirring mixer or the like. The raw material mixture prepared in this way is supplied to a device for the artificial zeolite generation step by a supply pump. In this case, it is best to warm up > (for example, about 80 to 100 ° C) on the way. c " In addition, artificial boiling is produced by contacting the heated reaction tube of the present invention
I 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 胃_ (請先閱讀背面之注意事項再填寫本頁) 訂---------線_ 經濟部智慧財產局員工消費合作社印製 491814 A7 B7 五、發明說明（18) 石的製造方法係連續的製造法，故前述的混合物與鹼性水 溶液之投入、混合，以及更進一步地，對於人工沸石生成 步驟之裝置的原料混合物之供給，皆藉由閥操作等來連續 地進行。此外，藉由後述的循環型之反應管來生成人工沸 石時，對於人工沸石生成步驟之裝置的原料混合物之供給 ，在送反應管中所生成之人工沸石至下一步驟後，將藉由 閥操作等來斷續地進行。 作爲欲實施本發明之加熱處理的熱源，雖可利用飽和 蒸氣、過熱蒸氣、紅外線放射、微波加熱、感應加熱，然 而以焚化灰作爲人工沸石的原料來使用時，因可靠近軸式 垃圾熔融爐、煉焦床式熔融爐、煤油式熔融爐、氣體燃燒 式熔融爐、氣化熔融爐、電弧式熔融爐、等離子式熔融爐 等之熔融爐來設置人工沸石的反應設備，故能藉由利用這 些爐的廢熱，.經濟地進行加熱處理。 在使用飽和蒸氣的情況下，雖然一般皆於耐壓反應容 器內進行反應，但是欲實施本發明之加熱處理，係於大氣 壓下加熱反應管至所定溫度，然後更進一步地由外部將取 代載熱體油之飽和蒸氣導入載熱體槽，故能確保反應溫度 0 在本發明中所謂的紅外線放射，係指藉由放射紅外線 來加熱耐壓反應容器或載熱體槽之方法。在此所謂的紅外 線，係指波長0.1〜1000鹘的電磁波，爲了進行加熱處理 ，以使用波長範圍於紅外線至遠紅外線之2.5〜30耪的電 磁波爲佳。爲了實施本發明，所使用之裝置只要能產生上 --------訂--------·線 (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） -21 · 經濟部智慧財產局員工消費合作社印製 491814 A7 _ B7 五、發明說明（19) 述電磁波即可，並無特別地限定。又，藉由倂用飽和蒸氣 之加熱與紅外線放射之加熱之加熱處理，能有效率地使耐 壓反應容器內或反應管內之鹼性水溶液的溫度上昇。 在本發明中所謂的感應加熱，係指以起因於磁束變化 所產生的感應電流之焦耳熱爲熱源的加熱方法，能利用於 耐壓反應容器或載熱體槽爲鐵等之導電性材料之情況。又 ，藉由倂用飽和蒸氣之加熱與感應加熱之加熱處理，能有 效率地使鹼性水溶液的溫度上昇。 欲實施本發明而使用的超音波處理，其音波的振動數 以由高音領域18kHz至超音波領域500kHz的振動數爲佳， 其強度並無特別地被限定，與超音波發振動器的性能相依 存。反應時，藉由於耐壓反應容器內或反應管內之鹼性水 溶液中施以超音波，使振動及氣蝕發生於該水溶液中，此 現象不僅具有促進沸石原料表面之鹼性水溶液循環之效果 ，並且亦具有使鹼性水溶液浸透至因沸石化反應所產生的 細孔之深處之效果。 在本發明中使用作爲人工沸石原料之煤灰方面，已知 原料粒子內的非結晶性矽酸鋁由原料粒子內擴散至鹼性水 溶液中之速度成爲反應速率決定者，以及鋁分子與可溶性 矽酸鹽的反應於粒子的表面進行，而與鹼性水溶液中之可 溶性矽酸鹽濃度相依存等。其結果，來自矽酸鋁鹽之可溶 性矽酸鹽的粒子內擴散，與產生於粒子表面之氧化鋁以及 可溶性矽酸鹽之固相反應，將於同一反應層內被連續地進 行，爲了確保一定品質的人工沸石，進行超音波處理以及 --------訂---------線 (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） -22- 491814 A7 B7 五、發明說明（20) 使反應溫度變高是有利的。 首先，在第一階段方面’以矽酸鋁鹽的沸石化爲目的 ，藉由原料與鹼性水溶液之混合，即藉超音波處理，將生 成之可溶性矽酸鹽由原料表面快速地除去’以促進新的鹼 性水溶液之擴散，而使沸石化於短時間內進行；在第二階 段方面，在可溶性矽酸鹽濃度變高的狀態下，藉由加熱來 進行與氧化鋁之反應。又，使含有鋁酸之鹼性廢液與含有 矽酸之鹼性廢液反應來製造人工沸石時’因反應不爲擴散 反應速率決定步驟，故合成反應於短時間內完成。 藉由原料之沸石化反應的進行而逐漸溶解於鹼性水溶 液中之可溶性矽酸鹽之濃度的調整，可藉由與原料混合之 鹼性水溶液的供給量來調整。又，欲進行反應槽內之鹼性 濃度的調整，可藉由調整鹼性水溶液中之鹼性濃度來進行 ，雖然在生成人工沸石上，能使用濃度0.5〜4.5N之強鹼 性，然而仍以使用2至4N的氫氧化鈉水溶液爲佳。又，爲 了加熱至1 00 °C以上，在使用飽和蒸氣的情況下，最好使 耐壓反應容器或載熱體槽中之壓力保持於2〜30kg/cm2，即 120〜23 0 °C下，而使反應順利地進行。 本發明之人工沸石，係藉由將供給於反應之含矽酸成 分以及/或鋁成分之物質與矽酸富集材或鋁富集材相以所定 的矽鋁比相配合後，再將與鹼性水溶液混合之原料混合物 放入耐壓反應容器，一邊施以超音波振動一邊加熱或加壓 使其反應之方法，或將前述的原料混合物，一邊施以超音 波振盪，一邊使其流動於被加熱的反應管內之方法而獲得 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -23- (請先閱讀背面之注意事項再填寫本頁) — II----訂---------線. 491814 A7 B7 五、發明說明（21) 者。 以下，將一邊參考圖面一邊說明有關藉由本發明之加 熱反應管接觸來製造人工沸石的製造方法以及其製造裝置 〇 第1圖係顯示藉由本發明之加熱反應管接觸來製造人 工沸石的製造方法之一例的流程圖，第2圖係顯示藉由本 發明之加熱反應管接觸來製造人工沸石的製造方法之一例 的系統圖，第3圖、第4圖係顯示人工沸石的生成裝置之結 構圖，第5圖係顯示反應管內之亂流的狀態之說明圖，第6 圖係顯示於反應管內設置隔板之一例的結構圖，第7圖係 顯示人工沸石的分離裝置之一例的結構圖，第8圖係顯示 人工沸石的脫水裝置之一例的結構圖。 /藉由本發明之加熱反應管接觸來製造人工沸石的製造 方法’如顯不於弟1圖、弟2圖中一般，將供給於反應之含 矽酸成分以及/或鋁成分之物質與矽酸富集材或鋁富集材相 以所定的矽鋁比相配合後，再藉由將前述的原料混合物順 序地通過與鹼性水溶液混合之原料混合物的準備步驟、人 工沸石的生成步驟、分離步驟、洗淨步驟、類型置換步驟 、洗淨步驟、脫水步驟之各步驟來製造之方法。 其次，將針對各步驟，詳細地說明人工沸石的連續製 造裝置。 (1 )原料混合物的準備_驟： 原料混合物的準備步驟，係將供給於反應之含矽酸成 -24- (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） 經濟部智慧財產局員工消費合作社印製 491814 A7 B7 五、發明說明（22) 分以及/或鋁成分之物質與矽酸富集材或鋁富集材相以所定 的矽鋁比相配合後，再與鹼性水溶液混合之步驟。 在第2圖中，1爲人工沸石的連續製造裝置，2爲原料 混合物準備裝置。原料混合物準備裝置2 ，具備有儲存製 造人工沸石之原料的原料貯藏槽3 ，將鹼性水溶液供給於 原料中之鹼性水溶液槽4，混合由前述的原料貯藏槽3導入 之原料與由前述的鹼性水溶液槽4導入之鹼性水溶液的原 料混合槽5，將矽酸富集材補給於前述原料混合槽5中之砂 酸富集槽5a，將鋁富集材補給於前述原料混合槽5中之銘 富集槽5b ，以及儲存被混合之原料，以便供給於隨後之步 驟的原料混合物供給槽6。 將則述的原料貞丁藏槽3中之原料與前述的驗性水溶液 槽Λ中之鹼性水溶液送入原料混合槽5中，在此，補給來自 矽酸富集槽5a之矽酸富集材及來自鋁富集槽5b之鋁富集材 。將調整矽鋁比後所得之原料混合物，送至欲供給原料混 合物於隨後步驟之原料混合物供給槽6中儲存。在人工沸 石的合成反應開始時，原料混合物將被送至其次所述之人 工沸石的生成步驟中。 (2 )人工沸石的生成步驟： 人工沸石的生成步驟，係將於前記原料混合物準備步 驟中所得之原料混合物導入設置於後述載熱體槽中之加熱 反應管內，並使其連續流動來合成沸石的步驟。人工沸石 的生成裝置B ’具備有進行人工沸石之合成反應的反應管7 本紙張尺度刺巾關家標準（CNS)A4規格（210 X 297公爱） 25- l· --------訂----^----•-線 IIP- (請先閱讀背面之注意事項再填寫本頁) 491814 五、發明說明（23) (請先閱讀背面之注意事項再填寫本頁) ’附設於前述反應管之端部的超音波振動器7a ，內藏前述 反應管7且作爲加熱用之載熱體槽8，被導入前述載熱體槽 8之載熱體油9 ，與過熱前述載熱體油之加熱器1〇，以及 使原料混合物循環於前述反應管內之回轉泵11。 由原料混合物準備步驟中送來的原料混合物，藉由回 轉泵11導入反應管7內，使其循環。爲了使被加熱器10所 加熱之載熱體油9循環於內藏前述反應管7之載熱體槽8內 ，前述反應管7被均一地加熱。又，於前述反應管7之端部 預事先設置超音波振動器7a，使前記原料混合物於該反應 管7內被合成爲甚至連粒子的細孔亦存在之沸石。在沸石 合成終了後所得之人工沸石的料漿，將藉由回轉泵1 1被送 至其次所說明之人工沸石的分離步驟中。 ,此外，在本人工沸石的連續製造裝置1方面，雖使用 藉加熱器10所加熱之載熱體油9來加熱反應管7 ，然而亦 可使用紅外線放射、飽和蒸氣、組合飽和蒸氣與紅外線放 射、微波加熱、組合飽和蒸氣與微波加熱、感應加熱、組 合飽和蒸氣與感應加熱來加熱載熱體槽8。 經齊部智慧財產局員工消費合作社印製 人工沸石的生成步驟，係欲使所供給之前記原料混合 物反應成爲人工沸石之步驟，前記原料混合物將連續或斷 續地被供給，而藉由此原料混合物連續地流過已設定成所 定溫度•壓力•流量等之反應管7來引發人工沸石的生成 反應。 在藉由本發明之加熱反應管接觸來製造人工沸石之連 續製造方法以及連續製造裝置上，其最大的特徵爲至少必 -26- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 491814 經濟部智慧財i局員工消費合作钍印製 A7 B7 五、發明說明（24) 須具有此人工沸石的生成步驟以及製造裝置。因此，只有 爲具有此人工沸石生成步驟之人工沸石的製造方法者，即 使於其前步驟或後步驟中包含有在本申請中所說明之各步 驟’或包含有說明以外之其他步驟及裝置亦可。 此外’在人工沸石生成步驟裝置中所謂「連續的」， 係表示幾乎不間斷地連續供給•通過之狀態，以及每一定 間隔的供給與通過皆連續地被進行之狀態。此外，使如後 述般的前記原料混合物於反應管中流動的情況，成爲後者 之狀態，即成爲每一定間隔的供給與通過皆連續地被進行 之狀態，在此亦有可能將其稱爲「斷續的」之情形。 人工沸石的生成反應，如顯示於第3圖、第4圖及第5 圖中一般，於所定的壓力·溫度之.條件下，藉由前記原料 混合物於反應管7中流動時所產生之渦流或亂流的作用來 促進之。藉由.此渦流或亂流，將極爲有效率地攪拌前記原 料混合物中之人工沸石原料與鹼性水溶液。 亂流的程度，依據構成前記原料混合物之固液比例， 即固體之人工沸石原料與液體之鹼性水溶液的比例，以及 那些原材料等的種類而相異，可被任意地設定。適宜的亂 流程度爲雷諾準數2千〜100萬，較好者爲8千〜5萬， 最好者爲1萬〜3萬，此時將能更加有效率地進行人工沸 石的生成反應。此外，雷諾準數可依據料漿的流速、反應 管7的內徑、料漿的密度、黏度及動黏度等之因子來作適 宜調整。因而，考慮這些來進行條件設定與反應管7的設 定。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -27- --------訂---------線 (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 491814 A7 B7 五、發明說明（25) 在反應管7方面，能設置隔板。有關隔板的狀態方面 ，並無特別地被限定。藉由設置隔板，能容易地進行亂流 的發生與雷諾準數的調整。作爲一例，可設置如第6圖所 示之形態的隔板。 如顯示於第2圖之系統圖、第3圖及第4圖之結構圖中 一般，反應管7係指考慮上述雷諾準數後所選定，具有所 定之內徑的所定長度之管。在其長度及內徑上，並無特別 地被限定，基於生產量或反應速度而被任意地設計。爲了 使人工沸石容易生成，針對如此做成的反應管7 ，將藉由 壓力調整方法將反應管調整至所定的壓力，並藉由下述的 加熱方法將反應管調整至所定的溫度。此壓力與溫度的關 係，最好基於飽和蒸氣壓曲線來設定。 .作爲欲生成人工沸石而施於前記原料混合物中之具體 壓力與溫度之範圍者，基於飽和蒸氣壓曲線，雖以使其由 壓力約8kg/cm (約0.8Mpa ) •溫度約175 t：至壓力約 16kg/cm (約1.6Mpa ) ·溫度約200 t：的範圍爲佳，但是即 使爲上述範圍以外者亦可，並無特別地被限定。此外，在 反應管7方面，採用具有能夠耐將前記原料混合物供給於 反應時所設定的壓力•溫度之材質或大小（厚度等）的物 質。 人工沸石製造時的加熱，可藉由載熱體油9 、飽和蒸 氣、紅外線放射、組合飽和蒸氣與紅外線放射、微波加熱 、組合飽和蒸氣與微波加熱、感應加熱、組合飽和蒸氣與 感應加熱、加熱爐等中之任一方法，於60 t〜230 °C間進 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -28- --------------------訂---------線 *41^ (請先閱讀背面之注意事項再填寫本頁) 491814 經濟部智慧財產局員工消費合作社印製 A7 B7___ 五、發明說明（26) 行。若使用如此般之加熱方法，則反應管7的全長將被均 一地加熱，因此前記原料混合物，自被供給於反應管7內 之時即被授與充分的溫度。而且，基於亂流作用亦得到充 分的攪拌。 其結果顯示，將前記原料混合物供給於反應管7後， 立刻能使反應開始進行，而促進人工沸石的生成反應，故 能達成反應時間縮短及製造效率提昇之效果。此外，在第2 圖之系統圖上，顯示出藉由載熱體油9來加熱反應管7之方 法的一例。其載熱體油9 ，藉由泵循環，於其中間，加熱 反應管7至所定的溫度。除如此般的循環類型外，亦可採 用將反應管浸泡於油浴中之方式等的種種方法。 通過反應管7內之前記原料混合物的速度，能利用泵 或利用詳述於後之壓送方法來調節。在前述人工沸石生成 步驟的裝置上，能設置變更反應管長之方法。在反應管7 之全長上，根據所定的條件將反應管7設定，然後將前記 原料混合物供給於反應管7中，雖可藉由因亂流所產生之 攪拌來促進反應，但是藉由變更反應管長之方法，或藉由 人工沸石原料及鹼性水溶液之各自種類或濃度、料漿的流 速、反應管的設定條件（溫度、時間、亂流的程度等）來 變更人工沸石的生成速度之情況，亦可基於其生成速度來 容易地控制反應時間。 作爲變更反應管長之方法，可採用藉由反應管7的配 管操作來時而增長時而縮短反應管7之長度的方法。作爲 反應管7的配管操作者，能舉出例如在反應管7上每隔一定 --------訂---------^ (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） -29- 491814 經齊部智慧財查¾員.X.消費合作f£印製 A7 B7___ 五、發明說明（27) 長度設置一個3方向活門，藉由其活門的開閉來操作之方 法。 又，亦有因人工沸石原料的種類或濃度，而使生成人 工沸石的時間變長，所設計之反應管7的長度不夠之情況 。在如此般的情況下，爲了使前記原料混合物更長時間地 於反應管7內反應，最好使到達反應管7之出口的前記原料 混合物之反應生成物再一次地回到反應管7之入口。 藉由如此般地使前記原料混合物流動於具有優秀反應 促進作用之反應管內’即使在使用不易生成人工沸石之種 類的人工沸石原料之情況下，亦可容易地生成人工沸石。 此外，藉由採用如此般的流動方法，將擁有能使反應管長 度縮短之利點。在循環前記原料混合物方面，採用於反應 管7之出口的附近設置分歧3方向活門等之流路的方法，並 且亦於反應管7之入口的附近設置分歧3方向活門等之流路 的方法，然後以旁通管連接其間等之方法。 此外，於如此般的流動式反應管7中生成人工沸石的 情況下，一旦將於反應管7中所生成的人工沸石送至其次 的步驟後，最好如同將新的前記原料混合物供給於反應管7 內般地操作泵。如此進行之方式，能夠進行所謂分批式人 工沸石的連續反應之狀態。然後，在採用如此般的狀態方 式時，配置二台以上之流動式的反應管7 ，將可更進一步 地提昇生產能力。在此情況下，將在各個流動式的反應管7 內所生成的人工沸石送至其次的步驟後，將使前記原料混 合物供給於各個流動式的反應管中。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 30 - -------丨—丨丨丨變--------訂·！ t (請先閱讀背面之注意事項再填寫本頁) 491814 A7 B7 五、發明說明（28) 在如此般的狀態的人工沸石製造裝置上，配置複數小 型的流動式的反應管7 ，每隔一定的週期將前記原料混合 (請先閱讀背面之注意事項再填寫本頁) 物斷續地供給於其反應管7內，使人工沸石連續地被生成 於其反應管7內，隨後在將所生成的人工沸石送至其次的 步驟後，再度地供給前述的原料混合物於其中。其結果顯 示’即使使用在人工沸石的生成上花費時間的種類之人工 沸石原料，亦能更一層地擴大生產能力。 可是，在含有鋁成分及矽成分之人工沸石原料方面， 已知 (a )藉由原料粒子內的反應所生成之鋁矽酸鹽，其由原 料粒子內擴散至鹼性水溶液中之速度將成爲反應速率決定 步驟之事，以及 (b )由鋁矽酸鹽所構成之人工沸石的生成反應，將於粒 子的表面進行.，而且其生成反應的速度將與鹼性水溶液的 濃度及鹼性水溶液中之鋁矽酸鹽的濃度相依存。 一坐齊平£0曰逢 1 η习s、r.肖費kn乍土，fS'J氏 在本發明中，鋁矽酸鹽的擴散速度與在粒子表面之人 工沸石的生成反應之速度，將藉由基於在全長皆被設定爲 均一條件之反應管7內之亂流的攬拌作用而被促進’並且 連續地被進行。 即，因爲在反應管7內的攪拌，將增大鹼性水溶液的 氫氧化物離子與生成之鋁矽酸鹽間的接觸機會，故能夠快 速地由原料表面除去所生成的鋁矽酸鹽。因此，促進了鋁 矽酸鹽由原料粒子內擴散（爲速率決定步驟的擴散）至驗 性水溶液中之現象，而能提高其速度。因此，因爲增加驗 -31 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 491814 A7 ____B7_ 五 '發明說明（29) 性水溶液中之鋁矽酸鹽的濃度，故亦促進人工沸石生成反 應的速度。而且，因其反應管7的全長皆被設定成均一的 溫度等之條件，故將原料供給於反應管7後，反應立刻開 始，進而促進了鋁矽酸鹽的擴散速度與人工沸石生成反應 的速度。 又，附加超音波振動於反應管7 ，亦可更進一步地促 進人工沸石的生成反應。因爲超音波振動具有與微視的強 攪拌相同之作用，故與上述相同，將增大鹼性水溶液的氫 氧化物離子與生成之鋁矽酸鹽間的接觸機會，故能夠快速 地由原料表面除去所生成的鋁矽酸鹽。因此，促進了鋁矽 酸鹽由原料粒子內擴散（爲速率決定步驟的擴散）至鹼性 水溶液中之現象，而能提高其速度。 此外，作爲欲更一層地促進人工沸石的生成反應之方 法，亦可於前述的原料混合物中配合所定量的人工沸石。 所配合之人工沸石，將成爲欲促進結晶生成反應之誘起因 子，而作爲所謂種結晶來作用。其結果，促進人工沸石的 粒成長，而能謀求縮短合成反應的時間與提昇製造效率。 所配合之人工沸石的量，雖因爲依據構成前述的原料 混合物之人工沸石原料的鋁成分與矽成分而相異，故不能 一槪地規定，然而在將煤灰使用於人工沸石原料的情況下 ，相對於人工沸石原料100質量部，最好使其含有1.0〜 5.0質量部的人工沸石。 因種結晶的添加所引起的人工沸石之粒成長的促進作 用，目前已如以下般地被推測。即，藉由種結晶的添加， 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -32- " " (請先閱讀背面之注意事項再填寫本頁) ·- --線· 491814 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（30) 種結晶之周圍的鋁矽酸鹽於種結晶上結晶成長。因此，藉 由種結晶與人工沸石原料的接觸，將減少存在於人工沸石 原料之周圍的鋁矽酸鹽濃度。藉由存在於如此般之人工沸 石原料表面之那些成分濃度的減少，促進了鋁矽酸鹽由原 料粒子內擴散（爲速率決定步驟的擴散）至鹼性水溶液中 之現象，而能提高其速度（擴散律速反應速度）。藉由如 上所述之作用，將考慮可更一層促進人工沸石之生成反應 的方法。 作爲使供給於反應管7之前記原料混合物中預先含有 所定量的人工沸石之方法者’可在由原料混合槽5至反應 管7的入口處之任一位置上設置人工沸石或含有人工沸石 之鹼性水溶液的投入口 P。此外’作爲種結晶者，可爲在 拿出反應管7後被含於所取出之鹼性水溶液中之人工沸石 ，亦可爲由其後之各步驟或配管途中所取出之人工沸石。 以此法所取出含有人工沸石之溶液或人工沸石，將添加於 被設置在前述位置之投入口 P中（參照第2圖）。 依據以上的方法，在本發明中，能有效率地確保一定 品質的人工沸石。此外，因前記原料混合物中之鹼性水溶 液的濃度以及鹼性水溶液中之鋁矽酸鹽的濃度，如上所述 將影響人工沸石生成反應之速度’故其濃度的調整將以如 下的方法來進行，就是從人工沸石生成步驟之後的取出口 中採取含有人工沸石的溶液，測定其鹼性水溶液的濃度以 及鹼性水溶液中之鋁矽酸鹽的濃度後，再藉由在調製前記 原料混合物時所投入之鹼性水溶液與在後述之人工沸石分 --------------------訂---------線 (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） -33- 經濟部智慧財產局員工消費合作社印製 491814 A7 ________ B7 五、發明說明（31) 離步驟中所回收之鹼性水溶液來進行調整。在以上已說明 之人工沸石生成步驟中所生成的人工沸石，將被送至其次 的人工沸石分離步驟中。此外，可設置冷卻器20於人工沸 石生成步驟與人工沸石分離步驟之間，藉由此冷卻器能冷 卻被加熱的料漿。 (3)人工沸石的分離步驟： 人工沸石的分離步驟，係指固液分離於前述的生成步 驟中所得的泥漿狀的混合物，即微細之人工沸石的固態物 與鹼反應之殘液。人工沸石分離裝置C ，具備有冷卻前述 合成終了後之人工沸石料漿的冷卻器20與人工沸石分離裝 置21 ，其間以導管20a相連接。在前述的人工沸石分離裝 置/21內，設置爲了分離前述人工沸石之料漿的分隔壁22， 並形成分開前述料漿中之水分和固態物之分離槽23與爲了 排出由前述料漿中分離所得之水分的排出部24。又，在前 述的人工沸石分離裝置21方面，於分離槽23的上部，事先 設置有作爲供給由壓力調節系統5 1而來之空氣的導入部之 空氣口 25，以促進於分離槽23內之固液分離。又，在分離 槽23的下部，事先設置有爲了將前述料漿脫水而得之固態 物送至其次之步驟的移送部26 ，藉由來自前述壓力調節系 統5 1之空氣以調節分離槽23內之壓力之事，將前述固態物 控制成壓送狀態，再藉由回轉泵27將其移送至其次的洗淨 步驟。 人工沸石的分離步驟，係指由具有人工沸石的鹼性水 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -34- ---------------------訂---------^ IAWI c請先閱讀背面之注咅？事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 491814 A7 B7 五、發明說明（32) 溶液中分離取出人工沸石之步驟，換言之，係除去鹼性水 溶液之步驟。此人工沸石的分離步驟，爲利用比重差之沉 降分離理論者，其於分離槽23內能連續地固液分離固體的 人工沸石與液體的鹼性水溶液。此時，若回收分離後的鹼 性水溶液再利用，則因能使廢棄物變少，故極佳。在此的 再利用，係藉由例如使回收的鹼性水溶液，時而回到前述 原料混合槽5中，時而回到連接人工沸石生成裝置B與人工 沸石分離裝置C之導管20a的途中之方法來進行。 此外，在調製前記原料混合物時，預先混入於原料中 之夾雜物或未燃碳等之微粒子，將浮游於分離槽23的上部 ，然後被排出於外部。爲了使那樣的微粒子更容易分離， 亦可一邊送入空氣一邊緩慢地進行攪拌。被分離的人工沸 石將送至其次的人工沸石洗淨步驟中。 (4 )人工沸石的洗淨步驟： 人工沸石的洗淨步驟，係指水洗在前述人工沸石分離 步驟中所得到的人工沸石固態物後，將附著於前述固態物 表面的成分除去之步驟。人工沸石的洗淨步驟，係使用人 工沸石洗淨裝置D來洗淨固液分離前述料漿所得之固態物 的步驟。前述人工沸石洗淨裝置D與前述的人工沸石分離 裝置21相同形態，在裝置內部，設置爲了分離料漿之分隔 壁29 ，並形成將由前述人工沸石分離步驟所送來的固態物 洗淨之洗淨槽30與排出部3 1。 積存於排出部31的水將被送至洗淨水供給槽31a。又 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 35- --------------------訂---------線· (請先閱讀背面之注意事項再填寫本頁) 491814I This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Stomach _ (Please read the precautions on the back before filling this page) Order --------- Line _ Ministry of Economy Wisdom Printed by the Consumer Affairs Cooperative of the Property Bureau 491814 A7 B7 V. Description of the invention (18) The stone manufacturing method is a continuous manufacturing method, so the aforementioned mixture and the alkaline aqueous solution are input, mixed, and further, the artificial zeolite generation step The supply of the raw material mixture in the apparatus is continuously performed by a valve operation or the like. In addition, when the artificial zeolite is generated by a circulation type reaction tube described later, the raw zeolite generated in the reaction tube is supplied to the next step of the supply of the raw material mixture in the device for the artificial zeolite generation step, and then the valve is controlled by a valve. The operation is performed intermittently. As a heat source to be subjected to the heating treatment of the present invention, although saturated steam, superheated steam, infrared radiation, microwave heating, and induction heating can be used, when incineration ash is used as a raw material of artificial zeolite, it can be used near the shaft-type refuse melting furnace. , Coke bed melting furnace, kerosene melting furnace, gas combustion melting furnace, gasification melting furnace, arc melting furnace, plasma melting furnace and other melting furnaces to set up artificial zeolite reaction equipment, so it can be used by these The waste heat of the furnace is economically heat-treated. In the case of using saturated steam, although the reaction is generally carried out in a pressure-resistant reaction vessel, if the heating treatment of the present invention is to be performed, the reaction tube is heated to a predetermined temperature under atmospheric pressure, and then the carrier heat is further replaced by the outside The saturated vapor of the body oil is introduced into the heating medium tank, so that the reaction temperature can be ensured. In the present invention, the so-called infrared radiation refers to a method of heating the pressure-resistant reaction container or the heating medium tank by radiating infrared rays. The infrared rays referred to herein refer to electromagnetic waves having a wavelength of 0.1 to 1000 鹘. For heat treatment, it is preferable to use electromagnetic waves having a wavelength ranging from 2.5 to 30 红外线 of infrared to far infrared. In order to implement the present invention, as long as the device used can produce on-line order (please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 Specification (210 X 297 mm) -21 · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 491814 A7 _ B7 V. Description of Invention (19) The electromagnetic waves mentioned above are not particularly limited. In addition, the temperature of the alkaline aqueous solution in the pressure-resistant reaction container or the reaction tube can be efficiently increased by the heat treatment using heating with saturated vapor and heating with infrared radiation. In the present invention, the so-called induction heating refers to a heating method that uses Joule heat caused by an induced current generated by a change in magnetic flux as a heat source, and can be used in a pressure-resistant reaction container or a heating medium tank made of conductive material such as iron. Happening. In addition, the temperature of the alkaline aqueous solution can be efficiently raised by the heating treatment with saturated steam heating and induction heating. The ultrasonic processing used to implement the present invention has a number of vibrations in the sonic range of 18 kHz to 500 kHz in the sonic range. The strength is not particularly limited, and is comparable to the performance of the ultrasonic vibrator. Dependence. During the reaction, vibration and cavitation occur in the aqueous solution due to the application of ultrasonic waves in the alkaline aqueous solution in the pressure-resistant reaction container or the reaction tube. This phenomenon not only has the effect of promoting the circulation of the alkaline aqueous solution on the surface of the zeolite raw material. It also has the effect of soaking the alkaline aqueous solution to the depth of the pores generated by the zeolization reaction. With regard to the use of coal ash as an artificial zeolite raw material in the present invention, it is known that the rate at which the amorphous aluminum silicate in the raw material particles diffuses from the raw material particles into the alkaline aqueous solution becomes the reaction rate determiner, and the aluminum molecules and soluble silicon The reaction of the acid salt occurs on the surface of the particles, and depends on the concentration of the soluble silicate in the alkaline aqueous solution. As a result, the intra-particle diffusion of the soluble silicate derived from the aluminum silicate salt and the solid-phase reaction of the alumina and the soluble silicate generated on the particle surface will be continuously performed in the same reaction layer. Quality artificial zeolite, ultrasonic treatment and -------- order --------- line (please read the precautions on the back before filling this page) This paper size applies to Chinese national standards ( CNS) A4 specification (210 X 297 mm) -22- 491814 A7 B7 V. Description of the invention (20) It is advantageous to increase the reaction temperature. First, in the first stage, "for the purpose of zeolite conversion of aluminum silicate, the raw material and alkaline aqueous solution are mixed, that is, by ultrasonic treatment, the soluble silicate produced is quickly removed from the surface of the raw material." Promote the diffusion of a new alkaline aqueous solution, so that zeolization proceeds in a short time. In the second stage, the reaction with alumina is carried out by heating while the concentration of the soluble silicate becomes high. In addition, when the alkaline waste liquid containing aluminate is reacted with the alkaline waste liquid containing silicic acid to produce artificial zeolite, the reaction is not a step for determining the diffusion reaction rate, so the synthesis reaction is completed in a short time. The concentration of the soluble silicate which is gradually dissolved in the alkaline aqueous solution by the progress of the zeolite reaction of the raw material can be adjusted by the supply amount of the alkaline aqueous solution mixed with the raw material. The adjustment of the alkaline concentration in the reaction tank can be performed by adjusting the alkaline concentration in the alkaline aqueous solution. Although an artificial alkaline zeolite can be used with a strong alkaline concentration of 0.5 to 4.5 N, it can still be adjusted. It is preferred to use a 2 to 4 N aqueous sodium hydroxide solution. In addition, in order to heat to above 100 ° C, when using saturated steam, it is best to keep the pressure in the pressure-resistant reaction container or the heating medium tank at 2 ~ 30 kg / cm2, that is, at 120 ~ 23 0 ° C. So that the reaction proceeds smoothly. The artificial zeolite of the present invention is prepared by mixing a material containing a silicic acid component and / or an aluminum component to be reacted with a silicic acid-rich material or an aluminum-rich material at a predetermined ratio of silicon and aluminum, and then The raw material mixture mixed with an alkaline aqueous solution is placed in a pressure-resistant reaction container, and is heated or pressurized to react by applying ultrasonic vibration, or the aforementioned raw material mixture is subjected to ultrasonic vibration while flowing. Obtained by the method in the heated reaction tube. This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) -23- (Please read the precautions on the back before filling this page) — II --- -Order --------- line. 491814 A7 B7 V. Invention description (21). Hereinafter, a manufacturing method and a manufacturing apparatus for manufacturing artificial zeolite by contacting the heating reaction tube of the present invention will be described with reference to the drawings. FIG. 1 shows a manufacturing method for manufacturing artificial zeolite by contacting the heating reaction tube of the present invention. An example of the flowchart, FIG. 2 is a system diagram showing an example of a method for manufacturing artificial zeolite by contacting the heated reaction tube of the present invention, and FIGS. 3 and 4 are structure diagrams of an artificial zeolite generation device. FIG. 5 is an explanatory diagram showing a state of turbulent flow in a reaction tube, FIG. 6 is a structural diagram showing an example of a partition plate provided in the reaction tube, and FIG. 7 is a structural diagram showing an example of a separation device of artificial zeolite Fig. 8 is a structural diagram showing an example of a dehydration device for artificial zeolite. / Manufacturing method for producing artificial zeolite by contacting the heated reaction tube of the present invention, 'as shown in Figure 1 and Figure 2, the material containing a silicic acid component and / or an aluminum component to be reacted with silicic acid After the phase of the enriched material or aluminum-enriched material is matched with a predetermined silica-aluminum ratio, the aforementioned raw material mixture is sequentially passed through a preparation step of a raw material mixture mixed with an alkaline aqueous solution, an artificial zeolite generation step, and a separation step. , A washing step, a type replacement step, a washing step, and a dehydration step. Next, each step will be described in detail for an artificial zeolite continuous production apparatus. (1) Preparation of raw material mixture: Steps for preparing the raw material mixture are to supply the reaction containing silicic acid to -24- (Please read the precautions on the back before filling this page) This paper size applies Chinese national standards ( CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 491814 A7 B7 V. Description of the invention (22) Substances and / or aluminum-containing substances and silicic acid-rich materials or aluminum-rich materials The phase is mixed with a predetermined ratio of silicon to aluminum, and then mixed with an alkaline aqueous solution. In Fig. 2, 1 is a continuous production apparatus of artificial zeolite, and 2 is a raw material mixture preparation apparatus. The raw material mixture preparing device 2 is provided with a raw material storage tank 3 storing raw materials for manufacturing artificial zeolite, an alkaline aqueous solution tank 4 that supplies an alkaline aqueous solution to the raw materials, and mixes the raw materials introduced from the aforementioned raw material storage tank 3 with the aforementioned The raw material mixing tank 5 of the alkaline aqueous solution introduced in the alkaline aqueous solution tank 4 supplies the silicic acid-rich material to the oxalic acid enrichment tank 5a in the aforementioned raw material mixing tank 5 and the aluminum-rich material to the aforementioned raw material mixing tank 5 The Zhongming enrichment tank 5b stores the raw materials to be mixed so as to be supplied to the raw material mixture supply tank 6 for subsequent steps. The raw materials in the raw material chrysanthemum storage tank 3 and the alkaline aqueous solution in the aforementioned aqueous solution tank Λ are sent to the raw material mixing tank 5, and the silicic acid enrichment from the silicic acid enrichment tank 5a is replenished. Material and the aluminum-enriched material from the aluminum-enriched tank 5b. The raw material mixture obtained after adjusting the silicon-aluminum ratio is sent to the raw material mixture supply tank 6 to be supplied in a subsequent step for storage. At the beginning of the synthetic zeolite synthesis reaction, the raw material mixture is sent to the artificial zeolite generation step described next. (2) Artificial zeolite generation step: The artificial zeolite generation step is to introduce the raw material mixture obtained in the preparative raw material mixture preparation step into a heating reaction tube installed in a heating medium tank described later and continuously flow to synthesize it. Steps of zeolite. Artificial zeolite generation device B 'is equipped with a reaction tube for the synthetic reaction of artificial zeolite. 7 paper standard stab towel housekeeping standard (CNS) A4 specification (210 X 297 public love) 25- l · ------- -Order ---- ^ ---- • -Line IIP- (Please read the precautions on the back before filling this page) 491814 V. Description of the invention (23) (Please read the precautions on the back before filling this page) 'The ultrasonic vibrator 7a attached to the end of the reaction tube contains the reaction tube 7 and is used as a heating medium tank 8 for heating, and is introduced into the heating medium oil 9 of the heating medium tank 8 and overheated. The heater 10 for the aforementioned heating medium oil, and the rotary pump 11 for circulating the raw material mixture in the aforementioned reaction tube. The raw material mixture sent in the raw material mixture preparation step is introduced into the reaction tube 7 by the return pump 11 and circulated. In order to circulate the heating medium oil 9 heated by the heater 10 in the heating medium tank 8 in which the reaction tube 7 is contained, the reaction tube 7 is uniformly heated. In addition, an ultrasonic vibrator 7a is provided in advance at the end of the reaction tube 7, so that the aforementioned raw material mixture is synthesized in the reaction tube 7 into a zeolite even with fine pores of particles. The slurry of the artificial zeolite obtained after the zeolite synthesis is completed will be sent to the artificial zeolite separation step described below by the rotary pump 11. In addition, in the continuous manufacturing apparatus 1 of the artificial zeolite, although the reaction tube 7 is heated by using the heating medium oil 9 heated by the heater 10, infrared radiation, saturated vapor, combined saturated vapor, and infrared radiation may be used. , Microwave heating, combined saturated steam and microwave heating, induction heating, combined saturated steam and induction heating to heat the heating medium tank 8. The production step of artificial zeolite printed by the Consumer Cooperative of the Intellectual Property Bureau of Qibu is a step to react the supplied raw material mixture into artificial zeolite. The raw material mixture will be supplied continuously or intermittently, and the raw material The mixture continuously flows through the reaction tube 7 which has been set to a predetermined temperature, pressure, flow rate, etc. to initiate a reaction for producing artificial zeolite. In the continuous manufacturing method and continuous manufacturing device for manufacturing artificial zeolite by contacting the heated reaction tube of the present invention, the biggest feature is that it must be at least -26- This paper size is applicable to China National Standard (CNS) A4 (210 X 297) (%) 491814 Consumers' cooperation of the Intellectual Property Bureau of the Ministry of Economic Affairs printed A7 B7 5. Description of the invention (24) The artificial zeolite production steps and manufacturing equipment must be provided. Therefore, only those who have an artificial zeolite production method having this artificial zeolite generation step, even if the steps described in the present application are included in the previous or subsequent steps, or steps and devices other than those described are included. can. In addition, the term "continuous" in the artificial zeolite production step device means a state in which supply and passage are almost continuously performed, and a state in which supply and passage are performed continuously at regular intervals. In addition, when the aforementioned raw material mixture flows in the reaction tube as described below, the latter state is obtained, that is, the state in which supply and passage are performed continuously at regular intervals. It may also be referred to herein as " Intermittent "situation. The artificial zeolite formation reaction is as shown in Figs. 3, 4, and 5, under the conditions of a predetermined pressure and temperature, the vortex generated when the raw material mixture flows in the reaction tube 7 under the conditions described above. Or the role of turbulence to promote it. With this vortex or turbulent flow, the artificial zeolite raw material and the alkaline aqueous solution in the raw material mixture mentioned above will be stirred very efficiently. The degree of turbulence varies according to the solid-liquid ratio constituting the above-mentioned raw material mixture, that is, the ratio of the solid artificial zeolite raw material to the liquid alkaline aqueous solution, and the types of those raw materials, etc., and can be arbitrarily set. The appropriate degree of turbulence is Reynolds number of 20 to 1 million, preferably 80 to 50,000, and most preferably 10,000 to 30,000. At this time, the artificial zeolite formation reaction can be performed more efficiently. In addition, the Reynolds number can be appropriately adjusted based on factors such as the flow velocity of the slurry, the inner diameter of the reaction tube 7, the density, viscosity, and dynamic viscosity of the slurry. Therefore, the conditions and the reaction tube 7 are set in consideration of these factors. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -27- -------- Order --------- Line (Please read the precautions on the back before (Fill in this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 491814 A7 B7 V. Description of the invention (25) In the aspect of the reaction tube 7, a partition can be installed. The state of the separator is not particularly limited. By providing a partition, the occurrence of turbulence and adjustment of the Reynolds number can be easily performed. As an example, a partition as shown in Fig. 6 may be provided. As shown in the system diagram in Figure 2, and in the structure diagrams in Figures 3 and 4, in general, the reaction tube 7 refers to a tube having a predetermined inner diameter and a predetermined length, which is selected after considering the above Reynolds criterion. The length and inner diameter are not particularly limited, and are arbitrarily designed based on the throughput or reaction speed. In order to facilitate the production of artificial zeolite, the reaction tube 7 thus prepared is adjusted to a predetermined pressure by a pressure adjustment method, and the reaction tube is adjusted to a predetermined temperature by a heating method described below. The relationship between this pressure and temperature is preferably set based on a saturated vapor pressure curve. As the specific pressure and temperature range to be applied to the raw material mixture mentioned above to produce artificial zeolite, based on the saturated vapor pressure curve, the pressure is about 8kg / cm (about 0.8Mpa). • Temperature is about 175 t: to The pressure is about 16 kg / cm (about 1.6 MPa). The temperature is about 200 t. The range is preferably, but it may be outside the above range and is not particularly limited. In addition, the reaction tube 7 is made of a material or a size (thickness, etc.) capable of withstanding the pressure and temperature set at the time of supplying the aforementioned raw material mixture to the reaction. The heating during the manufacture of artificial zeolite can be carried out by heat carrier oil9, saturated steam, infrared radiation, combined saturated steam and infrared radiation, microwave heating, combined saturated steam and microwave heating, induction heating, combined saturated steam and induction heating, and heating. Any one of the methods, such as furnace, between 60 t ~ 230 ° C, the paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -28- ----------- --------- Order --------- Line * 41 ^ (Please read the notes on the back before filling out this page) 491814 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7___ Five Description of the invention (26). If such a heating method is used, the entire length of the reaction tube 7 will be uniformly heated. Therefore, the raw material mixture described above will be given a sufficient temperature since it is supplied into the reaction tube 7. In addition, sufficient agitation was obtained based on the turbulence. As a result, it was shown that immediately after the above-mentioned raw material mixture is supplied to the reaction tube 7, the reaction can be started and the production reaction of artificial zeolite can be promoted, so that the effects of shortening the reaction time and improving the manufacturing efficiency can be achieved. In addition, an example of a method of heating the reaction tube 7 with the heating medium oil 9 is shown on the system diagram in FIG. 2. The heating medium oil 9 is circulated by the pump, and the reaction tube 7 is heated to a predetermined temperature in the middle. In addition to such a circulation type, various methods such as a method of immersing a reaction tube in an oil bath can be adopted. The speed of the raw material mixture recorded in the reaction tube 7 can be adjusted by a pump or a pressure feeding method described in detail later. A method for changing the length of the reaction tube can be provided in the apparatus for the artificial zeolite generation step. Throughout the entire length of the reaction tube 7, the reaction tube 7 is set according to predetermined conditions, and the foregoing raw material mixture is supplied to the reaction tube 7. Although the reaction can be promoted by stirring due to turbulence, the reaction can be changed by changing The method of tube length, or the situation of changing the rate of production of artificial zeolite by the type or concentration of artificial zeolite raw material and alkaline aqueous solution, the flow rate of slurry, and the setting conditions of the reaction tube (temperature, time, degree of turbulence, etc.) It is also possible to easily control the reaction time based on its generation speed. As a method for changing the length of the reaction tube, a method of shortening the length of the reaction tube 7 may be used as the tube length increases. As a piping operator of the reaction tube 7, for example, the reaction tube 7 can be provided at regular intervals -------- order --------- ^ (Please read the precautions on the back before filling (This page) This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) -29- 491814 Certified by the Ministry of Economics and Wisdom of the Ministry of Finance. X. Consumption cooperation f £ A7 B7___ 5. Description of the invention ( 27) A 3-direction valve is installed in the length, and the valve is operated by opening and closing the valve. In addition, depending on the type or concentration of the artificial zeolite raw material, the time for producing artificial zeolite may be longer, and the length of the designed reaction tube 7 may be insufficient. In such a case, in order to make the preformed raw material mixture react in the reaction tube 7 for a longer time, it is better to return the reaction product of the preformed raw material mixture that reaches the outlet of the reaction tube 7 to the inlet of the reaction tube 7 again. . By allowing the above-mentioned raw material mixture to flow in a reaction tube having an excellent reaction promoting effect as described above, even when an artificial zeolite material such as artificial zeolite is not easily produced, artificial zeolite can be easily produced. In addition, by adopting such a flow method, it will have the advantage of shortening the length of the reaction tube. In the circulation of the raw material mixture before the circulation, a method in which a flow path such as a branch 3 direction valve is provided near the outlet of the reaction tube 7 and a method in which a flow path such as a branch 3 direction valve is provided near the inlet of the reaction tube 7 is adopted. Then use a bypass pipe to connect between them. In addition, in the case where artificial zeolite is generated in such a flow-type reaction tube 7, once the artificial zeolite generated in the reaction tube 7 is sent to the next step, it is preferable to supply a new preamble raw material mixture to the reaction. Operate the pump in tube 7 as usual. In this manner, the so-called batch type artificial zeolite can be continuously reacted. Then, when adopting such a state mode, disposing two or more flow-type reaction tubes 7 will further increase the production capacity. In this case, after the artificial zeolite generated in each reaction tube 7 of the flow type is sent to the next step, the aforementioned raw material mixture is supplied to each reaction tube of the flow type. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 30-------- 丨 — 丨 丨 丨 Variable -------- Order ·! t (Please read the precautions on the back before filling out this page) 491814 A7 B7 V. Description of the invention (28) On such an artificial zeolite manufacturing device in this state, a plurality of small-sized flow-type reaction tubes 7 are arranged at regular intervals. The above mentioned materials are mixed (please read the notes on the back before filling this page). The material is intermittently supplied into its reaction tube 7, so that artificial zeolite is continuously generated in its reaction tube 7, and then the generated After the artificial zeolite is sent to the next step, the aforementioned raw material mixture is supplied again. As a result, it was shown that even if an artificial zeolite raw material of a type that takes time to generate artificial zeolite is used, the production capacity can be further expanded. However, in terms of artificial zeolite raw materials containing aluminum and silicon components, (a) it is known that the rate of diffusion of aluminosilicates from raw material particles into an alkaline aqueous solution will become The reaction rate determines the steps, and (b) the artificial zeolite formation reaction composed of aluminosilicate will be carried out on the surface of the particles, and the speed of the production reaction will be related to the concentration of the alkaline aqueous solution and the alkaline aqueous solution. The concentration of aluminosilicate is dependent on it. As soon as it sits flat, it is said that 1 s s, r. Xiao Fei, and fS'J. In the present invention, the diffusion rate of aluminosilicate and the reaction rate of the artificial zeolite on the particle surface, It will be promoted by the stirring effect based on the turbulent flow in the reaction tube 7 which is set to a uniform condition over the entire length, and is continuously performed. That is, since the agitation in the reaction tube 7 increases the chance of contact between hydroxide ions of the alkaline aqueous solution and the generated aluminosilicate, the generated aluminosilicate can be quickly removed from the surface of the raw material. Therefore, the phenomenon that aluminum silicate diffuses from the raw material particles (diffusion for the rate-determining step) into the aqueous solution is promoted, and the speed can be increased. Therefore, because of the increase in inspection -31-this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 491814 A7 ____B7_ Five 'invention description (29) the concentration of aluminosilicate in aqueous solution, so Promote the speed of artificial zeolite formation reaction. In addition, since the entire length of the reaction tube 7 is set to conditions such as a uniform temperature, the reaction starts immediately after the raw material is supplied to the reaction tube 7, thereby promoting the diffusion rate of the aluminosilicate and the reaction of the artificial zeolite. speed. In addition, the addition of ultrasonic vibration to the reaction tube 7 can further promote the production reaction of artificial zeolite. Because the ultrasonic vibration has the same effect as the strong stirring of the micro-vision, the same as above, it will increase the chance of contact between the hydroxide ion of the alkaline aqueous solution and the generated aluminosilicate, so it can quickly pass from the surface of the raw material. The formed aluminosilicate was removed. Therefore, the phenomenon that the aluminosilicate diffuses from the raw material particles (diffusion for the rate determining step) into the alkaline aqueous solution is promoted, and the speed can be increased. In addition, as a method for further promoting the production reaction of artificial zeolite, a predetermined amount of artificial zeolite may be added to the aforementioned raw material mixture. The compounded artificial zeolite will act as a so-called seed crystal, which will induce the crystal formation reaction. As a result, the grain growth of artificial zeolite is promoted, and the time for the synthesis reaction can be shortened and the production efficiency can be improved. The amount of the artificial zeolite to be blended differs depending on the aluminum component and the silicon component of the artificial zeolite material constituting the aforementioned raw material mixture, so it cannot be specified overnight. With respect to 100 parts by mass of the artificial zeolite raw material, it is preferable to contain 1.0 to 5.0 parts by mass of artificial zeolite. The effect of promoting the grain growth of artificial zeolites due to the addition of seed crystals has been estimated as follows. That is, with the addition of a crystal, this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -32- " " (Please read the precautions on the back before filling this page) ·- -Line · 491814 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (30) The aluminosilicate crystals grow around the crystals. Therefore, by contacting the seed crystal with the artificial zeolite raw material, the aluminosilicate concentration existing around the artificial zeolite raw material will be reduced. By reducing the concentration of those components present on the surface of such artificial zeolite raw materials, the phenomenon that the aluminosilicate diffuses from the raw material particles (diffusion for the rate-determining step) into the alkaline aqueous solution is promoted, and the speed can be increased. (Diffusion rate response speed). By the action described above, a method for further promoting the formation reaction of artificial zeolite will be considered. As a method for recording a predetermined amount of artificial zeolite in the raw material mixture before being supplied to the reaction tube 7, an artificial zeolite or an artificial zeolite containing artificial zeolite may be installed at any position from the raw material mixing tank 5 to the entrance of the reaction tube 7. The inlet P of the alkaline aqueous solution. In addition, as the seed crystal, the artificial zeolite contained in the taken-out alkaline aqueous solution after the reaction tube 7 is taken out, or the artificial zeolite taken out in the subsequent steps or on the way of the piping. The artificial zeolite-containing solution or artificial zeolite taken out in this way is added to the inlet P provided at the aforementioned position (see FIG. 2). According to the above method, in the present invention, artificial zeolite of a certain quality can be efficiently ensured. In addition, because the concentration of the alkaline aqueous solution in the raw material mixture and the concentration of the aluminosilicate in the alkaline aqueous solution will affect the rate of the artificial zeolite formation reaction as described above, the concentration adjustment will be performed in the following manner. That is, the solution containing artificial zeolite is taken from the outlet after the artificial zeolite generation step, and the concentration of the alkaline aqueous solution and the concentration of the aluminosilicate in the alkaline aqueous solution are measured, and then the raw material mixture is prepared by preparing The alkaline aqueous solution and the artificial zeolite to be described later are separated into a line (please read the note on the back first) Please fill in this page again for this matter) This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) -33- Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 491814 A7 ________ B7 V. Description of Invention (31) The alkaline aqueous solution recovered in the step is adjusted. The artificial zeolite produced in the artificial zeolite generation step described above will be sent to the subsequent artificial zeolite separation step. Further, a cooler 20 may be provided between the artificial zeolite generation step and the artificial zeolite separation step, whereby the heated slurry can be cooled by the cooler. (3) Separation step of artificial zeolite: The separation step of artificial zeolite refers to the slurry-like mixture obtained by the solid-liquid separation in the aforementioned generating step, that is, the residual liquid of fine solid artificial zeolite and alkali reaction. The artificial zeolite separation device C is provided with a cooler 20 for cooling the artificial zeolite slurry after the synthesis is completed, and an artificial zeolite separation device 21, and a duct 20a is connected therebetween. In the aforementioned artificial zeolite separation device / 21, a partition wall 22 for separating the slurry of the artificial zeolite is provided, and a separation tank 23 for separating water and solids in the slurry is formed and separated from the slurry for discharge. The obtained water discharge portion 24. In the artificial zeolite separation device 21 described above, an air port 25 is provided in the upper part of the separation tank 23 as an introduction part for supplying air from the pressure regulating system 51 in order to promote the inside of the separation tank 23. Solid-liquid separation. In the lower part of the separation tank 23, a transfer unit 26 for sending the solid matter obtained by dewatering the slurry to the next step is provided in advance, and the inside of the separation tank 23 is adjusted by the air from the pressure regulating system 51. In the case of pressure, the aforementioned solid substance is controlled to a pressure-feeding state, and then transferred to a subsequent washing step by a rotary pump 27. The separation step of artificial zeolite refers to alkaline paper with artificial zeolite. The size of the paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) -34- ------------ --------- Order --------- ^ IAWI c Please read the note on the back first? Please fill in this page again) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 491814 A7 B7 V. Description of the invention (32) The step of separating and removing artificial zeolite from the solution, in other words, the step of removing the alkaline aqueous solution. This artificial zeolite separation step is based on the theory of sedimentation separation using the difference in specific gravity. It can continuously and solidly separate the solid artificial zeolite from the liquid alkaline aqueous solution in the separation tank 23. In this case, if the alkaline aqueous solution after recovery and separation is reused, the amount of waste can be reduced, which is excellent. Recycling here is performed, for example, by returning the recovered alkaline aqueous solution to the raw material mixing tank 5 from time to time, or to return to the pipe 20a connecting the artificial zeolite generation device B and the artificial zeolite separation device C. Method to proceed. In addition, when preparing the raw material mixture described above, fine particles such as inclusions or unburned carbon mixed in the raw material in advance will float on the upper part of the separation tank 23 and then be discharged to the outside. In order to make such fine particles easier to separate, the air may be stirred slowly while being fed with air. The separated artificial zeolite is sent to the next artificial zeolite washing step. (4) Washing step of artificial zeolite: The washing step of artificial zeolite refers to the step of removing the components adhered to the surface of the solid after washing the solid of the artificial zeolite obtained in the artificial zeolite separation step. The washing step of artificial zeolite is a step of washing solid-liquid to separate the solid obtained by the aforementioned slurry using the artificial zeolite washing device D. The artificial zeolite cleaning device D has the same form as the artificial zeolite separation device 21 described above. Inside the device, a partition wall 29 for separating the slurry is provided, and a solid matter sent from the artificial zeolite separation step is washed. Clean tank 30 and discharge section 31. The water accumulated in the discharge section 31 is sent to the washing water supply tank 31a. And this paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 35- -------------------- Order ------- --Line · (Please read the notes on the back before filling in this page) 491814
經濟部智慧財產局員Η消費合作钍印製 五、發明說明（33) ，在前述的人工沸石洗淨裝置28方面，於洗淨槽3〇的上部 ，事先設置有作爲供給由壓力調節系統5 1而來之空氣的導 入部之空氣口 2 5 a ，以促進於洗淨槽3 0內洗淨料漿固態物 後之固液分離。又，在前述洗淨槽30的下部，事先設置有 爲了將前述料漿脫水而得之固態物送至其次之步驟的移送 部26b ，藉由來自前述壓力調節系統51之空氣以調節洗淨 槽30內之壓力之事，將前述固態物控制成壓送狀態，再藉 由回轉泵33將其移送至其次的人工沸石類型置換步驟中。 (5 )人工沸石的類型置換步驟： 人工沸石的類型置換步驟，係指將在前述人工沸石的 生成步驟中所合成之人工沸石的陽離子與其他的陽離子交 換之步驟。因製造時的人工沸石將變成爲供給於反應之鹼 性陽離子之類型，故相應於作爲目的之使用用途，有必要 將人工沸石陽離子置換，因此使用人工沸石的類型置換裝 置34來置換人工沸石的陽離子之步驟。 人工沸石的置換裝置34亦與分離裝置21或洗淨裝置28 相同形態，在人工沸石的類型置換裝置34內部，設置爲了 分離料漿之分隔壁29a，並形成將由前述人工沸石洗淨步驟 所送來之人工沸石固態物以其他的陽離子來置換之類型置 換槽35與排出部36。又，在前述的人工沸石的類型置換裝 置34方面，於類型置換槽35的上部，事先設置有作爲供給 由壓力調節系統5 1而來之空氣的導入部之空氣口 25b ，以 促進於類型置換槽35內陽離子置換料漿固態物後之固液分 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -36· --------訂---------線 IAW. (請先閱讀背面之注意事項再填寫本頁) 491814 A7 ___B7___ 五、發明說明（34) 離。又，在前述類型置換槽35的下部，事先設置有爲了將 被陽離子置換之料漿固態物送至其次之步驟的移送部37 ， 藉由來自前述壓力調節系統51之空氣以調節類型置換槽35 內之壓力之事，將前述固態物控制成壓送狀態，再藉由回 轉泵38將其移送至其次的洗淨步驟步驟中。 此人工沸石的類型置換步驟，係將吸附於人工沸石的 陽離子交換成爲所定之陽離子的步驟。因生成之人工沸石 通常在由氫氧化鈉所構成之鹼性水溶液中被處理，故若原 封不動地脫水人工沸石，則將可得到鈉類型的人工沸石。 此人工沸石的類型置換步驟，係將鈉類型的人工沸石 與其他的陽離子交換，置換成不同類型的人工沸石之步驟 。具體而言，欲使其變爲鈣類型時，將原類型的人工沸石 放置/於氯化鈣等之鈣鹽水溶液中使其離子交換即可，欲使 其變爲鐵類型時，將原類型的人工沸石放置於氯化鐵等之 鐵鹽水溶液中使其離子交換即可，欲使其變爲鎂類型時’ 將原類型的人工沸石放置於氯化鎂等之鎂鹽水溶液中使其 離子交換即可，欲使其變爲鉀類型時，將原類型的人工沸 石放置於氯化鉀等之鉀鹽水溶液中使其離子交換即可。藉 由以上的方法，即可置換成各種類型的人工沸石。因以此 法所得之各種類型的人工沸石，在其各自上’皆能利用於 各式各樣的用途，故能容易地製造相應其用途之類型的人 工沸石。如顯示於第2圖之系統圖一般’在人工沸石的類 型置換步驟中設置溶液槽34a，而在該溶液槽34a中設置釣 鹽水溶液槽、鐵鹽水溶液槽、鋁鹽水溶液槽、鎂鹽水溶液 -37- (請先閱讀背面之注意事項再填寫本頁) _線' 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 x 297公釐） 491814 A7 B7 五、發明說明（35) 槽等，藉由將這些水溶液投入類型置換槽35中，即可容易 地進行離子交換來置換成所期盼之類型。 (請先閱讀背面之注意事項再填寫本頁) 此外，被投入類型置換裝置34中之人工沸石，必須使 用由前述的人工沸石分離步驟中取出後，至少被洗淨一次 之人工沸石。例如，能使用固液分離型之人工沸石洗淨裝 置28來洗淨此人工沸石。 (6 )人工沸石的洗淨步驟： 經過人工沸石的類型置換步驟處理過後之人工沸石洗 淨步驟，係指洗淨除去在前述人工沸石的類型置換步驟之 處理中，附著於人工沸石表面之溶液的步驟。經過人工沸 石的類型置換步驟處理過後之洗淨步驟，係指使用人工沸 石洗淨裝置39 ，洗淨除去在前述人工沸石的類型置換步驟 之處理中，.附著於人工沸石表面之溶液的步驟。 ¾齊郢皆i讨4¾員X.消費合泎fi印製 以回轉泵38移送而來之陽離子置換型人工沸石，在洗 淨槽40中被洗淨後，將被固液分離的水收集於排出部4 1， 然後再將此水送至步驟外。又，在前述的人工沸石洗淨裝 置39方面，於洗淨槽40的上部，事先設置有作爲供給由壓 力調節系統51而來之空氣的導入部之空氣口 40a ，以促進 在洗淨槽40內洗淨料漿固態物後之固液分離。又，在前述 洗淨槽40的下部，事先設置有爲了將前述料漿脫水而得之 固態物送至其次之步驟的移送部42 ，藉由來自前述壓力調 節系統5 1之空氣以調節洗淨槽40內之壓力之事，將前述固 態物控制成壓送狀態，再藉由回轉泵43將其移送至其次的 -38- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 491814 經濟部智慧財產局員工消費合作社印製 A7 ______B7 ___ 五、發明說明（36) 人工沸石的脫水步驟中。 (7 )人工沸石的脫水步驟： 人工沸石的脫水步驟，係指脫水乾燥已完成最後洗淨 之人工沸石，使其成爲成品之步驟。前述人工沸石的脫冰 步驟，係脫水被類型置換過之人工沸石，使其成爲成品之 步驟。因被類型置換過的人工沸石，尙含有大量的水分， 故須將其脫水至所定之水分量。 人工沸石的脫水裝置，具備有脫水裝置44與成品槽45 ，在本發明中之人工沸石的脫水裝置44 ，係依據利用熱泵 方式之脫水理論而成。即，吸取設置於脫水裝置44中之脫 水槽46內的空氣以及/或水蒸氣來壓進行減壓後，加壓•加 熱吸取後之空氣以及/或水蒸氣，使其再度地返回存在有人 工沸石的脫水槽46中之旋管（所謂加熱旋管）內，使其與 人工沸石中的水分一同蒸發，藉由將水蒸氣凝結於其旋管 內後排出之法來脫水，然後藉由連續地重覆這些動作來脫 水人工沸石。 因人工沸石相應其使用狀態而需含有某一程度的水分 ，故需適宜地調節其脫水的程度。其脫水的程度，能藉由 於脫水槽46內之處理時間來調整。藉由如此做的方法，可 利用在加壓吸取後之空氣以及/或水蒸氣時所產生之熱來有 效率地進行脫水。 (8 )其他的步驟或裝置： 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） -39 - --------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 491814 A7 ______B7__ 五、發明說明（37) 就藉由本發明之加熱反應管接觸來製造人工沸石的連 續製造方法以及其連續製造裝置而言，在由人工沸石的生 成步驟至人工沸石的脫水步驟之間移送前記原料混合物或 人工沸石的方法上，能適宜地採用利用泵的大氣開放方式 或者是利用壓力差的壓送方式。在本發明中，最好能採用 因壓差所產生的壓送方式。 前述的壓送方式，係使各步驟的相互間產生壓力差， 再藉由此壓力差，使前記原料混合物或人工沸石由壓力高 之步驟自動地移送至壓力低之步驟的方式。因而，藉由調 整其壓力差與管的大小，能任意地設定移送速度。因此， 一面控制前記原料混合物或人工沸石的移送速度，不僅能 夠容易地壓送那些物質，亦能夠容易且有效率地進行人工 沸石，的製造。 特別是在本發明方面，因在人工沸石生成步驟裝置之 反應管內之前記原料混合物的攪拌作用，嚴重地關與到人 工沸石的生成反應，故將產生有所謂可藉由以壓送方式任 意且容易地調節前記原料混合物之速度來容易地控制人工 沸石生成反應之特別效果。 具備有如此般壓送方式之人工沸石連續製造裝置，在 各裝置上設置有壓力檢定操作，與基於該壓力檢定操作而 使各裝置的相互間有壓力差產生之壓力調整操作。例如， 可藉由使用由壓力傳感器所構成之壓力檢定操作來檢定壓 力後，亦可再藉由使用由液體或空氣之壓力調整系統5 1所 構成之壓力調整操作，以調節於各步驟之裝置間的壓力。 _40_ (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） 491814 A7 -------B7___ 五、發明說明（38) 特別是作爲壓力調整系統者，以使用空氣供給者爲佳，將 空氣進出於各裝置內，能容易地調整其內壓。 (請先閱讀背面之注意事項再填寫本頁) 在本發明中，不僅人工沸石生成步驟裝置的反應管7 中，即使於移送前記原料混合物或人工沸石時，亦最好能 使亂流產生般地設定各個配管的內徑或移送速度。如此， 藉由設計使亂流產生於設定各個配管的內徑或移送速度。 如此，藉由設計使亂流產生於各步驟裝置間之配管中的方 法，則在配管中亦能混合洗淨水或離子交換用溶液，使這 些物質充分地被攪拌而後處理。 例如，在人工沸石生成步驟與人工沸石分離步驟之間 ，藉由將加水稀釋的水溶液摻混於被回收之鹼性水溶液中 ，使於配管途中充分地攪拌，故能容易地進行於人工沸石 分離步驟中之固液分離。此外，在人工沸石分離步驟與人 工沸石冼淨步驟之間.，或在類型置換步驟後的配管中’藉 由摻入洗淨水，能更有效率地洗淨人工沸石。又，在人工 沸石類型置換步驟進行之前’藉由摻入離子交換用溶液’ 使離子交換容易進行’故能提昇類型置換效率。 作爲欲使連續製造變爲可能之附帶裝置’可相應其需 ί 要，於各步驟裝置中設置前記原料混合物濃度傳感器、鹼 j 濃度傳感器、離子傳感器、液面傳感器、水分傳感器等之 ； 傳感器。以使用如此般傳感器類所檢定之信號作爲基礎’ - 藉由材料的補給，可進行濃度調整或液面調整等。 ： 在本發明中，將謀求洗淨水的循環再利用。在本發明 ； 中，因洗淨步驟，通常被設置於分離步驟或類型置換步驟 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） -41 - 經濟部智慧財產局員工消費合作社印製 491814 Α7 _ Β7 五、發明說明（39) 之後，故將使洗淨後的水變成爲含有多量鈉離子者。使用 滲透膜等，即可將如上所述的洗淨水作爲洗淨水來再利用 〇 在本發明中，將謀求鹼性水溶液的再利用，即回收於 人工沸石分離步驟後被分離之鹼性水溶液，藉由使其返回 前述原本混合層5，即可再利用之。 以下，將顯示本發明之實施形態的一例，以便更具體 地說明本發明。此外，本發明的宗旨，並非只限於以下之 實施形態。 人工沸石係依據，如第1圖及第2圖所示般，藉由原料 混合物的準備步驟，混合調整爲所定之矽鋁比的人工沸石 原料與鹼性水溶液，然後使所得之前記原料混合物順序地 通過人工沸石生成裝置B、人工沸石分離裝置C、人工沸 石洗淨裝置D、人工沸石類型置換裝置E、人工沸石洗淨 裝置F、人工沸石脫水裝置G，而製成者，以下，將依順 序來說明。 首先’於原料混合物準備步驟中準備原料混合物。作 爲前記原料混合物之原料，可使用例如儲存於原料貯藏槽3 中之煤灰’與儲存於鹼性水溶液槽4中之4 8 %的氫氧化鈉 水溶液。將所定量的這些物資與稀釋水送至前述原料混合 槽5中’再k其稀釋至成爲丨3% (約3·5Ν)的氨氧化納水 溶液之同時’以攪拌器攪拌來調製前記原料混合物。 此原料混合物，係調整煤灰與氫氧化鈉水溶液，使其 成爲所定之比例者，而於考慮人工沸石的生成反應時，相 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -42- r---l· --------^----^---- 「請先閱讀背面<>i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 491814 A7 B7 五、發明說明（40) 對於煤灰1，在其比例上，以使氫氧化鈉水溶液成爲2〜 1 2者爲佳，最好成爲3〜8。其次，將調製好之前記原料 混合物送至經常保持一定量之原料混合物供給槽6中，一 邊攪拌一邊連續地供給於人工沸石的生成裝置B之反應管7 中。此外，使供給前記原料混合物之配管與人工沸石生成 步驟的出口配管相接觸，使加溫（例如，80t )前記原料 混合物之溫度，故可經濟地供給已被加溫之前記原料混合 物，而且由反應促進的觀點來看亦適宜。 在人工沸石生成裝置B中’藉由亂流，一邊擾伴被供 給之前記原料混合物，一邊將欲使反應之反應管7配置成 如第3圖、第4圖所示般的螺旋狀。在其反應管7的周 圍，爲了使反應管7內的前記原料混合物變成爲所定的反 應溫度（例如，175 °C )·所定的壓力（例如，約8 kg/cm2 )，使所定溫度（例如，200 °C )的載熱體油9循環 。反應管7的入口側，藉由前記原料混合物供給側之泵R 來加壓至所定的壓力，再如使前記原料混合物以任意的速 度向著反應管7出口側流動一般地，控制前記原料混合物 。在此，使反應管7的內徑成爲例如1.5英吋（約38mm )° 人工沸石藉由將前記原料混合物通過反應管7內而合 成。此外，在如第3圖、第4圖所示之人工沸石生成裝置B 中，採用例如使反應管7三段切換之反應管長變更操作。 含有已生成之人工沸石的鹼性水溶液，在通過配管被 送至人工沸石分離裝置21之間，與供給上述前記原料混合 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -43- -------------^----_----.· ^ IAWT (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 491814 A7 ___ B7 五、發明說明（41) 物之配管接觸，更進一步地於冷卻器20中被熱交換而冷卻 。更者，在其配管途中，設置投入加水於由人工沸石分離 步驟中所回收之鹼性水溶液中而生成之溶液的投入口 P。 反應時的加熱，除了於載熱體槽8內導入已加熱之載 熱體油9來加熱的方法外，藉由吹入加熱蒸氣、廢熱等， 亦可使反應溫度上昇。又，亦可利用紅外線放射、微波加 熱等來加熱載熱體槽。此外，在加熱反應時，在反應管7 上附設超音波振動機，亦可藉由超音波振動的附加來促進 沸石化反應。 含有被送至人工沸石分離裝置21之人工沸石的鹼性水 溶液，先於分離槽23內沉降由人工沸石所構成之固體部分 ，再與含有氫氧化鈉等之鹼性水溶液的液體部分相分離。 固體部分的人工沸石由分離槽23下方的入口被送至其次的 人工沸石洗淨裝置28。此時，雖能以壓送方式來移送，然 而以泥漿狀之人工沸石的計量控制作爲目的時，亦能倂用 泵來使用。 液體部分的氫氧化鈉水溶液，可藉由被幾個分隔壁22 分隔之排出部24中回收。此外，被回收的氫氧化鈉水溶液 ，或再次地被送回原料混合槽5，或被送回前述的投入口 P 。在前述分離槽23的上方，設置有空氣口 25，藉由來自壓 力調節系統5 1的空氣來調節分離槽23的內壓’以便控制壓 送狀態。 被送至人工沸石洗淨裝置28中之人工沸石’在其配管 途中加入洗淨水。被加入洗淨水之的人工沸石’在通過配 本紙張尺度適用中國國家標準（CNS)A4^格（210 X 297公釐） -44^ " 一 (請先閱讀背面之注意事項再填寫本頁) -----I i丨丨訂--------I . 491814 A7 B7 聲 I 时 i h t 土 P t 五、發明說明（42) 管內時，藉由配管內所發生之亂流作用進行攪拌，然後在 充分洗淨的情況下被投入洗淨槽30。此人工沸石洗淨裝置 28，具有與前述的人工沸石分離裝置2 1相同的形態，沉降 被洗淨的人工沸石後，藉由泵將其由洗淨槽下方的出口移 送至其次的類型置換裝置34中。洗淨液可藉由被幾個分隔 壁29a分隔之排出部36中回收，相應於需要，於過濾後被 送回洗淨水供給槽50。前述洗淨槽30的內壓，亦藉由與前 述分離槽23相同之構成來調整。 被送至人工沸石類型置換裝置34中之人工沸石，在其 配管途中，加入類型置換用之各種水溶液中的一種。此外 ，欲使其變爲鈉類型的人工沸石時，可原封不動地將其送 至其次步驟的脫水裝置44中。被加入類型置換用之人工沸 石，/將被投入類型置換裝置34中之類型置換槽35。此類型 置換裝置34，·亦具有與前述的人工沸石分離裝置21或人工 沸石洗淨裝置28相同的形態，沉降被洗淨的人工沸石後， 藉由泵將其由類型置換槽下方的出口移送至其次的人工沸 石洗淨步驟中。處理液可藉由被幾個分隔壁29a分隔之排出 部36中回收，相應於需要，於過濾後被送回置換液循環槽 52。類型置換槽35的內壓，亦藉由與前述分離槽23等相同 之構成來調整，以便控制其壓送狀態。 被送至人工沸石洗淨裝置39中之人工沸石，在其配管 途中加入洗淨水。被加入洗淨水之的人工沸石，在通過配 管內時，藉由配管內所發生之亂流作用進行攪拌，然後在 充分洗淨的情況下被投入洗淨槽40。此人工沸石洗淨裝置 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） _45· (請先閱讀背面之注意事項再填寫本頁) 491814 呈 1 丨才 i 邊藉由飽和蒸氣來加 A7 B7 五、發明說明（43) 39 ,具有與上述的人工沸石洗淨裝置28相同的形態，沉 降被洗淨的人工沸石後，藉由泵將其由洗淨槽下方的出口 移送至其次的人工沸石脫水步驟中。洗淨液可藉由被幾個 分隔壁39a分隔之排出部41中回收，相應於需要，於過濾 後被送回洗淨水供給槽5 3 。前述洗淨槽4 0的內壓，亦藉 由與前述洗淨槽30相同之構成來調整’以便控制其壓送狀 態。 被送至人工沸石脫水裝置G中之人工沸石，在脫水槽 46內被脫水。首先，吸取脫水槽內之空氣以及水蒸氣後， 以壓縮機47 (參照第8圖）加壓•加熱其空氣以及水蒸氣 ，然後再度使其回到存在有人工沸石之脫水槽46中的加熱 旋管內。人工沸石中的水分，藉由加熱旋管來蒸發。回到 加熱旋管內之水蒸氣，被凝結後排出。藉由如此般之熱泵 的原理，脫水人工沸石，然後將其由脫水槽下方移送至成 品槽45中，即可得人工沸石。 (實施例1 ) 於附帶攪拌機之1L容積的滅菌釜（東洋高壓股份有限 公司製）上設置超音波振動器（股份有限公司日本精機製 作所製，MODEL US -⑼GT )，以自動硏购將鹿耳島產之矽鋁 比約3.2的火山玻璃粉碎，將20g粉碎的火山玻璃以及2N 的氫氧化鈉水溶液200ml放入此反應容器中’關閉蓋子後’ 一邊施以600W、25kHz之超音波 熱至內部的溫度到達90 °C爲止。保持此狀態1 2小時後 -------I I I I I 1111111 ^ ' — — — — — — I— (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） -46 - 491814 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（44) 出內部的反應生成物。在不水洗此反應生成物下’藉由X 線繞射法確認其構造的結果’發現至細孔的丨朱處亦生成有 鈣十字沸石。此鈣十字沸石的陽離子交換容量爲410 c mol (+ ) kg — 1。 (比較例1 ) 在不施以超音波的條件下，使用與實施例1相同的方 法進行沸石化反應的結果，於不水洗被得到之反應生成物 下，藉由X線繞射法確認其構造的結果，並沒有在細孔的 深處發現沸石的轉換。此鈣十字沸石的陽離子交換容量爲 280 cmol ( + ) kg 一 1 〇 (實施例2 ) 以自動硏购將鹿耳島產之矽鋁比約3.2的火山玻璃粉碎 ，將20g粉碎的火山玻璃以及2N的氫氧化鈉水溶液200ml 放入於實施例1中所使用之反應容器中，關閉蓋子後，一 邊施以600W、25kHz之超音波，一邊藉由飽和蒸氣加壓來 加熱至內部的溫度到達200 °C爲止。保持此狀態0.5小時後 ，抽出蒸氣恢復至大氣壓，然後取出內部的反應生成物。 在不水洗此反應生成物下，藉由X線繞射法確認其構造的 結果，發現至細孔的深處亦生成有鈣十字沸石。此鈣十字 沸石的陽離子交換容量爲420 cmol ( + ) kg _ 1。 (比較例2 ) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -47- -------1——丨·--------訂----，-----·線· (請先閱讀背面之注意事項再填寫本頁) 491814 A7 ______ B7 五、發明說明（45) (請先閱讀背面之注意事項再填寫本頁) 在不施以超音波的條件下，使用與實施例2相同的方 法進行沸石化反應的結果，於不水洗被得到之反應生成物 下，藉由X線繞射法確認其構造的結果，並沒有在細孔的 深處發現沸石的轉換。此鈣十字沸石的陽離子交換容量爲 300 cmol ( + ) kg _ 1 〇 (實施例3 ) 將非結晶性矽酸鋁之含有量爲80 %而矽鋁比約2.0之 都市垃圾的焚化灰（東京都町田市淸掃局焚化場製）20g 以及2N的氫氧化鈉水溶液200ml放入於實施例1中所使用 之反應容器中，關閉蓋子後，一邊施以600W、25kHz之超 音波，一邊加熱至內部的溫度到達90 °C爲止。保持此狀態 2七小時後，取出內部的反應生成物。在不水洗此反應生成 物下，藉由X線繞射法確認其構造的結果，發現至細孔的 深處亦生成有羥基方鈉石。此羥基方鈉石的陽離子交換容 量爲 340 cmol ( + ) kg 一 1。 (比較例3 ) 經濟部智慧財產局員工消費合作社印製 在不施以超音波的條件下，使用與實施例3相同的方 法進行沸石化反應的結果，於不水洗被得到之反應生成物 下，藉由X線繞射法確認其構造的結果，並沒有在細孔的 深處發現沸石的轉換。此羥基方鈉石的陽離子交換容量爲 270cmol ( + ) kg 一 1〇 -48- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 491814 A7 B7 五、發明說明（46) (實施例4 ) 將非結晶性矽酸鋁之含有量爲80 %而矽鋁比約2.0之 都市垃圾的焚化灰（東京都町田市淸掃局焚化場製）20g 以及2N的氫氧化鈉水溶液200ml，放入設置有超音波振動 器（股份有限公司日本精機製作所製，MODEL US - 6GGT )之 反應容器中，關閉蓋子後，一邊施以600W、25kHz之超音 波，一邊藉由紅外線放射裝置（理學電機股份有限公司製 ，縱型紅外線爐）之紅外線放射來加熱至內部的溫度到達 90 °C爲止。保持此狀態24小時後，取出內部的反應生成物 。在不水洗此反應生成物下，藉由X線繞射法確認其構造 的結果，發現至細孔的深處亦生成有羥基方鈉石。此羥基 方鈉石的陽離子交換容量爲310 cmol ( + ) kg — 1。 (比較例4 ). 在不施以超音波的條件下，使用與實施例4相同的方 法進行沸石化反應的結果，於不水洗被得到之反應生成物 下，藉由X線繞射法確認其構造的結果，並沒有在細孔的 深處發現沸石的轉換。此羥基方鈉石的陽離子交換容量爲 280 cmol ( + ) kg — 1。 (實施例5 ) 將非結晶性矽酸鋁之含有量爲80 %而矽鋁比約2.0之 都市垃圾的焚化灰（東京都町田市淸掃局焚化場製）20g 以及2N的氫氧化鈉水溶液200ml，放入於實施例4中所使 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -49- (請先閱讀背面之注意事項再填寫本頁) — 訂---------線· 491814 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（47) 用之反應容器中，關閉蓋子後，一邊施以600 W、25 kHz之 超音波，一邊藉由微波加熱器（股份有限公司日立製作所 製，MRH — 4型）之微波加熱來加熱至內部的溫度到達90 °C爲止。保持此狀態24小時後，取出內部的反應生成物。 在不水洗此反應生成物下，藉由X線繞射法確認其構造的 結果，發現至細孔的深處亦生成有羥基方鈉石。此羥基方 鈉石的陽離子交換容量爲310 cmol ( + ) kg — 1。 (比較例5 ) 在不施以超音波的條件下，使用與實施例5相同的方 法進行沸石化反應的結果，於不水洗被得到之反應生成物 下，藉由X線繞射法確認其構造的結果，並沒有在細孔的 深處發現沸石的轉換。此羥基方鈉石的陽離子交換容量爲 280 cmol ( + ) kg ~ 1。 (實施例6 ) 將非結晶性矽酸鋁之含有量爲80 %而矽鋁比約2.0之 都市垃圾的焚化灰（東京都町田市淸掃局焚化場製）20g 以及2N的氫氧化鈉水溶液200ml，放入於實施例4中所使 用之反應容器中，關閉蓋子後，一邊施以600 W、25kHz之 超音波，一邊通電於電磁感應加熱器（松下電器產業股份 有限公司製，National Z — P57 )來加熱至內部的溫度到達 90 °C爲止。保持此狀態24小時後，取出內部的反應生成物 。在不水洗此反應生成物下，藉由X線繞射法確認其構造 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -50 _ -------参--------訂· —i轸 (請先閱讀背面之注意事項再填寫本頁) 491814 A7 _ B7 五、發明說明（48) 的結果，發現至細孔的深處亦生成有羥基方鈉石。此羥基 方鈉石的陽離子交換容量爲310 cmol ( + ) kg — 1。 (比較例6 ) 在不施以超音波的條件下，使用與實施例6相同的方 法進行沸石化反應的結果，於不水洗被得到之反應生成物 下，藉由X線繞射法確認其構造的結果，並沒有在細孔的 深處發現沸石的轉換。此羥基方鈉石的陽離子交換容量爲 280 cmol ( + ) kg _ 1 〇 (實施例7 ) 將非結晶性政酸銘之含有量爲8 0 %而政銘比約2.0之 都市垃圾的焚化灰（東京都町田市淸掃局焚化場製）20g 以及4N的氫氧化鈉水溶液200ml放入於實施例1中所使用 之反應容器中，關閉蓋子後，一邊施以600W、25kHz之超 音波，一邊藉由飽和蒸氣加壓來加熱至內部的溫度到達1 20 °C爲止。保持此狀態5小時後，抽出蒸氣恢復至大氣壓， 然後取出內部的反應生成物。在不水洗此反應生成物下， 藉由X線繞射法確認其構造的結果，發現至細孔的深處亦 生成有羥基方鈉石。此羥基方鈉石的陽離子交換容量爲380 cmol ( + ) kg 一 1。 (比較例7 ) 在不施以超音波的條件下，使用與實施例7相同的方 (請先閱讀背面之注意事項再填寫本頁) 0--------訂 i — — ^----線. 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -51 - 經濟部智慧財產局員工消費合作社印製 491814 A7 B7 五、發明說明（49) 法進行沸石化反應的結果，於不水洗被得到之反應生成物 下，藉由X線繞射法確認其構造的結果，並沒有在細孔的 深處發現沸石的轉換。此羥基方鈉石的陽離子交換容量爲 230 cmol ( + ) kg _ 1 〇 (實施例8 ) 於附帶攪拌機之1L容積的滅菌釜（東洋高壓股份有限 公司製）上設置超音波振動器（股份有限公司日本精機製 作所製，MODEL US - 6GGT )以及紅外線放射裝置（理學電機 股份有限公司製，縱型紅外線爐），將非結晶性矽酸鋁之 含有量爲80 %而矽鋁比約2.0之都市垃圾的焚化灰（東京 都町田市淸掃局焚化場製）20g以及4N的氫氧化鈉水溶液 200,ml放入此反應容器中，關閉蓋子後，一邊施以600W， 25kHz之超音波，一邊藉由紅外線放射來加熱至內部的溫度 到達1 20t爲止。保持此狀態5小時後，取出內部的反應生 成物。在不水洗此反應生成物下，藉由X線繞射法確認其 構造的結果，發現至細孔的深處亦生成有羥基方鈉石。此 羥基方鈉石的陽離子交換容量爲340 cmol ( + ) kg — 1。 (實施例9 ) 於附帶攪拌機之1L容積的滅菌釜（東洋高壓股份有限 公司製）上設置超音波振動器（股份有限公司日本精機製 作所製，MODEL US - 6GGT )以及微波加熱器（股份有限公司 曰立製作所製，MRH - 4型），將非結晶性矽酸鋁之含有 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -52- -------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 491814 A7 ___B7_五、發明說明（50) 量爲80 %而矽鋁比約2.0之都市垃圾的焚化灰（東京都町 田市淸掃局焚化場製）20g以及2N的氫氧化鈉水溶液 200ml放入此反應容器中，關閉蓋子後，一邊施以600W， 25kHz之超音波，一邊藉由微波加熱來加熱至內部的溫度到 達1 20 °C爲止。保持此狀態5小時後，取出內部的反應生成 物。在不水洗此反應生成物下，藉由X線繞射法確認其構 造的結果，發現至細孔的深處亦生成有羥基方鈉石。此羥 基方鈉石的陽離子交換容量爲340 cmol ( + ) kg — 1。 (實施例10 ) 於附帶攪拌機之1L容積的滅菌釜（東洋高壓股份有限 公司製）上設置超音波振動器（股份有限公司日本精機製 作所製，MODEL US - 60GT )以及電磁感應加熱器（松下電器 產業股份有限公司製.，National Z - P57 )，將非結晶性矽 酸鋁之含有量爲80 %而矽鋁比約2.0之都市垃圾的焚化灰 (東京都町田市淸掃局焚化場製）20g以及2N的氫氧化鈉 水溶液2 0 0 m 1放入此反應容器中，關閉蓋子後，一邊施以 600W、25kHz之超音波，一邊通電於感應加熱器來加熱至 ' 內部的溫度到達120t爲止。保持此狀態5小時後，取出內 | 部的反應生成物。在不水洗此反應生成物下，藉由X線繞 ; 射法確認其構造的結果，發現至細孔的深處亦生成有羥基 I ： 方鈉石。此羥基方鈉石的陽離子交換容量爲340 cmol ( + j - )kg 一 1。 (請先閱讀背面之注意事項再填寫本頁) ·# 訂： 線 馨 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -53- 491814 A7 __ B7 五、發明說明（51) (實施例11 ) (請先閱讀背面之注意事項再填寫本頁) 將非結晶性矽酸鋁之含有量爲80 %而矽鋁比約2.0之 都市垃圾的焚化灰（東京都町田市淸掃局焚化場製）20g 以及4N的氫氧化鈉水溶液200ml放入於實施例8中所使用 之反應容器中，關閉蓋子後，一邊施以600W、25kHz之超 音波，一邊藉由飽和蒸氣以及紅外線放射來加熱至內部的 溫度到達1 20 °C爲止。保持此狀態5小時後，取出內部的反 應生成物。在不水洗此反應生成物下，藉由X線繞射法確 認其構造的結果，發現至細孔的深處亦生成有羥基方鈉石 。此羥基方鈉石的陽離子交換容量爲350 cmol ( + ) kg 一1 (實施例12 ) 經濟郎智慧財產¾員工消費合作钍印製 將非結晶性矽酸鋁之含有量爲80 %而矽鋁比約2.0之 都市垃圾的焚化灰（東京都町田市淸掃局焚化場製）20g 以及2 N的氫氧化鈉水溶液2 0 0 m 1放入於實施例9中所使用 之反應容器中，關閉蓋子後，一邊施以600W、25kHz之超 音波，一邊藉由飽和蒸氣以及微波加熱來加熱至內部的溫 度到達1 20 °C爲止。保持此狀態5小時後，取出內部的反應 生成物。在不水洗此反應生成物下，藉由X線繞射法確認 其構造的結果，發現至細孔的深處亦生成有羥基方鈉石。 此羥基方鈉石的陽離子交換容量爲340 cmol ( + ) kg — 1。 (實施例13 ) -54- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 491814 A7 B7 五、發明說明（52) (請先閱讀背面之注意事項再填寫本頁) 將非結晶性矽酸鋁之含有量爲80 %而矽鋁比約2.0之 都市垃圾的焚化灰（東京都町田市淸掃局焚化場製）20g 以及2N的氫氧化鈉水溶液200ml放入於實施例10中所使用 之反應容器中，關閉蓋子後，一邊施以600 W、25 kHz之超 音波，一邊藉由飽和蒸氣以及感應加熱器的通電來加熱至 內部的溫度到達1 20 °C爲止。保持此狀態5小時後，取出內 部的反應生成物。在不水洗此反應生成物下，藉由X線繞 射法確認其構造的結果，發現至細孔的深處亦生成有羥基 方鈉石。此羥基方鈉石的陽離子交換容量爲340 cmol ( + )kg - 1 。 (實施例14 ) 經濟部智慧財產局員工消費合作社印製 將非結晶性矽酸鋁之含有量爲80 %而矽鋁比約2.0之 都市垃圾的焚化灰（東京都町田市淸掃局焚化場製）20g 以及4N的氫氧化鈉水溶液200ml放入於實施例1中所使用 之反應容器中，關閉蓋子後，一邊施以600W、25kHz之超 音波，一邊藉由飽和蒸氣加壓來加熱至內部的溫度到達200 °C爲止。保持此狀態0.5小時後，抽出蒸氣恢復至大氣壓， 然後取出內部的反應生成物。在不水洗此反應生成物下， 藉由X線繞射法確認其構造的結果，發現至細孔的深處亦 生成有羥基方鈉石。此羥基方鈉石的陽離子交換容量爲560 cmol ( + ) kg — 1 0 (比較例8 ) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -55 - 491814 A7 B7 五、發明說明（53) (請先閱讀背面之注意事項再填寫本頁) 在不施以超音波的條件下，使用與實施例1 4相同的方 法進行沸石化反應的結果，於不水洗被得到之反應生成物 下，藉由X線繞射法確認其構造的結果，並沒有在細孔的 深處發現沸石的轉換。此羥基方鈉石的陽離子交換容量爲 3 80 cmol ( + ) kg — 1。 (實施例15 ) 將非結晶性矽酸鋁之含有量爲95 %而矽鋁比約2.5之 飛灰（電源開發股份有限公司松浦發電所製，由飛灰協會 提供）20g以及4N的氫氧化鈉水溶液200ml放入於實施例1 中所使用之反應容器中，關閉蓋子後，一邊施以600W、 25 kHz之超音波，一邊藉由飽和蒸氣加壓來加熱至內部的溫 度，到達1 20 °C爲止。保持此狀態3小時後，抽出蒸氣恢復至 大氣壓，然後取出內部的反應生成物。在不水洗此反應生 成物下，藉由X線繞射法確認其構造的結果，發現至細孔 的深處亦生成有鈣十字沸石。此鈣十字沸石的陽離子交換 容量爲 350 cmol ( + ) kg — 1。 經濟部智慧財產局員工消費合作社印制衣 (比較例9 ) 在不施以超音波的條件下，使用與實施例1 5相同的方 法進行沸石化反應的結果，於不水洗被得到之反應生成物 下，藉由X線繞射法確認其構造的結果，並沒有在細孔的 深處發現沸石的轉換。此鈣十字沸石的陽離子交換容量爲 240 cmol ( + ) kg — 1。 56- 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 491814 A7 _ B7 五、發明說明（54) (實施例16 ) 將非結晶性矽酸鋁之含有量爲95 %而矽鋁比約2.5之 飛灰（電源開發股份有限公司松浦發電所製，由飛灰協會 提供）20g以及4N的氫氧化鈉水溶液200ml放入於實施例1 中所使用之反應容器中，關閉蓋子後，一邊施以600W、 25kHz之超音波，一邊藉由飽和蒸氣加壓來加熱至內部的溫 度到達200 t爲止。保持此狀態0.5小時後，抽出蒸氣恢復 至大氣壓，然後取出內部的反應生成物。在不水洗此反應 生成物下，藉由X線繞射法確認其構造的結果，發現至細 孔的深處亦生成有鈣十字沸石。此鈣十字沸石的陽離子交 換容量爲 380 cmol ( + ) kg — 1。 (比較例10.) 在不施以超音波的條件下，使用與實施例1 6相同的方 法進行沸石化反應的結果，於不水洗被得到之反應生成物 下，藉由X線繞射法確認其構造的結果，並沒有在細孔的 深處發現沸石的轉換。此鈣十字沸石的陽離子交換容量爲 230 cmol ( + ) kg — 1 〇 (實施例17 ) 將垃圾固態化燃料的焚化灰（由東京都町田市淸掃局 焚化場提供）l〇〇g以及3.5N的氫氧化鈉水溶液240ml放入 於實施例1中所使用之反應容器中，關閉蓋子後’ 一邊施 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -57- — — — — — Ilill — ϊ ·1111111 « — — 111 — ' (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 491814 A7 B7 五、發明說明（55) 以600W、25kHz之超音波，一邊藉由飽和蒸氣來加熱至內 部的溫度到達80〜90 °C爲止。保持此狀態24小時後，取 出內部的反應生成物，再以水將過剩的氫氧化鈉洗淨，自 然乾燥後得到粉末。藉由X線繞射法，發現至細孔的深處 亦生成有羥基方鈉石。此羥基方鈉石的陽離子交換容量爲 3 60 cmol ( + ) kg " 1 ° (比較例1 1 ) 在不施以超音波的條件下，使用與實施例1 7相同的方 法進行沸石化反應的結果，將被得到的反應生成物中之過 剩的氫氧化鈉以水洗淨，自然乾燥後得到粉末。藉由X線 糸凭射法確S忍此粉末構造的結果’並沒有在細孔的深處發現 沸石的轉換。此羥基方鈉石的陽離子交換容量爲230 cmol (+ ) kg 一 1。 (實施例18 ) 將垃圾固態化燃料的焚化灰（由東京都町田市淸掃局 焚化場提供）100g以及3·5N的氫氧化鈉水溶液240ml放入 於實施例1中所使用之反應容器中，關閉蓋子後，一邊施 以600 W、25 kHz之超音波，一邊藉由飽和蒸氣加壓來加熱 至內部的溫度到達1 20〜1 25 °C爲止。保持此狀態2小時後 ，抽出蒸氣恢復至大氣壓，然後取出內部的反應生成物， 再以水將過剩的氫氧化鈉洗淨，自然乾燥後得到粉末。藉 由X線繞射法，發現至細孔的深處亦生成有羥基方鈉石。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -58- ------------------- — 訂-------- (請先閱讀背面之注意事項再填寫本頁) 491814 A7 _B7 _ 五、發明說明（56) 此羥基方鈉石的陽離子交換容量爲370 cmol ( + ) kg 1。 (比較例1 2 ) 在不施以超音波的條件下，使用與實施例1 8相同的方 法進行沸石化反應的結果，將被得到的反應生成物中之過 剩的氫氧化鈉以水洗淨，自然乾燥後得到粉末。藉由X線 繞射法確認此粉末構造的結果，並沒有在細孔的深處發現 沸石的轉換。此羥基方鈉石的陽離子交換容量爲240 cmol (+ ) kg — 1 。 (實施例19 ) 以自動硏购將鹿耳島產之矽鋁比約3.2的火山玻璃粉碎 ，將.20g粉碎的火山玻璃以及5g的玻璃粉末（西日本環境 開發協同組合製）放入於實施例1中所使用之反應容器中 ，再由其上方加入2N的氫氧化鈉水溶液200ml，關閉蓋子 後，一邊施以600W、25kHz之超音波，一邊藉由飽和蒸氣 來加熱至內部的溫度到達9(TC爲止。保持此狀態1 2小時後 ，取出內部的反應生成物，在不水洗此反應生成物下，藉 5 由X線繞射法確認其構造的結果，發現至細孔的深處亦生 a t 成有八面沸石。此八面沸石的陽離子交換容量爲300 cmol ί ^ ( + ) kg 1。 Μ ^ (比較例1 3 ) ^ 在不施以超音波的條件下，使用與實施例1 9相同的方 •59· (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） 491814 A7 B7 五、發明說明（57) 法進行沸石化反應的結果’於不水洗被得到之反應生成物 下，藉由X線繞射法確認其構造的結果，並沒有在細孔的 深處發現沸石的轉換。此八面沸石的陽離子交換容量爲2 1 0 cmol ( + ) kg 1。 (實施例20 ) ^ 以自動硏购將鹿耳島產之矽鋁比約3.2的火山玻璃粉碎 ，將20g粉碎的火山玻璃以及5g的鋁渣滓（由社團法人輕 金屬協會提供）放入於實施例1中所使用之反應容器中’ 在由其上方加入2N的氫/氧化鈉水溶液200ml，關閉蓋子後 ，一邊施以600 W、25 kHz之超音波，一邊藉由飽和蒸氣來 加熱至內部的溫度到達9 0 °C爲止。保持此狀態1 2小時後’ 取出內部的反應生成物，在不水洗此反應生成物下，藉由 X線繞射法確認其構造的結果，發現至細孔的深處亦生成 有鈣十字沸石。此鈣十字沸石的陽離子交換容量爲390 cmol ( + ) kg —】。 (比較例14 ) 土 在不施以超音波的條件下，使用與實施例20相同的方 法進行沸石化反應的結果，於不水洗被得到之反應生成物 下，藉由X線繞射法確認其構造的結果’並沒有在細孔的 深處發現沸石的轉換。此鈣十字沸石的陽離子交換容量爲 280 cmol ( + ) kg - 1 〇 -60 - (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） 經濟部智慧財產局員工消費合作社印製 491814 A7 B7 五、發明說明（58) (實施例21 ) 將非結晶性矽酸鋁之含有量爲80 %而矽鋁比約2.0之 都市垃圾的焚化灰（東京都町田市淸掃局焚化場製）20g 以及1 〇g的玻璃粉末（西日本環境開發協同組合製）放入 於實施例1中所使用之反應容器中，再由其上方加入3.5N 的氫氧化鈉水溶液240ml，關閉蓋,後，一邊施以600W、 2 5kHz之超音波，一邊藉由飽和蒸氣來加熱至內部的溫度到 達80〜90 °C爲止。保持此狀態20小時後，取出內部的反 應生成物，再以水將此反應生成物中之過剩的氫氧化鈉洗 淨，自然乾燥後得到粉末。藉由X線繞射法確認此粉末構 造的結果，發現至細孔的深處亦生成有鈣十字沸石。此鈣 十字沸石的陽離子交換容量爲370 cmol ( + ) kg — 1。 (比較例15 ). 在不施以超音波的條件下，使用與實施例2 1相同的方 法進行沸石化反應的結果，於不水洗被得到之反應生成物 下，藉由X線繞射法確認其構造的結果，並沒有在細孔的 深處發現沸石的轉換。此鈣十字沸石的陽離子交換容量爲 210 cmol ( + ) kg 一 1 〇 (實施例22 ) 將非結晶性矽酸鋁之含有量爲80 %而矽鋁比約2.0之 都市垃圾的焚化灰（東京都町田市淸掃局焚化場製）20g 以及20g的玻璃粉末（西日本環境開發協同組合製）放入 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -61 - ϋ ϋ n ϋ n n n i·— ϋ I 1^1 · Bmmmm I 1 n ·1 an 1 一 δ, I ϋ ϋ i^i n ϋ n I (請先閱讀背面之注意事項再填寫本頁) 491814 A7 B7 五、發明說明（59) 於實施例1中所使用之反應容器中，再由其上方加入3.5N 的氫氧化鈉水溶液240ml，關閉蓋子後，一邊施以600W、 2 5kHz之超音波，一邊藉由飽和蒸氣來加熱至內部的溫度到 達80〜90 °C爲止。保持此狀態30小時後，取出內部的反 應生成物，再以水將此反應生成物中之過剩的氫氧化鈉洗 淨，自然乾燥後得到粉末。藉由\線繞射法確認此粉末構 造的結果，發現至細孔的深處亦生成有八面沸石。此八面 沸石的陽離子交換容量爲240 cmol ( + ) kg — 1。 (比較例16 ) 在不施以超音波的條件下，使用與實施例22相同的方 法進行沸石化反應的結果，於不水洗被得到之反應生成物 下 '藉由X線繞射法確認其構造的結果，並沒有在細孔的 深處發現沸石的轉換。此八面沸石的陽離子交換容量爲1 90 cmol ( + ) kg — 1 〇 (實施例23 ) 將非結晶性矽酸鋁之含有量爲80 %而矽鋁比約2.0之 都市垃圾的焚化灰（東京都町田市淸掃局焚化場製）20g 以及20g的玻璃粉末（西日本環境開發協同組合製）放入 於實施例4中所使用之反應容器中，再由其上方加入3.5N 的氫氧化鈉水溶液240ml後，一邊施以600W、25kHz之超 音波，一邊藉由紅外線放射裝置（理學電機股份有限公司 製，縱型紅外線爐）之紅外線放射來加熱至內部的溫度到 -62- (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） 491814 A7 ____B7___ 五、發明說明（60) 達80〜90 °C爲止。保持此狀態20小時後，取出內部的反 應生成物，再以水將此反應生成物中之過剩的氫氧化鈉洗 淨，自然乾燥後得到粉末。藉由X線繞射法確認此粉末構 造的結果，發現至細孔的深處亦生成有鈣十字沸石。此鈣 十字沸石的陽離子交換容量爲360 cmol ( + ) kg — 1。 (比較例1 7 ) I 在不施以超音波的條件下，使用與實施例23相同的方 ] ! 法進行沸石化反應的結果，將被得到的反應生成物中之過 ) 剩的氫氧化鈉以水洗淨，自然乾燥後得到粉末。藉由X線 繞射法確認此粉末構造的結果，並沒有在細孔的深處發現 沸石的轉換。此鈣十字沸石的陽離子交換容量爲290 cmol (+ X kg — 1 。 ] (實施例24 ) I 將非結晶性矽酸鋁之含有量爲80 %而矽鋁比約2.0之 1 ] 都市垃圾的焚化灰（東京都町田市淸掃局焚化場製）20g j I 以及i〇g的玻璃粉末（西日本環境開發協同組合製）放入 ] 於實施例4中所使用之反應容器中，再由其上方加入3.5N 的氫氧化鈉水溶液240ml後，一邊施以600W、25kHz之超 音波，一邊藉由微波加熱器（股份有限公司日立製作所製 ，MRH — 4型）之微波加熱來加熱至內部的溫度到達80〜 90 °C爲止。保持此狀態20小時後，取出內部的反應生成物 ，再以水將此反應生成物中之過剩的氫氧化鈉洗淨，自然 -----I--II--I ·1111111 ^' — — — — — 1 — (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） · 63 經濟部智慧財產局員工消費合作社印製 491814 A7 ___—_____ B7 五、發明說明（61) 乾燥後得到粉末。藉由X線繞射法確認此粉末構造的結果 ’發現至細孔的深處亦生成有鈣十字沸石。此鈣十字沸石 的陽離子交換容量爲380 cmol ( + ) kg —、 (比較例1 8 ) 在不施以超音波的條件下，使。用與實施例24相同的方 法進行沸石化反應的結果，將被得到的反應生成物中之過 剩的氫氧化鈉以水洗淨，自然乾燥後得到粉末。藉由X線 繞射法確認此粉末構造的結果，並沒有在細孔的深處發現 沸石的轉換。此錦十字沸石的陽離子交換容量爲2 6 0 c m ο 1 (+ ) kg — 1 。 (實施例25 ) 將非結晶性矽酸鋁之含有量爲80 %而矽鋁比約2.0之 都市垃圾的焚化灰（東京都町田市淸掃局焚化場製）20g 以及20g的玻璃粉末（西日本環境開發協同組合製）放入 於實施例4中所使用之反應容器中，再由其上方加入3 · 5 N 的氫氧化鈉水溶液240ml後，一邊施以600W、25kHz之超 音波，一邊通電於電磁感應加熱器（松下電器產業股份有 限公司製，National Z - P57 )來加熱至內部的溫度到達80 〜90t爲止。保持此狀態20小時後，取出內部的反應生成 物，再以水將此反應生成物中之過剩的氫氧化鈉洗淨，自 然乾燥後得到粉末。藉由X線繞射法確認此粉末構造的結 果，發現至細孔的深處亦生成有鈣十字沸石。此鈣十字沸 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -64- --------訂---------線 (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 491814 A7 _ B7 五、發明說明（62) 石的陽離子交換容量爲330 cmol ( + ) kg — 1。 (比較例19 ) 在不施以超音波的條件下，使用與實施例25相同的方 法進行沸石化反應的結果，將被得到的反應生成物中之過 剩的氫氧化鈉以水洗淨，自然乾燥後得到粉末。藉由X線 繞射法確認此粉末構造的結果，並沒有在細孔的深處發現 沸石的轉換。此耗十字沸石的陽離子交換容量爲2 8 0 c m ο 1 (+ ) kg — 1 。 (實施例26 ) 將非結晶性矽酸鋁之含有量爲80 %而矽鋁比約2.0之 都市垃圾的焚化灰（東京都町田市淸掃局焚化場製）20g 以及5g的玻璃粉末（西日本環境開發協同組合製）放入於 實施例1中所使用之反應容器中，再由其上方加入4N的氫 氧化鈉水溶液200ml，關閉蓋子後，一邊施以600W、 2 5kHz之超音波，一邊藉由飽和蒸氣加壓來加熱至內部的溫 度到達1 20 °C爲止。保持此狀態5小時後，抽出蒸氣恢復至 大氣壓，然後取出內部的反應生成物。在不水洗此反應生 成物下，藉由X線繞射法確認其構造的結果，發現至細孔 的深處亦生成有鈣十字沸石。此鈣十字沸石的陽離子交換 容量爲 340cmol ( + ) kg— 1σ (比較例2 0 ) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -65- -------!i#------- 丨訂----^----·-線-♦- (請先閱讀背面之注意事項再填寫本頁) 491814 A7 B7 五、發明說明（63) 在不施以超音波的條件下，使用與實施例26相同的方 法進行沸石化反應的結果，於不水洗被得到之反應生成物 下，藉由X線繞射法確認其構造的結果，並沒有在細孔的 深處發現沸石的轉換。此鈣十字沸石的陽離子交換容量爲 210cmol( + ) kg 一 1〇 (實施例27 ) 將非結晶性矽酸鋁之含有量爲80 %而矽鋁比約2.0之 都市垃圾的焚化灰（東京都町田市淸掃局焚化場製）20g 以及5 g的玻璃粉末（西日本環境開發協同組合製）放入於 實施例8中所使用之反應容器中，再由其上方加入4N的氫 氧化鈉水溶液200ml，關閉蓋子後，一邊施以600W、 2 5kHz之超音波，一邊藉由飽和蒸氣以及紅外線放射來加熱 至內部的溫度到達1 20 °C爲止。保持此狀態5小時後，抽出 蒸氣恢復至大氣壓，然後取出內部的反應生成物。在不水 洗此反應生成物下，藉由X線繞射法確認其構造的結果， 至 聲 發現至細孔的深處亦生成有鈣十字沸石以及少量的羥基方 鈉石。此鈣十字沸石以及羥基方鈉石的陽離子交換容量爲 360 cmol ( + ) kg 一 1 〇 (實施例28 ) 將非結晶性矽酸鋁之含有量爲80 %而矽鋁比約2.0之 都市垃圾的焚化灰（東京都町田市淸掃局焚化場製）20g 以及5g的玻璃粉末（西日本環境開發協同組合製）放入於 -66- (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） 經濟部智慧財產局員工消費合作社印製 491814 A7 B7 五、發明說明（64) 實施例9中所使用之反應容器中，再由其上方加入4N的氫 氧化鈉水溶液2 0 0 m 1，關閉蓋子後，一邊施以6 0 0 W、 25 kHz之超音波，一邊藉由飽和蒸氣以及微波加熱來加熱至 內部的溫度到達1 20t爲止。保持此狀態5小時後，抽出蒸 氣恢復至大氣壓，然後取出內部的反應生成物。在不水洗 此反應生成物下，藉由X線繞射法確認其構造的結果，發 現至細孔的深處亦生成有鈣十字沸石。此鈣十字沸石的陽 離子交換容量爲410 cmol ( + ) kg — 1。 (比較例21 ) 在不施以超音波的條件下，使用與實施例28相同的方 法進行沸石化反應的結果，於不水洗被得到之反應生成物 下/藉由X線繞射法確認其構造的結果，並沒有在細孔的 深處發現沸石的轉換。此鈣十字沸石的陽離子交換容量爲 3 20 cmol ( + ) kg ~ 1 ° (實施例29 ) 將非結晶性矽酸鋁之含有量爲80 %而矽鋁比約2.0之 都市垃圾的焚化灰（東京都町田市淸掃局焚化場製）20g 以及5g的玻璃粉末（西日本環境開發協同組合製）放入於 實施例1 0中所使用之反應容器中，再由其上方加入4 N的氫 氧化鈉水溶液2 0 0 m 1，關閉蓋子後，一邊施以6 0 0 W、 25kHz之超音波，一邊藉由飽和蒸氣以及電磁感應加熱器的 通電來加熱至內部的溫度到達1 20 t爲止。保持此狀態5小 --------------------訂---------線 (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） -67- 491814 A7 B7 五、發明說明（65) (請先閱讀背面之注意事項再填寫本頁) 時後，抽出蒸氣恢復至大氣壓，然後取出內部的反應生成 物。在不水洗此反應生成物下，藉由X線繞射法確認其構 造的結果，發現至細孔的深處亦生成有錦十字沸石。此銘 十字沸石的陽離子交換容量爲390 cmol ( + ) kg — 1。 (實施例30 ) 將非結晶性矽酸鋁之含有量爲80 %而矽鋁比約2.0之 都市垃圾的焚化灰（東京都町田市淸掃局焚化場製）20g 以及5g的廢矽藻土（麒麟麥酒股份有限公司取手工場製） 放入於實施例1中所使用之反應容器中，再由其上方加入 4N的氫氧化鈉水溶液200ml，關閉蓋子後，一邊施以600W 、25kHz之超音波，一邊藉由飽和蒸氣來加熱至內部的溫 度到達80〜90 °C爲止。保持此狀態20小時後，取出內部 的反應生成物。在不水洗此反應生成物下，藉由X線繞射 法確認其構造的結果，發現至細孔的深處亦生成有鈣十字 沸石。此鈣十字沸石的陽離子交換容量爲380 cmol ( + ) kg】。 經濟部智慧財產局員工消費合作社印制衣 (比較例22 ) 在不施以超音波的條件下，使用與實施例3 0相同的方 法進行沸石化反應的結果，於不水洗被得到之反應生成物 下，藉由X線繞射法確認其構造的結果，並沒有在細孔的 深處發現沸石的轉換。此鈣十字沸石的陽離子交換容量爲 270 cmol ( + ) kg — 1 0 -68- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 491814 A7 ___ B7____ 五、發明說明（66) (實施例3 1 )Member of the Intellectual Property Bureau of the Ministry of Economic Affairs, “Consumption Cooperation”, and 5. V. Description of Invention (33) In the aforementioned artificial zeolite cleaning device 28, an upper part of the cleaning tank 30 is provided with a pressure regulating system 5 1 as a supply in advance. The air port 25a of the incoming air introduction part promotes the solid-liquid separation after washing the slurry solids in the washing tank 30. A lower portion of the cleaning tank 30 is provided in advance with a transfer unit 26b for sending the solid matter obtained by dewatering the slurry to the next step, and the cleaning tank is adjusted by air from the pressure regulating system 51. For the pressure within 30, the aforementioned solid matter is controlled to a pressure feed state, and then transferred to a next artificial zeolite type replacement step by a rotary pump 33. (5) Type replacement step of artificial zeolite: The type replacement step of artificial zeolite refers to a step of replacing the cations of the artificial zeolite synthesized in the aforementioned artificial zeolite generation step with other cations. The artificial zeolite at the time of production will become the type of basic cations supplied to the reaction. Therefore, it is necessary to replace the artificial zeolite cations according to the intended use. Therefore, the artificial zeolite type replacement device 34 is used to replace the artificial zeolite. Cation step. The artificial zeolite replacement device 34 is also in the same form as the separation device 21 or the washing device 28. Inside the artificial zeolite type replacement device 34, a partition wall 29a for separating the slurry is formed, and formed by the artificial zeolite washing step. The artificial zeolite solids are replaced with other cations to replace the tank 35 and the discharge portion 36. In the type replacement device 34 of the artificial zeolite described above, an air port 25b is provided in advance in the upper part of the type replacement tank 35 as an introduction part for supplying air from the pressure adjustment system 51 to promote type replacement. The solid-liquid fraction of the slurry after the solids are replaced by cations in the tank 35. The paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) -36 · -------- Order ----- ---- Line IAW. (Please read the notes on the back before filling out this page) 491814 A7 ___B7___ V. Description of Invention (34) Leaving. In addition, a transfer unit 37 is provided in the lower part of the type replacement tank 35 in advance to send the slurry solids replaced by cations to the next step, and the type replacement tank 35 is adjusted by the air from the pressure regulating system 51. As for the internal pressure, the aforementioned solid matter is controlled to a pressure-feeding state, and then transferred to the next washing step by the rotary pump 38. This type replacement step of artificial zeolite is a step of exchanging cations adsorbed on artificial zeolite to predetermined cations. Since the generated artificial zeolite is usually treated in an alkaline aqueous solution composed of sodium hydroxide, if the artificial zeolite is dehydrated intact, a sodium-type artificial zeolite can be obtained. This type of artificial zeolite replacement step is a step in which sodium-type artificial zeolite is exchanged with other cations and replaced with a different type of artificial zeolite. Specifically, if it is to be changed to calcium type, the original type of artificial zeolite may be placed / exchanged in a calcium salt aqueous solution such as calcium chloride, and if it is to be changed to iron type, the original type may be changed. The artificial zeolite can be ion-exchanged in an iron salt aqueous solution such as ferric chloride. If it is to be changed to a magnesium type, the original type of artificial zeolite can be ion-exchanged in an aqueous magnesium salt solution such as magnesium chloride. However, if it is desired to change it to a potassium type, the original type of artificial zeolite may be placed in a potassium salt aqueous solution such as potassium chloride and ion-exchanged. By the above method, it can be replaced with various types of artificial zeolites. Since the various types of artificial zeolites obtained in this way can be used for various applications in their respective areas, the types of artificial zeolites corresponding to their uses can be easily manufactured. As shown in the system diagram in FIG. 2, generally, a solution tank 34a is provided in the type replacement step of artificial zeolite, and a saltwater solution tank, an iron salt solution tank, an aluminum salt solution tank, and a magnesium salt solution solution are provided in the solution tank 34a. -37- (Please read the precautions on the back before filling this page) _Line 'This paper size is applicable to China National Standard (CNS) A4 (21〇x 297 mm) 491814 A7 B7 V. Description of Invention (35) Slot By putting these aqueous solutions into the type replacement tank 35, it is possible to easily perform ion exchange to replace the desired type. (Please read the precautions on the reverse side before filling out this page.) In addition, the artificial zeolite that is put into the type replacement device 34 must use the artificial zeolite that has been taken out at least once after being removed in the aforementioned artificial zeolite separation step. For example, the artificial zeolite washing device 28 of the solid-liquid separation type can be used to wash the artificial zeolite. (6) Washing step of artificial zeolite: The washing step of artificial zeolite after the type replacement step of artificial zeolite means washing and removing the solution attached to the surface of artificial zeolite during the processing of the type replacement step of artificial zeolite. A step of. The washing step after the type replacement step of the artificial zeolite refers to the step of washing and removing the solution attached to the surface of the artificial zeolite in the treatment of the type replacement step of the artificial zeolite using the artificial zeolite washing device 39. ¾ 郢 一 郢 i 4 4¾ members X. Consumption 泎 fi Printed cation-replaced artificial zeolite transferred by rotary pump 38. After being washed in the washing tank 40, the water separated by solid and liquid is collected in Drain 41, and then send this water out of the step. In the aforementioned artificial zeolite cleaning device 39, an air port 40a is provided in the upper part of the cleaning tank 40 as an introduction part for supplying air from the pressure regulating system 51 in advance, so as to facilitate the cleaning tank 40. Solid-liquid separation after internal washing of slurry solids. In addition, a lower part of the cleaning tank 40 is provided with a transfer unit 42 for sending the solid matter obtained by dewatering the slurry to a next step in advance, and the cleaning is adjusted by the air from the pressure regulating system 51. Regarding the pressure in the tank 40, the aforementioned solid matter is controlled to be in a pressure-feeding state, and then transferred to the next -38 by a rotary pump 43. This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (%) 491814 A7 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ______B7 ___ V. Description of the invention (36) In the dehydration step of artificial zeolite. (7) Dehydration step of artificial zeolite: The dehydration step of artificial zeolite refers to the step of dehydrating and drying the artificial zeolite that has been finally washed to make it into a finished product. The aforementioned de-icing step of the artificial zeolite is a step of dehydrating the artificial zeolite that has been replaced with a type to make it into a finished product. Because of the type of artificial zeolite that has been replaced, thorium contains a large amount of water, so it must be dehydrated to a predetermined moisture content. The artificial zeolite dehydration device includes a dewatering device 44 and a finished product tank 45. The artificial zeolite dehydration device 44 in the present invention is based on a dehydration theory using a heat pump method. That is, the air and / or water vapor in the dewatering tank 46 provided in the dewatering device 44 is sucked and decompressed, and then the air and / or water vapor after being sucked is pressurized and heated to return it to the existence of artificial. In the spiral tube (so-called heating coil) in the zeolite dewatering tank 46, it is evaporated together with the moisture in the artificial zeolite, and the water vapor is dehydrated by condensing water vapor in the spiral tube and then discharged. Repeat these actions to dehydrate the artificial zeolite. Because artificial zeolite needs a certain amount of water according to its use state, the degree of dehydration needs to be appropriately adjusted. The degree of dehydration can be adjusted by the processing time in the dehydration tank 46. By doing so, dehydration can be efficiently performed by using the heat generated when the air and / or water vapor is sucked after being pressurized. (8) Other steps or devices: This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 public love) -39--------- Order --------- line (Please read the precautions on the back before filling this page) 491814 A7 ______B7__ V. Description of the invention (37) As for the continuous manufacturing method for manufacturing artificial zeolite by contacting the heated reaction tube of the present invention and its continuous manufacturing device, In the method of transferring the raw material mixture or the artificial zeolite from the artificial zeolite generation step to the artificial zeolite dehydration step, an air opening method using a pump or a pressure feeding method using a pressure difference can be suitably used. In the present invention, it is preferable to use a pressure feeding method due to a pressure difference. The aforementioned pressure feeding method is a method in which a pressure difference is generated between the steps, and the pressure difference is used to automatically transfer the aforementioned raw material mixture or artificial zeolite from a step with a high pressure to a step with a low pressure. Therefore, the feeding speed can be arbitrarily set by adjusting the pressure difference and the size of the tube. Therefore, while controlling the transfer speed of the aforementioned raw material mixture or artificial zeolite, it is possible not only to easily feed those materials, but also to manufacture the artificial zeolite easily and efficiently. In particular, in the aspect of the present invention, because the stirring action of the raw material mixture is recorded in the reaction tube of the artificial zeolite generation step device, the reaction with the production of artificial zeolite is severely closed. Therefore, the so-called And it is easy to adjust the speed of the aforementioned raw material mixture to easily control the special effect of the artificial zeolite formation reaction. The artificial zeolite continuous manufacturing device having such a general pressure feeding method is provided with a pressure verification operation on each device and a pressure adjustment operation that causes a pressure difference between the devices based on the pressure verification operation. For example, after the pressure can be verified by using a pressure verification operation composed of a pressure sensor, the device at each step can also be adjusted by using a pressure adjustment operation composed of a liquid or air pressure adjustment system 51. Pressure. _40_ (Please read the notes on the back before filling this page) This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) 491814 A7 ------- B7___ V. Description of Invention (38) Especially as a pressure adjustment system, it is preferable to use an air supplier, and the air can be easily adjusted by putting air in and out of each device. (Please read the precautions on the back before filling this page.) In the present invention, not only the reaction tube 7 of the artificial zeolite production step device, but also the turbulent flow should be generated even when the raw material mixture or artificial zeolite is transferred. Set the inner diameter or transfer speed of each piping. In this way, turbulence is generated by designing the inner diameter or the transfer speed of each pipe by design. In this way, by designing a method for generating a turbulent flow in the piping between the devices in each step, the piping can also be mixed with washing water or an ion exchange solution, so that these substances are sufficiently stirred and then processed. For example, between the artificial zeolite generation step and the artificial zeolite separation step, an aqueous solution diluted with water is mixed with the recovered alkaline aqueous solution to sufficiently stir the pipe during the piping, so that the artificial zeolite separation can be easily performed. The solid-liquid separation in the step. In addition, between the artificial zeolite separation step and the artificial zeolite decontamination step, or in the piping after the type replacement step, by adding washing water, the artificial zeolite can be washed more efficiently. In addition, before the artificial zeolite type replacement step is performed, "the ion exchange is easily performed by incorporating an ion exchange solution", so that the type replacement efficiency can be improved. As an attached device to make continuous manufacturing possible, corresponding to the needs, a pre-mixed raw material mixture concentration sensor, an alkali j concentration sensor, an ion sensor, a liquid level sensor, and a moisture sensor may be provided in each step of the device; sensors. Based on the signals detected by such sensors, it is possible to adjust the concentration or liquid level by replenishing the material. : In the present invention, recycling of washing water is sought. In the present invention, because of the washing step, it is usually set in the separation step or the type replacement step. The paper size applies the Chinese National Standard (CNS) A4 specification (210 χ 297 mm). Printed by the cooperative 491814 Α7 _ B7 5. After the description of the invention (39), the washed water will be changed to a person containing a large amount of sodium ions. The osmosis membrane can be used as the washing water as described above. In the present invention, the alkaline aqueous solution is reused, that is, the alkaline that is recovered after the artificial zeolite separation step is separated. The aqueous solution can be reused by returning it to the original mixed layer 5 described above. An example of an embodiment of the present invention will be shown below to explain the present invention more specifically. The gist of the present invention is not limited to the following embodiments. Based on the artificial zeolite system, as shown in Figure 1 and Figure 2, through the preparation process of the raw material mixture, the artificial zeolite raw material adjusted to a predetermined silica-aluminum ratio and the alkaline aqueous solution are mixed, and then the sequence of the raw material mixture obtained before is obtained. The artificial zeolite generation device B, artificial zeolite separation device C, artificial zeolite cleaning device D, artificial zeolite type replacement device E, artificial zeolite cleaning device F, and artificial zeolite dehydration device G are produced by the following methods. Order to explain. First, a raw material mixture is prepared in a raw material mixture preparation step. As the raw material of the raw material mixture described above, for example, coal ash 'stored in the raw material storage tank 3 and a 48% sodium hydroxide aqueous solution stored in the alkaline aqueous solution tank 4 can be used. The quantitative amounts of these materials and dilution water are sent to the aforementioned raw material mixing tank 5 'while it is diluted to become a 3% (about 3.5N) aqueous solution of sodium ammonium hydroxide' while stirring with a stirrer to prepare the aforementioned raw material mixture . This raw material mixture is a mixture of coal ash and sodium hydroxide aqueous solution so that it becomes a predetermined ratio. When considering the formation reaction of artificial zeolite, the size of the paper is applicable to China National Standard (CNS) A4 (210 X 297 mm). ) -42- r --- l · -------- ^ ---- ^ ---- "Please read the back first < > I will fill in this page again for the matters of interest} Printed by the Employees ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 491814 A7 B7 V. Description of the invention (40) For coal ash 1, the proportion of sodium hydroxide solution will be 2 It is better to be 1 to 2 and it is better to be 3 to 8. Next, the previously prepared raw material mixture is sent to a raw material mixture supply tank 6 which always maintains a certain amount, and is continuously supplied to the reaction tube 7 of the artificial zeolite production apparatus B while stirring. In addition, the piping for supplying the raw material mixture in contact with the outlet pipe of the artificial zeolite generation step is brought into contact with the temperature of the raw material mixture in the heating (for example, 80t), so that the raw material mixture that has been heated can be economically supplied. The viewpoint of reaction promotion is also suitable. In the artificial zeolite production apparatus B ', the reaction tube 7 to be reacted is arranged in a spiral shape as shown in Figs. 3 and 4 by a turbulent flow while the raw material mixture previously supplied is disturbed. Around the reaction tube 7, in order to change the premixed raw material mixture in the reaction tube 7 to a predetermined reaction temperature (for example, 175 ° C) and a predetermined pressure (for example, about 8 kg / cm2), the predetermined temperature (for example, , 200 ° C) heat carrier oil 9 cycles. The inlet side of the reaction tube 7 is pressurized to a predetermined pressure by a pump R on the supply side of the preceding raw material mixture, and the preceding raw material mixture is controlled as if the preceding raw material mixture is caused to flow toward the outlet side of the reaction tube 7 at an arbitrary speed. Here, the inner diameter of the reaction tube 7 is, for example, 1. 5 inches (about 38 mm) of artificial zeolite is synthesized by passing the aforementioned raw material mixture into the reaction tube 7. In addition, in the artificial zeolite generating apparatus B shown in Figs. 3 and 4, for example, a reaction tube length changing operation in which the reaction tube 7 is switched in three stages is used. The alkaline aqueous solution containing the artificial zeolite that has been generated is sent to the artificial zeolite separation device 21 through a pipe and mixed with the above-mentioned raw materials. This paper is in accordance with China National Standard (CNS) A4 (210 X 297 mm). -43- ------------- ^ ----_----. · ^ IAWT (Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 491814 A7 ___ B7 V. Description of the invention (41) The piping of the object is further in the cooler 20 It is cooled by heat exchange. In addition, during the piping, a feeding port P is provided for feeding a solution produced by adding water to the alkaline aqueous solution recovered in the artificial zeolite separation step. The heating during the reaction can be performed by introducing heated heating oil 9 into the heating medium tank 8 for heating, and by blowing heated steam, waste heat, or the like, the reaction temperature can be increased. Further, the heating medium tank may be heated by infrared radiation, microwave heating, or the like. In addition, during the heating reaction, an ultrasonic vibration machine is attached to the reaction tube 7, and the zeolization reaction can also be promoted by the addition of ultrasonic vibration. The alkaline aqueous solution containing the artificial zeolite sent to the artificial zeolite separation device 21 first settles a solid portion composed of the artificial zeolite in the separation tank 23, and then separates it from the liquid portion of the alkaline aqueous solution containing sodium hydroxide and the like. The artificial zeolite in the solid portion is sent from the inlet below the separation tank 23 to the next artificial zeolite washing device 28. At this time, although it can be transferred by pressure feeding, it can also be used with a pump when it is used for the purpose of measuring the slurry-like artificial zeolite. The sodium hydroxide aqueous solution in the liquid portion can be recovered in the discharge portion 24 partitioned by the partition walls 22. In addition, the recovered sodium hydroxide aqueous solution is returned to the raw material mixing tank 5 again, or is returned to the aforementioned input port P. Above the aforementioned separation tank 23, an air port 25 is provided, and the internal pressure of the separation tank 23 is adjusted by the air from the pressure adjustment system 51 to control the pressure feeding state. The artificial zeolite 'sent to the artificial zeolite washing device 28 is added with washing water during the piping. The artificial zeolite added to the washing water is applicable to the Chinese National Standard (CNS) A4 ^ (210 X 297 mm) -44 ^ " one (please read the precautions on the back before filling this page) ) ----- I i 丨 丨 Order -------- I. 491814 A7 B7 Acoustic I hour i h t Soil P t V. Description of the invention (42) In the pipe, it is stirred by the turbulent flow effect in the pipe, and then it is put into the washing tank 30 with sufficient washing. This artificial zeolite washing device 28 has the same form as the artificial zeolite separation device 21 described above. After the washed artificial zeolite is settled, it is transferred by a pump from an outlet below the washing tank to a next type replacement device. 34 in. The washing liquid can be recovered by the discharge portion 36 partitioned by a plurality of partition walls 29a, and is returned to the washing water supply tank 50 after filtering according to need. The internal pressure of the cleaning tank 30 is also adjusted by the same configuration as the separation tank 23 described above. The artificial zeolite sent to the artificial zeolite type replacement device 34 is added with one of various aqueous solutions for type replacement during the piping. In addition, when it is desired to change it to a sodium-type artificial zeolite, it may be sent to the dehydration device 44 in the next step as it is. The artificial zeolite to be added to the type replacement is to be put into the type replacement tank 35 in the type replacement device 34. This type of replacement device 34 also has the same form as the aforementioned artificial zeolite separation device 21 or artificial zeolite cleaning device 28. After the washed artificial zeolite is settled, it is transferred by an outlet below the type replacement tank by a pump To the next artificial zeolite washing step. The treatment liquid can be recovered by the discharge portion 36 partitioned by the plurality of partition walls 29a, and is returned to the replacement liquid circulation tank 52 after filtering according to need. The internal pressure of the type replacement tank 35 is also adjusted by the same structure as the aforementioned separation tank 23 and the like so as to control the pressure feeding state thereof. The artificial zeolite sent to the artificial zeolite washing device 39 is added with washing water during the piping. The artificial zeolite to which the washing water is added passes through the piping, is stirred by the turbulent flow occurring in the piping, and is then put into the washing tank 40 with sufficient washing. The paper size of this artificial zeolite cleaning device is in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 mm) _45 · (Please read the precautions on the back before filling this page) 491814 1 丨 才 i By saturation Steam is added to A7 B7 V. Description of the invention (43) 39 It has the same form as the artificial zeolite washing device 28 described above. After the washed artificial zeolite is settled, it is transferred by the pump through the outlet below the washing tank. To the next artificial zeolite dehydration step. The washing liquid can be recovered in the discharge portion 41 partitioned by several partition walls 39a, and is returned to the washing water supply tank 5 3 after filtering, as needed. The internal pressure of the aforementioned washing tank 40 is also adjusted by using the same structure as that of the aforementioned washing tank 30 so as to control the pressure feeding state. The artificial zeolite sent to the artificial zeolite dewatering device G is dehydrated in the dewatering tank 46. First, the air and water vapor in the dewatering tank are sucked, and the air and water vapor are pressurized and heated by a compressor 47 (refer to FIG. 8), and then returned to the heating in the dewatering tank 46 containing artificial zeolite. Inside the coil. The water in the artificial zeolite is evaporated by heating the coil. The water vapor in the heating coil is condensed and discharged. With the principle of such a heat pump, the artificial zeolite is dehydrated and then transferred from the lower part of the dehydration tank to the finished product tank 45 to obtain the artificial zeolite. (Example 1) An ultrasonic vibrator (manufactured by Nippon Seiki Co., Ltd., MODEL US -⑼GT) was installed on a 1-liter sterilization autoclave (manufactured by Toyo High Pressure Co., Ltd.) with a stirrer to purchase Luer ears automatically. The silicon to aluminum ratio of the island is about 3. 2 volcanic glass was pulverized. 20g of volcanic volcanic glass and 200ml of 2N sodium hydroxide aqueous solution were put into this reaction container 'after the lid was closed' while applying 600W, 25kHz ultrasonic heat until the internal temperature reached 90 ° C . Keep in this state for 12 hours ------- IIIII 1111111 ^ '— — — — — — I— (Please read the notes on the back before filling this page) The paper size applies to Chinese National Standard (CNS) A4 Specifications (210 X 297 mm) -46-491814 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention (44) The internal reaction product. Without washing the reaction product with water, ‘the result of confirming its structure by the X-ray diffraction method’, it was found that phillipsite was also formed at the pores of the pores. The cation exchange capacity of this phillipsite is 410 c mol (+) kg — 1. (Comparative Example 1) The results of zeolite reaction using the same method as in Example 1 without applying ultrasonic waves were confirmed by X-ray diffraction method under the reaction product obtained without washing with water. As a result of the construction, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this phillipsite is 280 cmol (+) kg-10 (Example 2). The volcanic glass of 2 was pulverized. 20 g of pulverized volcanic glass and 200 ml of a 2N sodium hydroxide aqueous solution were put into the reaction container used in Example 1. After closing the lid, a 600 W, 25 kHz ultrasonic wave was applied while borrowing. Pressurize with saturated steam until the internal temperature reaches 200 ° C. Keep this state 0. After 5 hours, the vapor was extracted to return to atmospheric pressure, and then the internal reaction product was taken out. The structure of the reaction product was confirmed by X-ray diffraction without washing the reaction product with water. It was found that phillipsite was also formed to the depth of the pores. The cation exchange capacity of this phillipsite is 420 cmol (+) kg _ 1. (Comparative Example 2) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -47- ------- 1—— 丨 · -------- Order- -, ----- · Line · (Please read the precautions on the back before filling this page) 491814 A7 ______ B7 V. Invention Description (45) (Please read the precautions on the back before filling this page) The results of zeolite reaction using the same method as in Example 2 under the condition of applying ultrasonic waves, and the results of confirming the structure by X-ray diffraction method under the reaction product obtained without washing with water were not found. The conversion of zeolite was found deep in the pores. The cation exchange capacity of this phillipsite is 300 cmol (+) kg -1 (Example 3) The content of amorphous aluminum silicate is 80% and the ratio of silicon to aluminum is about 2. 20 g of incineration ash from municipal waste (manufactured by the Municipal Sweeping Bureau Incineration Plant, Machida, Tokyo) and 200 ml of a 2N aqueous sodium hydroxide solution were placed in the reaction container used in Example 1. After closing the lid, 600 W was applied. , 25kHz ultrasonic wave, while heating until the internal temperature reaches 90 ° C. After keeping this state for 2 hours, the reaction product inside was taken out. As a result of confirming the structure by X-ray diffraction without washing the reaction product with water, it was found that hydroxysodalite was also formed to the depth of the pores. The cation exchange capacity of this hydroxy sodalite is 340 cmol (+) kg-1. (Comparative Example 3) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, using the same method as in Example 3 without applying ultrasonic waves, under the reaction product obtained without washing As a result of confirming the structure by the X-ray diffraction method, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this hydroxy sodalite is 270cmol (+) kg-10-48- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 491814 A7 B7 V. Description of the invention (46) (Example 4) The content of amorphous aluminum silicate was 80% and the ratio of silicon to aluminum was about 2. 20 g of incineration ash from municipal waste (manufactured by Miyata City, Tokyo Municipal Bureau of Incineration Plant) and 200 ml of 2N sodium hydroxide aqueous solution, placed in an ultrasonic vibrator (manufactured by Nippon Seiki Co., Ltd., MODEL US-6GGT In the reaction container of), after the lid is closed, while applying ultrasonic waves of 600W and 25kHz, it is heated to the internal temperature of 90 by infrared radiation from an infrared radiation device (manufactured by Rigaku Electric Co., Ltd., a vertical infrared furnace). ° C. After keeping this state for 24 hours, the internal reaction product was taken out. As a result of confirming the structure by X-ray diffraction without washing the reaction product with water, it was found that hydroxysodalite was also formed to the depth of the pores. The cation exchange capacity of this hydroxy sodalite is 310 cmol (+) kg — 1. (Comparative Example 4). The results of zeolite reaction were performed using the same method as in Example 4 without applying ultrasonic waves, and the results of the structure were confirmed by X-ray diffraction method under the reaction product obtained without washing, and No zeolite conversion was found deep within the pores. The cation exchange capacity of this hydroxy sodalite is 280 cmol (+) kg — 1. (Example 5) The content of amorphous aluminum silicate was 80% and the ratio of silicon to aluminum was about 2. 20 g of incineration ash from municipal waste (manufactured by the municipal incineration plant of Machida City, Tokyo) and 200 ml of a 2N aqueous sodium hydroxide solution were placed in Example 4 so that the paper size was in accordance with China National Standard (CNS) A4 (210 X 297 mm) -49- (Please read the notes on the back before filling out this page) — Order --------- line · 491814 Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 5 Explanation of the invention (47) In the reaction container used, after the lid is closed, a microwave heater (manufactured by Hitachi, Ltd., MRH-4) is used for microwave heating while applying a 600 W, 25 kHz ultrasonic wave. Come to heat until the internal temperature reaches 90 ° C. After keeping this state for 24 hours, the internal reaction product was taken out. As a result of confirming the structure by X-ray diffraction without washing the reaction product with water, it was found that hydroxysodalite was also formed to the depth of the pores. The cation exchange capacity of this hydroxy sodalite is 310 cmol (+) kg — 1. (Comparative Example 5) The results of performing a zeolite reaction using the same method as in Example 5 without applying ultrasonic waves were confirmed by X-ray diffraction method under the reaction product obtained without washing with water. As a result of the construction, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this hydroxy sodalite is 280 cmol (+) kg ~ 1. (Example 6) The content of amorphous aluminum silicate was 80% and the ratio of silicon to aluminum was about 2. 20 g of incineration ash from municipal waste (manufactured by the Municipal Sweeping Bureau Incineration Plant, Machida, Tokyo) and 200 ml of a 2N aqueous sodium hydroxide solution were placed in the reaction container used in Example 4, and the lid was closed while being applied. Ultrasonic waves of 600 W and 25 kHz were heated by an electromagnetic induction heater (manufactured by Matsushita Electric Industrial Co., Ltd., National Z — P57) until the internal temperature reached 90 ° C. After keeping this state for 24 hours, the internal reaction product was taken out. Without washing the reaction product with water, confirm its structure by X-ray diffraction. The paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) -50 _ ------- ref.- ------- Order · —i 轸 (Please read the notes on the back before filling this page) 491814 A7 _ B7 V. As a result of the description of the invention (48), it is found that hydroxyl groups are also formed to the depth of the pores Sodalite. The cation exchange capacity of this hydroxy sodalite is 310 cmol (+) kg — 1. (Comparative Example 6) The results of performing the zeolite reaction using the same method as in Example 6 without applying ultrasonic waves were confirmed by X-ray diffraction method under the reaction product obtained without washing with water. As a result of the construction, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this hydroxy sodalite is 280 cmol (+) kg -1 (Example 7) The content of the non-crystalline acid acid salt is 80% and the ratio of the acid crystal is about 2. 20 g of incineration ash from municipal waste (manufactured by the Tokyo Metropolitan Municipal Sweeping Bureau Incineration Plant) and 200 ml of 4N aqueous sodium hydroxide solution were placed in the reaction container used in Example 1. After closing the lid, 600 W was applied. , 25kHz ultrasonic wave, while heating by saturated steam pressure until the internal temperature reaches 120 ° C. After keeping this state for 5 hours, the vapor was extracted to return to atmospheric pressure, and then the reaction product inside was taken out. As a result of confirming the structure by X-ray diffraction without washing the reaction product with water, it was found that hydroxysodalite was also formed to the depth of the pores. The cation exchange capacity of this hydroxy sodalite is 380 cmol (+) kg-1. (Comparative Example 7) The same method as in Example 7 was used without applying ultrasonic waves (please read the precautions on the back before filling this page) 0 -------- Order i — — ^ ----line. Printed by the Intellectual Property Bureau of the Ministry of Economy ’s Consumer Cooperatives The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -51-Printed by the Intellectual Property Bureau of the Ministry of Economy ’s Consumer Cooperatives 491814 A7 B7 49) As a result of the zeolite reaction carried out by the method, the structure of the reaction product obtained without washing was confirmed by X-ray diffraction method, and no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this hydroxy sodalite is 230 cmol (+) kg _ 1 〇 (Example 8) An ultrasonic vibrator (limited by shares) Made by Japan Seiki Co., Ltd., MODEL US-6GGT) and infrared radiation device (manufactured by Rigaku Electric Co., Ltd., vertical infrared furnace), the content of amorphous aluminum silicate is 80% and the ratio of silicon to aluminum is about 2. 20 g of incineration ash from municipal waste (manufactured by the Tokyo Municipal Machida Municipal Sweeping Bureau Incineration Plant) and 200, ml of 4N sodium hydroxide aqueous solution were placed in the reaction container, and after closing the lid, a 600W, 25 kHz ultrasonic wave was applied. , While heating by infrared radiation until the internal temperature reaches 120 t. After keeping this state for 5 hours, the internal reaction product was taken out. As a result of confirming the structure by X-ray diffraction without washing the reaction product with water, it was found that hydroxysodalite was also formed to the depth of the pores. The cation exchange capacity of this hydroxy sodalite is 340 cmol (+) kg — 1. (Example 9) A 1-liter capacity autoclave (manufactured by Toyo High Pressure Co., Ltd.) equipped with a stirrer was provided with an ultrasonic vibrator (manufactured by Nippon Seiki Co., Ltd., MODEL US-6GGT) and a microwave heater (manufactured by Co., Ltd.) Made by Yueli Manufacturing Co., Ltd., MRH-4 type), the non-crystalline aluminum silicate is included in this paper. The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) -52- ------- ------------ Order --------- line (please read the notes on the back before filling this page) 491814 A7 ___B7_V. Description of the invention (50) The quantity is 80 % And the ratio of silicon to aluminum is about 2. 20 g of incineration ash from municipal waste (manufactured by the Municipal Sweeping Bureau Incineration Plant, Machida, Tokyo) and 200 ml of 2N aqueous sodium hydroxide solution were placed in this reaction container. After closing the lid, a 600 W, 25 kHz ultrasonic wave was applied. It is heated by microwave heating until the internal temperature reaches 120 ° C. After keeping this state for 5 hours, the internal reaction product was taken out. The structure of the reaction product was confirmed by X-ray diffraction without washing the reaction product with water. It was found that hydroxysodalite was also formed to the depth of the pores. The cation exchange capacity of this hydroxy sodalite is 340 cmol (+) kg — 1. (Example 10) A 1-liter capacity autoclave (manufactured by Toyo High Pressure Co., Ltd.) equipped with a stirrer was provided with an ultrasonic vibrator (manufactured by Nippon Seiki Co., Ltd., MODEL US-60GT) and an electromagnetic induction heater (Panasonic Industry corporation system. , National Z-P57), the content of amorphous aluminum silicate is 80% and the ratio of silicon to aluminum is about 2. 20 g of incineration ash from municipal waste (manufactured by the Municipal Sweeping Bureau Incineration Plant, Machida, Tokyo) and 2N sodium hydroxide aqueous solution 2 0 m 1 was placed in the reaction vessel, and the lid was closed while applying 600 W at 25 kHz. The ultrasonic wave is heated while the induction heater is energized until the internal temperature reaches 120t. After keeping in this state for 5 hours, remove the reaction product from the inner part. Without washing the reaction product with water, the structure of the reaction was confirmed by X-ray winding; it was found that hydroxyl I: sodalite was also formed to the depth of the pores. The cation exchange capacity of this hydroxy sodalite is 340 cmol (+ j-) kg-1. (Please read the precautions on the back before filling this page) · # Order: The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) -53- 491814 A7 __ B7 V. Description of the invention ( 51) (Example 11) (Please read the precautions on the back before filling this page) The content of amorphous aluminum silicate is 80% and the ratio of silicon to aluminum is about 2. 20 g of incineration ash from municipal waste (manufactured by the Municipal Sweeping Bureau, Machida, Tokyo) and 200 ml of 4N aqueous sodium hydroxide solution were placed in the reaction container used in Example 8. After closing the lid, 600 W was applied. , 25kHz ultrasonic wave, while heating by saturated steam and infrared radiation until the internal temperature reaches 1 20 ° C. After remaining in this state for 5 hours, the internal reaction product was taken out. Without washing the reaction product with water, the structure was confirmed by the X-ray diffraction method, and it was found that hydroxysodalite was also formed to the depth of the pores. The cation exchange capacity of this hydroxy sodalite is 350 cmol (+) kg-1 (Example 12) Economic property intellectual property ¾ employee consumption cooperation 钍 print the content of amorphous aluminum silicate to 80% and silicon aluminum Than about 2. 20 g of incineration ash from municipal waste (manufactured by the Municipal Sweeping Bureau Incineration Plant, Machida, Tokyo) and 2 N sodium hydroxide aqueous solution 2 0 0 m 1 was placed in the reaction container used in Example 9, and the lid was closed While applying a 600W, 25kHz ultrasonic wave, it was heated by saturated steam and microwave heating until the internal temperature reached 120 ° C. After keeping this state for 5 hours, the internal reaction product was taken out. As a result of confirming the structure by X-ray diffraction without washing the reaction product with water, it was found that hydroxysodalite was also formed to the depth of the pores. The cation exchange capacity of this hydroxy sodalite is 340 cmol (+) kg — 1. (Example 13) -54- This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 491814 A7 B7 V. Description of the invention (52) (Please read the precautions on the back before filling this page) The content of amorphous aluminum silicate is 80% and the ratio of silicon to aluminum is about 2. 20 g of incineration ash from municipal waste (manufactured by the Municipal Sweeping Bureau Incineration Plant, Machida, Tokyo) and 200 ml of a 2N aqueous sodium hydroxide solution were placed in the reaction container used in Example 10. After closing the lid, 600 was applied. W, 25 kHz ultrasonic waves are heated by saturated steam and induction heaters until the internal temperature reaches 120 ° C. After remaining in this state for 5 hours, the internal reaction product was taken out. As a result of confirming the structure by X-ray diffraction without washing the reaction product with water, it was found that hydroxysodalite was also formed to the depth of the pores. The cation exchange capacity of this hydroxy sodalite is 340 cmol (+) kg-1. (Example 14) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The content of amorphous aluminum silicate is 80% and the ratio of silicon to aluminum is about 2. 20 g of incineration ash from municipal waste (manufactured by the Tokyo Metropolitan Municipal Sweeping Bureau Incineration Plant) and 200 ml of 4N aqueous sodium hydroxide solution were placed in the reaction container used in Example 1. After closing the lid, 600 W was applied. , 25kHz ultrasonic wave, while heating by saturated steam pressure until the internal temperature reaches 200 ° C. Keep this state 0. After 5 hours, the vapor was extracted to return to atmospheric pressure, and then the internal reaction product was taken out. As a result of confirming the structure by X-ray diffraction without washing the reaction product with water, it was found that hydroxysodalite was also formed to the depth of the pores. The cation exchange capacity of this hydroxy sodalite is 560 cmol (+) kg — 1 0 (Comparative Example 8) The paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) -55-491814 A7 B7 Five 2. Description of the invention (53) (Please read the precautions on the back before filling in this page.) The results of zeolite reaction using the same method as in Example 14 without using ultrasonic waves were obtained without washing. As a result of confirming the structure of the reaction product by the X-ray diffraction method, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this hydroxy sodalite is 3 80 cmol (+) kg — 1. (Example 15) The content of amorphous aluminum silicate was 95% and the ratio of silicon to aluminum was about 2. 5 of the fly ash (produced by Matsuura Power Generation Co., Ltd., Power Supply Development Co., Ltd., provided by the fly ash association) 20g and 200ml of 4N sodium hydroxide aqueous solution were put into the reaction container used in Example 1, after closing the lid, apply Using 600W, 25 kHz ultrasonic waves, pressurized by saturated steam to heat the internal temperature to 120 ° C. After maintaining this state for 3 hours, the vapor was extracted to return to atmospheric pressure, and then the internal reaction product was taken out. Without washing the reaction product with water, the structure was confirmed by the X-ray diffraction method, and it was found that phillipsite was also formed to the depth of the pores. The cation exchange capacity of this phillipsite is 350 cmol (+) kg — 1. The clothing printed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (Comparative Example 9) The results of the zeolite reaction using the same method as in Example 15 were performed without applying ultrasonic waves, and the reaction was obtained without washing. The structure was confirmed by X-ray diffraction method under the object, and no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this phillipsite is 240 cmol (+) kg — 1. 56- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 491814 A7 _ B7 V. Description of the invention (54) (Example 16) Will be non-crystalline The content of flexible aluminum silicate is 95% and the ratio of silicon to aluminum is about 2. 5 of the fly ash (produced by Matsuura Power Generation Co., Ltd., Power Supply Development Co., Ltd., provided by the fly ash association) 20g and 200ml of 4N sodium hydroxide aqueous solution were put into the reaction container used in Example 1, after closing the lid, apply Using 600W, 25kHz ultrasonic waves, while heating with saturated steam, the internal temperature reaches 200 t. Keep this state 0. After 5 hours, the vapor was extracted to return to atmospheric pressure, and then the internal reaction product was taken out. The structure of the reaction product was confirmed by X-ray diffraction without washing the reaction product with water. It was found that phillipsite was also formed to the depth of the pores. The cation exchange capacity of this phillipsite is 380 cmol (+) kg — 1. (Comparative Example 10. ) The results of zeolite reaction using the same method as in Example 16 without applying ultrasonic waves, and confirming the results of its structure by X-ray diffraction method under the reaction product obtained without washing with water. No zeolite conversion was found in the depth of the pores. The cation exchange capacity of this phillipsite is 230 cmol (+) kg — 10 (Example 17). Incineration ash of solid waste fuel (provided by the Incineration Plant of Sweeping Bureau, Machida City, Tokyo) 100 g and 3 . 240ml of 5N sodium hydroxide aqueous solution was put into the reaction container used in Example 1. After closing the lid, the size of this paper was applied to Chinese National Standard (CNS) A4 (210 X 297 mm) -57- — — — — — Ilill — ϊ · 1111111 «— — 111 — '(Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 491814 A7 B7 V. Description of Invention (55) 600W , 25kHz ultrasonic wave, while heating with saturated steam until the internal temperature reaches 80 ~ 90 ° C. After keeping this state for 24 hours, the internal reaction product was taken out, and then excess sodium hydroxide was washed with water and dried naturally to obtain a powder. By the X-ray diffraction method, it was found that hydroxysodalite was also formed to the depth of the pores. The cation exchange capacity of this hydroxy sodalite is 3 60 cmol (+) kg " 1 ° (Comparative Example 1 1). The zeolite reaction was performed using the same method as in Example 17 without applying ultrasonic waves. As a result, excess sodium hydroxide in the obtained reaction product was washed with water and dried to obtain a powder. The results of this powder structure were confirmed by X-rays and radiography, and no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this hydroxy sodalite is 230 cmol (+) kg-1. (Example 18) 100 g of solid waste incineration ash (provided by the incinerator of Machida City, Tokyo) and 240 ml of a 3.5N sodium hydroxide aqueous solution were placed in the reaction container used in Example 1. After closing the lid, while applying a 600 W, 25 kHz ultrasonic wave, pressurize it with saturated steam to heat it to an internal temperature of 120 to 125 ° C. After maintaining this state for 2 hours, the steam was extracted to return to atmospheric pressure, and then the reaction product inside was taken out. The excess sodium hydroxide was washed with water, and dried to obtain a powder. By the X-ray diffraction method, it was found that hydroxy sodalite was also formed to the depth of the pores. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -58- ------------------- — Order ------- -(Please read the notes on the back before filling this page) 491814 A7 _B7 _ V. Description of the invention (56) The cation exchange capacity of this hydroxy sodalite is 370 cmol (+) kg 1. (Comparative Example 12) As a result of performing a zeolite reaction using the same method as in Example 18 without applying ultrasonic waves, excess sodium hydroxide in the obtained reaction product was washed with water The powder was obtained after natural drying. As a result of confirming the powder structure by the X-ray diffraction method, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this hydroxy sodalite is 240 cmol (+) kg — 1. (Example 19) The ratio of silicon and aluminum produced by Kagoshima was approximately 3. The volcano glass shattered 2 20g of pulverized volcanic glass and 5g of glass powder (manufactured by Nippon Environment Development Co., Ltd.) were placed in the reaction container used in Example 1, and then 200ml of 2N sodium hydroxide aqueous solution was added from above. After closing the lid, Apply a 600W, 25kHz ultrasonic wave, and heat it with saturated steam until the internal temperature reaches 9 ° C. After maintaining this state for 12 hours, remove the internal reaction product, without washing the reaction product with water. As a result of confirming its structure by X-ray diffraction method, it was found that the faujasite was also formed at the depth of the pores. The cation exchange capacity of this faujasite was 300 cmol ^ (+) kg 1. Μ ^ (Comparative Example 1 3) ^ Without using ultrasonic waves, use the same formula as in Example 19 • 59 · (Please read the precautions on the back before filling this page) This paper size applies Chinese national standards (CNS) A4 specification (210 X 297 mm) 491814 A7 B7 V. Description of the invention (57) The result of the zeolite reaction '57 The reaction product obtained without washing was confirmed by X-ray diffraction method Construct the result, and The conversion of zeolite was found in the depth of the pores. The cation exchange capacity of this faujasite was 2 10 cmol (+) kg 1. (Example 20) ^ The ratio of silicon to aluminum produced by Kagoshima was automatically purchased. About 3. 2 volcanic glass was crushed. 20 g of pulverized volcanic glass and 5 g of aluminum dross (provided by the Light Metal Association of Japan) were placed in the reaction container used in Example 1. '2 N hydrogen / sodium oxide was added above it. After 200 ml of the aqueous solution was closed, a 600 W, 25 kHz ultrasonic wave was applied, and the internal temperature was heated to 90 ° C with saturated steam. After remaining in this state for 12 hours, 'the reaction product inside was taken out, and the structure of the reaction product was confirmed by X-ray diffraction method without washing the reaction product. It was found that phillipsite was also formed to the depth of the pores. . The cation exchange capacity of this phillipsite is 390 cmol (+) kg —]. (Comparative Example 14) The result of zeolite reaction using the same method as in Example 20 without applying ultrasonic waves to the soil was confirmed by the X-ray diffraction method under the reaction product obtained without washing with water. As a result of its construction, no zeolite conversion was found deep within the pores. The cation exchange capacity of this phillipsite is 280 cmol (+) kg-1 〇-60-(Please read the precautions on the back before filling this page) This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297) (Mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 491814 A7 B7 V. Description of the Invention (58) (Example 21) The content of amorphous aluminum silicate is 80% and the ratio of silicon to aluminum is about 2. 20 g of incineration ash from municipal waste (manufactured by the Tokyo Metropolitan Municipal Sweeping Bureau Incineration Plant) and 10 g of glass powder (manufactured by West Japan Environmental Development Cooperative) were placed in the reaction container used in Example 1, and Join from above 3. 240 ml of a 5N sodium hydroxide aqueous solution, closed the lid, and then applied a 600 W, 2 5 kHz ultrasonic wave while heating to a temperature of 80 to 90 ° C with saturated steam. After keeping this state for 20 hours, the internal reaction product was taken out, and excess sodium hydroxide in the reaction product was washed with water, and dried to obtain a powder. As a result of confirming the powder structure by the X-ray diffraction method, it was found that phillipsite was also formed to the depth of the pores. The cation exchange capacity of this phillipsite is 370 cmol (+) kg — 1. (Comparative Example 15). The results of the zeolite reaction were performed using the same method as in Example 21 without applying ultrasonic waves, and the results of the structure were confirmed by X-ray diffraction method under the reaction product obtained without washing, No zeolite conversion was found deep within the pores. The cation exchange capacity of this phillipsite is 210 cmol (+) kg-10 (Example 22) The content of amorphous aluminum silicate is 80% and the ratio of silicon to aluminum is about 2. 0g of municipal waste incineration ash (manufactured by the municipal incineration plant of Machida City, Tokyo) 20g and 20g of glass powder (manufactured by the West Japan Environment Development Cooperative Combination) put into this paper standard applicable to China National Standard (CNS) A4 (210 X 297 mm) -61-ϋ ϋ n ϋ nnni · — ϋ I 1 ^ 1 · Bmmmm I 1 n · 1 an 1 δ, I ϋ ϋ i ^ in ϋ n I (Please read the notes on the back before filling (This page) 491814 A7 B7 V. Description of the invention (59) In the reaction vessel used in Example 1, add 3. 240ml of 5N sodium hydroxide aqueous solution. After closing the lid, apply 600W, 2 5kHz ultrasonic waves, and then heat the internal temperature to 80 ~ 90 ° C with saturated steam. After keeping this state for 30 hours, the internal reaction product was taken out, and the excess sodium hydroxide in the reaction product was washed with water, and dried to obtain a powder. As a result of confirming the structure of the powder by the \ line diffraction method, it was found that faujasite was also formed to the depth of the pores. The cation exchange capacity of this faujasite is 240 cmol (+) kg — 1. (Comparative Example 16) The results of performing the zeolization reaction using the same method as in Example 22 without applying ultrasonic waves were confirmed by X-ray diffraction method under the reaction product obtained without washing with water. As a result of the construction, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this faujasite is 1 90 cmol (+) kg — 10 (Example 23) The content of amorphous aluminum silicate is 80% and the ratio of silicon to aluminum is about 2. 20 g of incineration ash from municipal waste (manufactured by the Municipal Sweeping Bureau Incineration Plant of Machida City, Tokyo) and 20 g of glass powder (manufactured by Nippon Environment Development Co., Ltd.) were placed in the reaction container used in Example 4, and then Join 3. After 240 ml of a 5N aqueous sodium hydroxide solution, 600 W, 25 kHz ultrasonic waves are applied, and the internal temperature is heated to -62 by infrared radiation from an infrared radiation device (manufactured by Rigaku Corporation, vertical infrared furnace). -(Please read the precautions on the back before filling in this page) The paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 491814 A7 ____B7___ 5. Description of the invention (60) up to 80 ~ 90 ° C . After keeping this state for 20 hours, the internal reaction product was taken out, and excess sodium hydroxide in the reaction product was washed with water, and dried to obtain a powder. As a result of confirming the powder structure by the X-ray diffraction method, it was found that phillipsite was also formed to the depth of the pores. The cation exchange capacity of this phillipsite is 360 cmol (+) kg — 1. (Comparative Example 17) I The same method as in Example 23 was used without applying ultrasonic waves. As a result of the zeolization reaction, the excess of the obtained reaction product was obtained. The sodium was washed with water and dried naturally to obtain a powder. As a result of confirming the powder structure by the X-ray diffraction method, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this phillipsite is 290 cmol (+ X kg — 1.) (Example 24) I The content of amorphous aluminum silicate is 80% and the ratio of silicon to aluminum is about 2. 0-1] Municipal waste incineration ash (manufactured by the Municipal Sweep Bureau Incineration Plant, Machida, Tokyo) 20g j I and i0g of glass powder (made by the West Japan Environment Development Cooperative Combination) were put in] Used in Example 4 In the reaction vessel, add 3. After 240 ml of a 5N sodium hydroxide aqueous solution, a 600 W, 25 kHz ultrasonic wave was applied, and the internal temperature reached 80 by microwave heating using a microwave heater (Mitachi Hitachi, Ltd., MRH-4). Up to 90 ° C. After keeping it in this state for 20 hours, take out the internal reaction product, and then wash the excess sodium hydroxide in the reaction product with water. Naturally I--II--I · 1111111 ^ '— — — — — 1 — (Please read the notes on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) · 63 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 491814 A7 ___—_____ B7 V. Description of the invention (61) The powder is obtained after drying. As a result of confirming the powder structure by the X-ray diffraction method, it was found that phillipsite was also formed to the depth of the pores. The cation exchange capacity of this phillipsite was 380 cmol (+) kg — (Comparative Example 18). As a result of carrying out the zeolite reaction in the same manner as in Example 24, excess sodium hydroxide in the obtained reaction product was washed with water, and dried to obtain a powder. As a result of confirming the powder structure by the X-ray diffraction method, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this crocodile zeolite is 260 c m ο 1 (+) kg — 1. (Example 25) The content of amorphous aluminum silicate was 80% and the ratio of silicon to aluminum was about 2. 20 g of incineration ash from municipal waste (manufactured by the Municipal Sweeping Bureau Incineration Plant of Machida City, Tokyo) and 20 g of glass powder (manufactured by Nippon Environment Development Co., Ltd.) were placed in the reaction container used in Example 4 After adding 240 ml of a 3 · 5 N aqueous sodium hydroxide solution, a 600 W, 25 kHz ultrasonic wave was applied, and an electromagnetic induction heater (National Z-P57, manufactured by Matsushita Electric Industrial Co., Ltd.) was applied to heat the internal The temperature reaches 80 ~ 90t. After keeping this state for 20 hours, the internal reaction product was taken out, and then excess sodium hydroxide in the reaction product was washed with water, and dried to obtain a powder. The results of this powder structure were confirmed by the X-ray diffraction method, and it was found that phillipsite was also formed to the depth of the pores. This calcium cross-boiler paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) -64- -------- Order --------- Line (Please read the back first Please pay attention to this page, please fill in this page) Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 491814 A7 _ B7 V. Description of the invention (62) The cation exchange capacity of the stone is 330 cmol (+) kg — 1. (Comparative Example 19) As a result of performing a zeolite reaction using the same method as in Example 25 without applying ultrasonic waves, the excess sodium hydroxide in the obtained reaction product was washed with water and naturally A powder was obtained after drying. As a result of confirming the powder structure by the X-ray diffraction method, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this cross-zeolite is 2 0 0 c m ο 1 (+) kg — 1. (Example 26) The content of amorphous aluminum silicate was 80% and the ratio of silicon to aluminum was about 2. 20 g of incineration ash from municipal waste (manufactured by the Municipal Sweep Bureau Incineration Plant, Machida, Tokyo) and 5 g of glass powder (manufactured by Nippon Environmental Development Cooperative Group) were placed in the reaction container used in Example 1, and then 200ml of 4N sodium hydroxide aqueous solution was added above, and after closing the lid, while applying ultrasonic waves of 600W and 25kHz, it was heated by saturated steam pressure until the internal temperature reached 120 ° C. After keeping this state for 5 hours, the vapor was extracted to return to atmospheric pressure, and then the reaction product inside was taken out. Without washing the reaction product with water, the structure was confirmed by the X-ray diffraction method, and it was found that phillipsite was also formed to the depth of the pores. The cation exchange capacity of this phillipsite is 340cmol (+) kg— 1σ (Comparative Example 20). The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -65- ------ -! i # ------- 丨 Order ---- ^ ---- · -line- ♦-(Please read the notes on the back before filling out this page) 491814 A7 B7 V. Description of the invention (63 ) The results of zeolite reaction using the same method as in Example 26 without applying ultrasonic waves, and confirming the results of the structure by X-ray diffraction method under the reaction product obtained without washing, No zeolite conversion was found deep within the pores. The cation exchange capacity of this phillipsite is 210 cmol (+) kg-10 (Example 27) The content of amorphous aluminum silicate is 80% and the ratio of silicon to aluminum is about 2. 20 g of incineration ash from municipal waste (manufactured by the Municipal Sweeping Bureau Incineration Plant of Machida, Tokyo) and 5 g of glass powder (manufactured by Nippon Environmental Development Cooperative Group) were placed in the reaction container used in Example 8, and 200 ml of a 4N sodium hydroxide aqueous solution was added to the top, and after closing the lid, a supersonic wave of 600 W and 25 kHz was applied, and the internal temperature was heated to 120 ° C by saturated vapor and infrared radiation. After keeping this state for 5 hours, the vapor was extracted to return to atmospheric pressure, and then the internal reaction product was taken out. Without washing the reaction product with water, the structure was confirmed by X-ray diffraction, and it was found that the phillipsite and a small amount of hydroxy sodalite were also formed in the depth of the pores. The cation exchange capacity of this phillipsite and hydroxy sodalite is 360 cmol (+) kg to 10 (Example 28) .The content of amorphous aluminum silicate is 80% and the ratio of silicon to aluminum is about 2. 0g of municipal waste incineration ash (manufactured by the Municipal Sweeping Bureau Incineration Plant, Machida, Tokyo) 20g and 5g of glass powder (manufactured by the West Japan Environment Development Cooperative Combination) put in -66- (Please read the precautions on the back before filling in this Page) This paper size is in accordance with China National Standard (CNS) A4 (210 x 297 mm). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 491814 A7 B7 V. Description of the invention (64) The reaction container used in Example 9 In addition, a 4N sodium hydroxide aqueous solution of 200 m 1 was added from above, and after closing the lid, a 600 W, 25 kHz ultrasonic wave was applied, and heated to the inside by saturated steam and microwave heating. The temperature reaches 1 20t. After keeping this state for 5 hours, the steam was extracted to return to atmospheric pressure, and then the internal reaction product was taken out. Without washing the reaction product with water, the structure was confirmed by the X-ray diffraction method, and it was found that phillipsite was also formed deep in the pores. The anion exchange capacity of this phillipsite is 410 cmol (+) kg — 1. (Comparative Example 21) The results of zeolite reaction using the same method as in Example 28 were performed without applying ultrasonic waves. The reaction products obtained without washing were confirmed by X-ray diffraction method. As a result of the construction, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this phillipsite is 3 20 cmol (+) kg ~ 1 ° (Example 29) The content of amorphous aluminum silicate is 80% and the ratio of silicon to aluminum is about 2. 20 g and 5 g of glass powder (manufactured by Nippon Environmental Development and Cooperative Development Co., Ltd.) of incineration ash (made by Machida City Sweeping Bureau Incineration Plant, Tokyo) was placed in the reaction container used in Example 10 A 4 N sodium hydroxide aqueous solution of 200 m 1 was added to the top, and after closing the lid, a 600 W, 25 kHz ultrasonic wave was applied, and the interior was heated by saturated steam and the electric current of an electromagnetic induction heater. The temperature reaches 1 20 t. Keep in this state 5 small -------------------- order --------- line (Please read the precautions on the back before filling this page) This Paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -67- 491814 A7 B7 V. Description of invention (65) (Please read the precautions on the back before filling this page) After taking out the steam to recover After reaching atmospheric pressure, the reaction product inside was taken out. Without washing the reaction product with water, the structure was confirmed by the X-ray diffraction method, and it was found that crocodite was also formed to the depth of the pores. This inscription Cross zeolite has a cation exchange capacity of 390 cmol (+) kg — 1. (Example 30) The content of amorphous aluminum silicate was 80% and the ratio of silicon to aluminum was about 2. 20 g of incineration ash from municipal waste (manufactured by the incineration plant of Machida City, Tokyo) and 5 g of waste diatomite (manufactured by Kirin Barley Co., Ltd.) were placed in the reaction container used in Example Then, 200 ml of a 4N sodium hydroxide aqueous solution was added from above, and after closing the lid, a supersonic wave of 600 W and 25 kHz was applied, and the internal temperature was heated to 80 to 90 ° C by saturated steam. After keeping this state for 20 hours, the internal reaction product was taken out. The structure of the reaction product was confirmed by X-ray diffraction without washing the reaction product with water. It was found that phillipsite was also formed to the depth of the pores. The cation exchange capacity of this phillipsite is 380 cmol (+) kg]. Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (Comparative Example 22) The results of the zeolite reaction using the same method as in Example 30 without applying ultrasonic waves were generated by the reaction obtained without washing. The structure was confirmed by X-ray diffraction method under the object, and no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this phillipsite is 270 cmol (+) kg — 1 0 -68- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 491814 A7 ___ B7____ 5. Description of the invention (66 ) (Example 31)
將非結晶性砂酸鋁之含有量爲8 0 %而砂銘比約2.0之 都市垃圾的焚化灰（東京都町田市淸掃局焚化場製）2 0 g 以及5 g的廢砂藻土（麒麟麥酒股份有限公司取手工場製） 放入於實施例4中所使用之反應容器中，再由其上方加入 4N的氫氧化鈉水溶液200ml，關閉蓋子後，一邊施以600W 、25kHz之超音波，一邊藉由紅外線放射裝置（理學電機 股份有限公司製，縱型紅外線爐）之紅外線放射來加熱至 內部的溫度到達80〜90 °C爲止。保持此狀態20小時後， 取出內部的反應生成物。在不水洗此反應生成物下，藉由 X線繞射法確認其構造的結果，發現至細孔的深處亦生成 有鈣，十字沸石。此鈣十字沸石的陽離子交換容量爲370 cmol ( + ) kg Γ 1 〇 (實施例32 ) 將非結晶性矽酸鋁之含有量爲80 %而矽鋁比約2.0之 都市垃圾的焚化灰（東京都町田市淸掃局焚化場製）20g ； 以及5 g的廢矽藻土（麒麟麥酒股份有限公司取手工場製） 放入於實施例4中所使用之反應容器中，再由其上方加入 4N的氫氧化鈉水溶液200ml後，一邊施以600W、25kHz之 : 超音波，一邊藉由微波加熱器（股份有限公司日立製作所 : 製，MRH — 4型）之微波加熱來加熱至內部的溫度到達80 : 〜90 °C爲止。保持此狀態20小時後，取出內部的反應生成 -69- (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） 經濟部智慧財產局員工消費合作社印製 491814 A7 __________ B7 五、發明說明（67) 物。在不水洗此反應生成物下，藉由X線繞射法確認其構 造的結果，發現至細孔的深處亦生成有鈣十字沸石。此鈣 十字沸石的陽離子父換容量爲320 cmol ( + ) kg1。 (比較例23 ) 在不施以超音波的條件下，使用與實施例3 2相同的方 法進行沸石化反應的結果，於不水洗被得到之反應生成物 下，藉由X線繞射法確認其構造的結果，並沒有在細孔的 深處發現沸石的轉換。此銘十字沸石的陽離子交換容量爲 260 cmol ( + ) kg — 1。 (實施例33 ) /將非結晶性矽酸鋁之含有量爲80 %而矽鋁比約2.0之 都市垃圾的焚化灰（東京都町田市淸掃局焚化場製）20g 以及5 g的廢矽藻土（麒麟麥酒股份有限公司取手工場製） 放入於實施例4中所使用之反應容器中，再由其上方加入 4N的氫氧化鈉水溶液200ml後，一邊施以600W、25kHz之 超音波，一邊通電於電磁感應加熱器（松下電器產業股份 有限公司製，National Z - P57 )來加熱至內部的溫度到達 80〜90 °C爲止。保持此狀態20小時後，取出內部的反應生 成物。在不水洗此反應生成物下，藉由X線繞射法確認其 構造的結果，發現至細孔的深處亦生成有鈣十字沸石。此 錦十字沸石的陽離子交換容量爲340 cmol ( + ) kg — 1。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -70- --------------------訂--------- (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 491814 A7 B7 五、發明說明（68) (實施例34 ) 將非結晶性矽酸鋁之含有量爲80 %而矽鋁比約2.0之 都市垃圾的焚化灰（東京都町田市淸掃局焚化場製）20g 以及5g的鋁渣滓（由社團法人輕金屬協會提供）放入於實 施例1中所使用之反應容器中，再由其上方加入4N的氫氧 化鈉水溶液200ml，關閉蓋子後，一邊施以600W、25kHz 之超音波，一邊藉由飽和蒸氣來加熱至內部的溫度到達80 〜90 °C爲止。保持此狀態20小時後，取出內部的反應生成 物。在不水洗此反應生成物下，藉由X線繞射法確認其構 造的結果，發現至細孔的深處亦生成有羥基方鈉石。此羥 基方鈉石的陽離子交換容量爲480 cmol ( + ) kg — 1。 (比較例2 4 ) 在不施以超音波的條件下，使用與實施例34相同的方 法進行沸石化反應的結果，於不水洗被得到之反應生成物 下，藉由X線繞射法確認其構造的結果，並沒有在細孔的 深處發現沸石的轉換。此羥基方鈉石的陽離子交換容量爲 320 cmol ( + ) kg _ 1。 (實施例3 5 ) 將非結晶性矽酸鋁之含有量爲80 %而矽鋁比約2.0之 都市垃圾的焚化灰（東京都町田市淸掃局焚化場製）20g 以及5g的鋁渣滓（由社團法人輕金屬協會提供）放入於實 施例4中所使用之反應容器中，再由其上方加入4N的氫氧 --------------------訂---------線 (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） -71 - 491814 A7 ___B7_ 五、發明說明（69) 化鈉水溶液200ml後，一邊施以600W、25kHz之超音波’ 一邊藉由紅外線放射裝置（理學電機股份有限公司製’縱 型紅外線爐）之紅外線放射來加熱至內部的溫度到達80〜 90 °C爲止。保持此狀態20小時後，取出內部的反應生成物 。在不水洗此反應生成物下，藉由X線繞射法確認其構造 的結果，發現至細孔的深處亦生成有羥基方鈉石。此羥基 方鈉石的陽離子交換容量爲480 cmol ( + ) kg — 1。 (實施例36 ) 將非結晶性矽酸鋁之含有量爲80 %而矽鋁比約2.0之 都市垃圾的焚化灰（東京都町田市淸掃局焚化場製）20g 以及5g的鋁渣滓（由社團法人輕金屬協會提供）放入於實 施例4中所使用之反應容器中，再由其上方加入4N的氫氧 化鈉水溶液200ml後，一邊施以600W、25kHz之超音波’ 一邊藉由微波加熱器（股份有限公司日立製作所製，MRH 一 4型）之微波加熱來加熱至內部的溫度到達80〜90 °C爲 止。保持此狀態20小時後，取出內部的反應生成物。在不 水洗此反應生成物下，藉由X線繞射法確認其構造的結果 ，發現至細孔的深處亦生成有羥基方鈉石。此羥基方鈉石 的陽離子交換容量爲480 cmol ( + ) kg — 1。 (比較例25 ) 在不施以超音波的條件下，使用與實施例36相同的方 法進行沸石化反應的結果，於不水洗被得到之反應生成物 --------------裝—— (請先閱讀背面之注意事項再填寫本頁) 入一0- --線· 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -72- 經濟部智慧財產局員工消費合作社印製 491814 A7 _ _ B7 五、發明說明（70) 下，藉由X線繞射法確認其構造的結果，並沒有在細孔的 深處發現沸石的轉換。此羥基方鈉石的陽離子交換容量爲 310 cmol ( + ) kg 1〇 (實施例37 ) 將非結晶性矽酸鋁之含有量爲80 %而矽鋁比約2.0之 都市垃圾的焚化灰（東京都町田市淸掃局焚化場製）20g 以及5 g的錦渣淳（由社團法人輕金屬協會提供）放入於實 施例4中所使用之反應容器中，再由其上方加入4N的氫氧 化鈉水溶液200ml後，一邊施以600W、25kHz之超音波， 一邊通電於電磁感應加熱器（松下電器產業股份有限公司 製，National Z — P57 )來加熱至內部的溫度到達80〜90 °C爲止。保持此狀態20小時後，取出內部的反應生成物。 在不水洗此反.應生成物下，藉由X線繞射法確認其構造的 結果，發現至細孔的深處亦生成有羥基方鈉石。此羥基方 鈉石的陽離子交換容量爲3 2 0 c m ο 1 ( + ) k g — 1。 (實施例3 8 ) 將非結晶性矽酸鋁之含有量爲95 %而矽鋁比約2.5之 飛灰（電源開發股份有限公司松浦發電所製，由飛灰協會 提供）20g以及10g的玻璃粉末（西日本環境開發協同組合 製）充分混合後，放入於實施例1中所使用之反應容器中 ，再由其上方加入3.5N的氫氧化鈉水溶液240ml，關閉蓋 子後，一邊施以600W、25kHz之超音波，一邊藉由飽和蒸 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -73- --------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 491814 A7 B7 五、發明說明（71) (請先閱讀背面之注意事項再填寫本頁) 氣來加熱至內部的溫度到達80〜90 °C後，反應30小時。 反應後，以水將過剩的氫氧化鈉洗淨，自然乾燥後得到粉 末。藉由X線繞射法確認此粉末構造的結果，發現至細孔 的深處亦生成有八面沸石。此八面沸石的陽離子交換容量 爲 3 60 cmol ( + ) kg — 1 〇 (比較例26 ) 在不施以超音波的條件下，使用與實施例38相同的方 法進行沸石化反應的結果，將被得的反應生成物中之過剩 的氫氧化鈉以水洗淨，自然乾燥後得到粉末。藉由X線繞 射法確認此粉末構造的結果，並沒有在細孔的深處發現沸 石的轉換。此八面沸石的陽離子交換容量爲240 cmol ( + )kg - 1 。 (實施例39 ) 經濟部智慧財產局員工消費合作社印製 將非結晶性矽酸鋁之含有量爲95 %而矽鋁比約2.5之 飛灰（電源開發股份有限公司松浦發電所製，由飛灰協會 提供）20g以及5g的玻璃粉末（西日本環境開發協同組合 製）混合，使其矽鋁比約成爲4後，再放入於實施例1中所 使用之反應容器中，然後由其上方加入4N的氫氧化鈉水溶 液200ml，關閉蓋子後，一邊施以600W、25kHz之超音波 ，一邊藉由飽和蒸氣加壓來加熱至內部的溫度到達1 2(TC 爲止。保持此狀態1小時後，抽出蒸氣恢復至大氣壓’然 後取出內部的反應生成物。在不水洗此反應生成物下，藉 -74- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 491814 A7 B7 五、發明說明（72) 由X線繞射法確認其構造的結果，發現至細孔的深處亦生 成有八面沸石。此八面沸石的陽離子交換容量爲310 cmol (+ ) kg — 1 。 (比較例27 ) 在不施以超音波的條件下，使用與實施例26相同的方 法進行沸石化反應的結果，於不水洗被得到之反應生成物 下，藉由X線繞射法確認其構造的結果，並沒有在細孔的 深處發現沸石的轉換。此八面沸石的陽離子交換容量爲3 1 0 cmol ( + ) kg 1 〇 (實施例40 ) ，將非結晶性矽酸鋁之含有量爲95 %而矽鋁比約2.5之 飛灰（電源開發股份有限公司松浦發電所製，由飛灰協會 提供）20g以及5g的玻璃粉末（西日本環境開發協同組合 製）混合，使其矽鋁比約成爲4後，再由其上方加入4N的 氫氧化鈉水溶液200ml，關閉蓋子後，一邊施以600W、 2 5kHz之超音波，一邊藉由飽和蒸氣加壓來加熱至內部的溫 度到達200 °C爲止。保持此狀態0.5小時後，抽出蒸氣恢復 至大氣壓，然後取出內部的反應生成物。在不水洗此反應 生成物下，藉由X線繞射法確認其構造的結果’發現至細 孔的深處亦生成有八面沸石。此八面沸石的陽離子交換容 量爲 300 cmol ( + ) kg 一 1。 -75- (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） 491814 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明（73) (比較例28 ) 在不施以超音波的條件下，使用與實施例40相同的方 法進行沸石化反應的結果，於不水洗被得到之反應生成物 下，藉由X線繞射法確認其構造的結果，並沒有在細孔的 深處發現沸石的轉換。此八面沸石的陽離子交換容量爲220 cmol ( + ) kg 一 1 〇 (實施例41 ) 將非結晶性矽酸鋁之含有量爲95 %而矽鋁比約2.5之 飛灰（電源開發股份有限公司松浦發電所製，由飛灰協會 提供）20g以及5g的鋁渣滓（由社團法人輕金屬協會提供 )放入於實施例1中所使用之反應容器中，使其矽鋁比約 成爲2後，再由其上方加入4N的氫氧化鈉水溶液200ml， 關閉蓋子後，一邊施以600 W、25 kHz之超音波，一邊藉由 飽和蒸氣加壓來加熱至內部的溫度到達1 20 °C爲止。保持 此狀態1小時後，抽出蒸氣恢復至大氣壓，然後取出內部 的反應生成物。在不水洗此反應生成物下，藉由X線繞射 法確認其構造的結果，發現至細孔的深處亦生成有羥基方 鈉石。此羥基方鈉石的陽離子交換容量爲470 cmol ( + ) kg — 1。 (比較例29 ) 在不施以超音波的條件下，使用與實施例4 1相同的方 法進行沸石化反應的結果，於不水洗被得到之反應生成物 (請先閱讀背面之注意事項再填寫本頁) 丨· tr----I ——----------------------- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -76- 491814 經濟部智慧財產局員工消費合作社印製 A7 —__B7 ___ 五、發明說明（74) 下’藉由X線繞射法確認其構造的結果，並沒有在細孔的 深處發現沸石的轉換。此羥基方鈉石的陽離子交換容量爲 260 cmol ( + ) kg 一 1 〇 (實施例42 ) 將50g的玻璃粉末（西日本環境開發協同組合製）混 合於50g的垃圾固態化燃料的焚化灰（由東京都町田市淸 掃局焚化場提供）中，然後放入實施例1的反應容器中， 再添加3.5N的氫氧化鈉水溶液240ml於此容器中，關閉蓋 子後，一邊施以600 W、25kHz之超音波，一邊藉由飽和蒸 氣來加熱至內部的溫度到達90〜95 °C爲止。保持此狀態5 小時後，以水將反應生成物中之過剩的氫氧化鈉洗淨，自 然乾燥後得到粉末。藉由X線繞射法確認此粉末構造的結 果，發現至細孔的深處亦生成有鈣十字沸石。此鈣十字沸 石的陽離子交換容量爲360 cmol ( + ) kg — 1。 (比較例3 1 ) 在不施以超音波的條件下，使用與實施例42相同的方 法進行沸石化反應的結果，將被得到的反應生成物中之過 剩的氫氧化鈉以水洗淨，自然乾燥後得到粉末。藉由X線 繞射法確認此粉末構造的結果，並沒有在細孔的深處發現 沸石的轉換。此鈣十字沸石的陽離子交換容量爲210 cmol (+ ) kg - 1 。 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -77- -------^------------訂----^----線 (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 491814 A7 B7 五、發明說明（75) (實施例43 ) 將70g的廢矽藻土（麒麟麥酒股份有限公司取手工場 製）混合於30g的垃圾固態化燃料的焚化灰（由東京都町 田市淸掃局焚化場提供）中，然後放入實施例1的反應容 器中，再添加3.5N的氫氧化鈉水溶液240ml於此容器中， 關閉蓋子後，一邊施以600W、25 kHz之超音波，一邊藉由 飽和蒸氣來加熱至內部的溫度到達90〜95 °C爲止。保持此 狀態1 2小時後，以水將反應生成物中之過剩的氫氧化鈉洗 淨，自然乾燥後得到粉末。藉由X線繞射法確認此粉末構 造的結果，發現至細孔的深處亦生成有鈣十字沸石。此鈣 十字沸石的陽離子交換容量爲310 cmol ( + ) kg ~ 1。 (比較例32 ) 在不施以超音波的條件下，使用與實施例43相同的方 法進行沸石化反應的結果，將被得到的反應生成物中之過 剩的氫氧化鈉以水洗淨，自然乾燥後得到粉末。藉由X線 繞射法確認此粉末構造的結果，並沒有在細孔的深處發現 沸石的轉換。此鈣十字沸石的陽離子交換容量爲210 cmol (+ ) kg — 1。 (實施例44 ) 在藉由本發明之加熱反應管接觸來製造人工沸石的製 造裝置之反應管上設置超音波振動器（股份有限公司日本 精機製作所製，MODEL US _ 6GGT ) ’於原料混合物準備步驟 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -78- I ϋ ϋ n I n *l-i -ϋ ϋ «ϋ n · 1 ϋ n n I ϋ^OJ 1« ϋ n n ϋ 1 mmmme I (請先閱讀背面之注意事項再填寫本頁) 491814 A7 B7 i、發明說明（76) 裝置方面，將已粉碎之鹿耳島產且矽鋁比約3.2之火山玻璃 2 0kg與2N的氫氧化鈉水溶液200L相互混合，於下述的條 件下，使用人工沸石生成裝置來進行人工沸石的合成。 驗濃度：2N的氫氧化鈉水溶液 反應溫度：90T： 反應時間：1 2小時 超音波振動的頻率：25 kHz 反應終了後，藉由X線繞射法確認反應生成物構造的 結果，發現至細孔的深處亦生成有以鈣十字沸石爲主體之 物質。此以鈣十字沸石爲主體之物質的陽離子交換容量爲 410cmol ( + ) kg-1。 (比較例33 ) 在不施以超音波的條件下，使用與實施例44相同的方 法進行沸石化反應。藉由X線繞射法確認所得之反應生成 物構造的結果，並沒有在細孔的深處發現沸石的轉換。此 以鈣十字沸石爲主體之物質的陽離子交換容量爲280 cmol (+ ) kg —丨。 (實施例45 ) 在藉由本發明之加熱反應管接觸來製造人工沸石的製 造裝置之反應管上設置超音波振動器（股份有限公司日本 精機製作所製，MODEL US - 6G0T ) ’於原料混合物準備步驟 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) 經濟部智慧財產局員工消費合作社印製An incineration ash of municipal waste containing 80% of non-crystalline aluminum oxalate and a sand ratio of about 2.0 (manufactured by the incineration plant of Machida City, Tokyo) 20 g and 5 g of waste sand algal soil ( Kirin Barley Co., Ltd. (made by hand-made farm) was placed in the reaction container used in Example 4, and then 200ml of 4N sodium hydroxide aqueous solution was added from above. After closing the lid, a 600W, 25kHz ultrasonic wave was applied. It is heated by infrared radiation from an infrared radiation device (a vertical infrared furnace manufactured by Rigaku Electric Co., Ltd.) until the internal temperature reaches 80 to 90 ° C. After keeping this state for 20 hours, the internal reaction product was taken out. As a result of confirming the structure by X-ray diffraction without washing the reaction product with water, calcium and cross zeolite were also found to the depth of the pores. The cation exchange capacity of this phillipsite is 370 cmol (+) kg Γ 1 0 (Example 32). Incineration ash (Tokyo) of non-crystalline aluminum silicate with a content of 80% and a silicon to aluminum ratio of about 2.0 20 g of Machida City Sweeping Bureau Incineration Plant); and 5 g of waste diatomaceous earth (manufactured by Kirin Barley Co., Ltd.) were placed in the reaction vessel used in Example 4, and 4N was added from above After applying 200ml of sodium hydroxide aqueous solution, while applying 600W, 25kHz: ultrasonic waves, the microwave was heated by a microwave heater (Hitachi Manufacturing Co., Ltd., MRH-4 type) to the internal temperature of 80 : Up to ~ 90 ° C. After keeping in this state for 20 hours, take out the internal reaction to generate -69- (Please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Wisdom of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Property Bureau 491814 A7 __________ B7 V. Description of Invention (67). Without washing the reaction product with water, the structure was confirmed by the X-ray diffraction method, and it was found that phillipsite was also formed to the depth of the pores. The cation parent exchange capacity of this phillipsite is 320 cmol (+) kg1. (Comparative Example 23) The results of performing the zeolite reaction using the same method as in Example 32 without applying ultrasonic waves were confirmed by the X-ray diffraction method under the reaction product obtained without washing with water. As a result of its construction, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this Ming Zeolite is 260 cmol (+) kg — 1. (Example 33) / 20 g of waste incineration ash (manufactured by the municipal incineration plant of Machida City, Tokyo) with an amorphous silicon silicate content of 80% and an aluminum-silicon ratio of about 2.0 and 5 g of waste silicon Algal soil (manufactured by Kirin Barley Co., Ltd.) was placed in the reaction container used in Example 4, and 200 ml of a 4N sodium hydroxide aqueous solution was added from above, and a 600 W, 25 kHz ultrasonic wave was applied, While energizing an electromagnetic induction heater (National Z-P57, manufactured by Matsushita Electric Industrial Co., Ltd.), heating was performed until the internal temperature reached 80 to 90 ° C. After keeping this state for 20 hours, the internal reaction product was taken out. The structure of the reaction product was confirmed by X-ray diffraction without washing the reaction product with water. It was found that phillipsite was also formed to the depth of the pores. The cation exchange capacity of this zeolite is 340 cmol (+) kg — 1. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -70- -------------------- Order ------- -(Please read the notes on the back before filling out this page) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 491814 A7 B7 V. Description of the invention (68) (Example 34) The content of non-crystalline aluminum silicate 20 g of incineration ash (manufactured by the Municipal Sweeping Bureau Incineration Plant, Machida City, Tokyo) of 80% and a silicon-to-aluminum ratio of about 2.0 g and 5 g of aluminum dross (provided by the Japan Light Metal Association) were used in Example In a reaction vessel, 200 ml of a 4N sodium hydroxide aqueous solution was added from above. After closing the lid, a 600 W, 25 kHz ultrasonic wave was applied, and the internal temperature was heated to 80 to 90 ° C with saturated steam. . After keeping this state for 20 hours, the internal reaction product was taken out. The structure of the reaction product was confirmed by X-ray diffraction without washing the reaction product with water. It was found that hydroxysodalite was also formed to the depth of the pores. The cation exchange capacity of this hydroxy sodalite is 480 cmol (+) kg — 1. (Comparative Example 2 4) The results of performing the zeolite reaction using the same method as in Example 34 without applying ultrasonic waves were confirmed by the X-ray diffraction method under the reaction product obtained without washing. As a result of its construction, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this hydroxy sodalite is 320 cmol (+) kg _ 1. (Example 3 5) 20 g of incineration ash (manufactured by the Municipal Sweeping Bureau Incineration Plant of Machida City, Tokyo) containing 80% of non-crystalline aluminum silicate and 80% silicon-aluminum ratio and 5 g of aluminum dross ( (Provided by the Association of Light Metals), put it into the reaction container used in Example 4, and then add 4N hydrogen and oxygen from the top -------------------- Order --------- line (please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -71-491814 A7 ___B7_ 5 Explanation of the invention (69) After 200ml of sodium sulfide aqueous solution is applied, 600W, 25kHz ultrasonic waves are applied while heating to the internal temperature by infrared radiation from an infrared radiation device ('Vertical Infrared Furnace' manufactured by Rigaku Electric Co., Ltd.). It reaches 80 ~ 90 ° C. After keeping this state for 20 hours, the internal reaction product was taken out. As a result of confirming the structure by X-ray diffraction without washing the reaction product with water, it was found that hydroxysodalite was also formed to the depth of the pores. The cation exchange capacity of this hydroxy sodalite is 480 cmol (+) kg — 1. (Example 36) 20 g of incineration ash (manufactured by the Municipal Sweeping Bureau Incineration Plant of Machida City, Tokyo) containing 80% of amorphous aluminum silicate with a content of 80% of amorphous aluminum silicate and 5 g of aluminum dross (from (Provided by the Japan Light Metal Association) was placed in the reaction container used in Example 4, and 200 ml of a 4N sodium hydroxide aqueous solution was added from above, and a 600 W, 25 kHz ultrasonic wave was applied while a microwave heater was applied. (Hitachi Co., Ltd., MRH-4) manufactured by microwave heating until the internal temperature reaches 80 ~ 90 ° C. After keeping this state for 20 hours, the internal reaction product was taken out. The structure of the reaction product was confirmed by X-ray diffraction without washing the reaction product with water. It was found that hydroxysodalite was also formed to the depth of the pores. The cation exchange capacity of this hydroxy sodalite is 480 cmol (+) kg — 1. (Comparative Example 25) As a result of performing a zeolite reaction using the same method as in Example 36 without applying ultrasonic waves, the reaction product obtained without washing was washed with water ----------- --- Packing-(Please read the precautions on the back before filling this page) Enter a 0--line · This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -72- Economy Printed by the Ministry of Intellectual Property Bureau's Consumer Cooperative 491814 A7 _ _ B7 V. Description of the invention (70), the results of its structure were confirmed by X-ray diffraction method, and no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this hydroxy sodalite is 310 cmol (+) kg 1 0 (Example 37). Incineration ash (Tokyo) of non-crystalline aluminum silicate with a content of 80% and a silica-alumina ratio of about 2.0 20 g and 5 g of Kinzuna Jun (provided by the Japan Light Metal Association) were placed in the reaction vessel used in Example 4, and 4N sodium hydroxide was added from above. After 200 ml of the aqueous solution, a 600 W, 25 kHz ultrasonic wave was applied, and an electromagnetic induction heater (National Z-P57, manufactured by Matsushita Electric Industrial Co., Ltd.) was applied to heat until the internal temperature reached 80 to 90 ° C. After keeping this state for 20 hours, the internal reaction product was taken out. Without washing the reaction product with water, the structure was confirmed by the X-ray diffraction method, and it was found that hydroxysodalite was also formed to the depth of the pores. The cation exchange capacity of this hydroxy sodalite is 3 2 0 c m ο 1 (+) k g — 1. (Example 3 8) 20g and 10g of fly ash (made by Matsuura Power Generation Co., Ltd., produced by Power Supply Development Corporation Matsuura Power Generation Co., Ltd.) with a content of 95% of amorphous aluminum silicate and a silicon-alumina ratio of about 2.5 The powder (manufactured by Nippon Environment Development Co., Ltd.) was thoroughly mixed, and then placed in the reaction container used in Example 1. Then, 240 ml of a 3.5 N sodium hydroxide aqueous solution was added from above. After closing the lid, 600 W, Ultrasonic wave at 25kHz, while applying the standard of China National Standards (CNS) A4 (210 X 297 mm) by saturated steaming paper size -73- ------------------ --Order --------- line (please read the notes on the back before filling this page) 491814 A7 B7 V. Description of the invention (71) (please read the notes on the back before filling this page) Gas Come to heat until the internal temperature reaches 80 ~ 90 ° C, and react for 30 hours. After the reaction, the excess sodium hydroxide was washed with water and dried naturally to obtain a powder. As a result of confirming the powder structure by the X-ray diffraction method, it was found that faujasite was also formed to the depth of the pores. The cation exchange capacity of this faujasite was 3 60 cmol (+) kg — 10 (Comparative Example 26). The results of zeolite reaction using the same method as in Example 38 were performed without applying ultrasonic waves. The excess sodium hydroxide in the obtained reaction product was washed with water and dried naturally to obtain a powder. As a result of confirming the powder structure by the X-ray diffraction method, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this faujasite is 240 cmol (+) kg-1. (Example 39) The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed a fly ash with an amorphous aluminum silicate content of 95% and a silicon-aluminum ratio of about 2.5 (manufactured by Songpu Power Generation Co., Ltd. of Power Development Co., Ltd. Provided by the Ash Association) 20g and 5g of glass powder (manufactured by Nippon Environment Development Co., Ltd.) are mixed so that the silicon-aluminum ratio becomes about 4, and then placed in the reaction container used in Example 1, and then added from above 200ml of 4N sodium hydroxide aqueous solution. After closing the lid, apply 600W, 25kHz ultrasonic waves, and pressurize with saturated steam to increase the internal temperature to 12 (TC. Keep in this state for 1 hour, draw out Return the vapor to atmospheric pressure 'and take out the internal reaction product. Without washing the reaction product with water, borrow -74- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 491814 A7 B7 V. Explanation of the invention (72) As a result of confirming the structure by the X-ray diffraction method, it was found that faujasite was also formed to the depth of the pores. The cation exchange capacity of this faujasite was 310 cmol (+) kg — 1 (Comparative Example 27) As a result of performing a zeolite reaction using the same method as in Example 26 without applying ultrasonic waves, the reaction product obtained without washing was confirmed by X-ray diffraction method. As a result of the structure, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this faujasite was 3 1 0 cmol (+) kg 1 0 (Example 40). 20g and 5g glass powder (made by West Japan Environmental Development Cooperative Combination) of fly ash (produced by Matsuura Power Generation Co., Ltd. Power Supply Development Co., Ltd., supplied by Fly Ash Association) with a content of 95% and a silicon-alumina ratio of 2.5 After the aluminum ratio becomes approximately 4, 200 ml of a 4N sodium hydroxide aqueous solution is added from above. After closing the lid, a 600 W, 25 kHz ultrasonic wave is applied, and the internal temperature is heated to 200 with saturated steam pressure. Up to ° C. After maintaining this state for 0.5 hours, extract the steam to return to atmospheric pressure, and then take out the internal reaction product. Without washing the reaction product, confirm the structure by X-ray diffraction method. Faujasite is also formed in the depth of the pores. The cation exchange capacity of this faujasite is 300 cmol (+) kg-1. -75- (Please read the precautions on the back before filling this page) This paper size applies China National Standard (CNS) A4 Specification (210 X 297 mm) 491814 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (73) (Comparative Example 28) Without ultrasonic waves, As a result of carrying out the zeolite reaction using the same method as in Example 40, the structure of the reaction product obtained without being washed with water was confirmed by the X-ray diffraction method, and no zeolite was found in the depth of the pores. Conversion. This faujasite zeolite has a cation exchange capacity of 220 cmol (+) kg-10 (Example 41). The content of non-crystalline aluminum silicate is 95% and the fly ash content is about 2.5. 20g and 5g of aluminum dross (provided by the Fly Ash Association) provided by the company's Matsuura Power Plant (provided by the Light Metal Association of Japan) were placed in the reaction vessel used in Example 1 so that the silicon-to-aluminum ratio was approximately 2. Then, 200 ml of 4N sodium hydroxide aqueous solution was added from above, and after closing the lid, a supersonic wave of 600 W, 25 kHz was applied, and the internal temperature was heated to 120 ° C by pressurizing with saturated steam. After keeping this state for 1 hour, the vapor was extracted to return to atmospheric pressure, and then the reaction product inside was taken out. As a result of confirming the structure by X-ray diffraction without washing the reaction product with water, it was found that hydroxysodalite was also formed to the depth of the pores. The cation exchange capacity of this hydroxy sodalite is 470 cmol (+) kg — 1. (Comparative Example 29) The results of the zeolite reaction were carried out using the same method as in Example 41 without applying ultrasonic waves, and the reaction product obtained was not washed with water (please read the precautions on the back before filling (This page) 丨 · tr ---- I --------------------------- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) -76- 491814 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 —__ B7 ___ V. Description of the invention (74) The result of confirming its structure by X-ray diffraction method is not in the fine holes Depth of zeolite was found in the depths. The cation exchange capacity of this hydroxy sodalite is 260 cmol (+) kg-10 (Example 42). 50 g of glass powder (manufactured by Nippon Environmental Development Co., Ltd.) is mixed with 50 g of incinerated ash (from (Provided by the Incineration Plant, Sweeping Bureau, Machida, Tokyo), and then placed in the reaction container of Example 1. Then, 240 ml of a 3.5 N sodium hydroxide aqueous solution was added to this container. After closing the lid, 600 W, 25 kHz was applied. The ultrasonic wave is heated by saturated steam until the internal temperature reaches 90 to 95 ° C. After remaining in this state for 5 hours, excess sodium hydroxide in the reaction product was washed with water and dried naturally to obtain a powder. The results of this powder structure were confirmed by the X-ray diffraction method, and it was found that phillipsite was also formed to the depth of the pores. The cation exchange capacity of this calcite is 360 cmol (+) kg — 1. (Comparative Example 31) As a result of performing a zeolite reaction using the same method as in Example 42 without applying ultrasonic waves, the excess sodium hydroxide in the obtained reaction product was washed with water. A powder was obtained after natural drying. As a result of confirming the powder structure by the X-ray diffraction method, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this phillipsite is 210 cmol (+) kg-1. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -77- ------- ^ ------------ Order ---- ^- -Line (Please read the notes on the back before filling this page) Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 491814 A7 B7 V. Invention Description (75) (Example 43) 70g of waste diatomaceous earth (Kirin Ale Co., Ltd. (manufactured by the company) is mixed with 30g of incineration ash (provided by the Municipal Bureau of Sweeping Bureau, Machida City, Tokyo) and put into the reaction container of Example 1 and added 3.5N 240 ml of sodium hydroxide aqueous solution was placed in this container. After closing the lid, a supersonic wave of 600 W and 25 kHz was applied, and the internal temperature was heated to 90 to 95 ° C with saturated steam. After remaining in this state for 12 hours, excess sodium hydroxide in the reaction product was washed with water and dried naturally to obtain a powder. As a result of confirming the powder structure by the X-ray diffraction method, it was found that phillipsite was also formed to the depth of the pores. The cation exchange capacity of this phillipsite is 310 cmol (+) kg ~ 1. (Comparative Example 32) As a result of performing a zeolite reaction using the same method as in Example 43 without applying ultrasonic waves, the excess sodium hydroxide in the obtained reaction product was washed with water, naturally A powder was obtained after drying. As a result of confirming the powder structure by the X-ray diffraction method, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this phillipsite is 210 cmol (+) kg — 1. (Example 44) An ultrasonic vibrator (manufactured by Nippon Seiki Co., Ltd., MODEL US _ 6GGT) was installed on a reaction tube of a manufacturing apparatus for manufacturing artificial zeolite by contacting the heated reaction tube of the present invention. This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) -78- I ϋ ϋ n I n * li -ϋ ϋ «ϋ n · 1 ϋ nn I ϋ ^ OJ 1« ϋ nn ϋ 1 mmmme I (Please read the precautions on the back before filling out this page) 491814 A7 B7 i. Description of the invention (76) For the device, the volcanic glass 20kg and 2N produced by Kagoshima, which has been crushed, has a ratio of 3.2 to silicon 200 L of a sodium hydroxide aqueous solution were mixed with each other, and artificial zeolite was synthesized using an artificial zeolite generating apparatus under the following conditions. Test concentration: 2N sodium hydroxide aqueous solution. Reaction temperature: 90T: Reaction time: 12 hours. Frequency of ultrasonic vibration: 25 kHz. After the reaction, the structure of the reaction product was confirmed by X-ray diffraction method. A substance mainly composed of phillipsite was also formed in the depth of the pores. The cation exchange capacity of this substance, mainly phillipsite, is 410 cmol (+) kg-1. (Comparative Example 33) The zeolite reaction was carried out in the same manner as in Example 44 without using ultrasonic waves. As a result of confirming the structure of the obtained reaction product by the X-ray diffraction method, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this substance, mainly phillipsite, is 280 cmol (+) kg — 丨. (Example 45) An ultrasonic vibrator (manufactured by Nippon Seiki Co., Ltd., MODEL US-6G0T) was installed on a reaction tube of a manufacturing apparatus for manufacturing artificial zeolite by contacting the heated reaction tube of the present invention. 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) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs
v一«»JI I I «1 ϋ I I ϋ I I i I tm— emt I I I an _1 an ϋ n n ϋ ϋ ϋ a^i I ϋρ ϋ I -79· 491814 經濟部智慧財產局員工消費合作社印製 A7 B7 i、發明說明（77) 裝置方面，將已粉碎之鹿耳島產且矽鋁比約3.2之火山玻璃 20kg與2Ν的氫氧化鈉水溶液200L相互混合，於下述的條 件下，使用人工沸石生成裝置來進行人工沸石的合成。 鹼濃度：2 N的氫氧化鈉水溶液 反應溫度：200 °C 反應時間：1小時 超音波振動的頻率：25 kHz 反應終了後，藉由X線繞射法確認反應生成物構造的 結果，發現至細孔的深處亦生成有以鈣十字沸石爲主體之 物質。此以鈣十字沸石爲主體之物質的陽離子交換容量爲 4 2 0 cmο1 ( + ) kg " 1 ° (比較例34 ) 在不施以超音波的條件下，使用與實施例45相同的方 法進行沸石化反應。藉由X線繞射法確認所得之反應生成 物構造的結果，並沒有在細孔的深處發現沸石的轉換。此 以鈣十字沸石爲主體之物質的陽離子交換容量爲3〇〇 cmol (+ ) kg 1 ， (實施例4 6 ) 在藉由本發明之加熱反應管接觸來製造人工沸石的製 造裝置之反應管上設置超音波振動器（股份有限公司日本 精機製作所製，MODEL US - 6GGT )，於原料混合物準備步驟 裝置方面’將非結晶性矽酸鋁之含有量爲80 %而矽錫比約 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -80- --------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 491814 經濟部智慧財產局員工消費合作社印製 A7 ___B7_______ 五、發明說明（78) 2.0之都市垃圾的焚化灰（東京都町田市淸掃局焚化場製） 20kg與2N的氫氧化鈉水溶液200L相互混合，於下述的條 件下，使用人工沸石生成裝置來進行人工沸石的合成。 鹼濃度：2N的氫氧化鈉水溶液 反應溫度：90 °C 反應時間：24小時 超音波振動的頻率：25 kHz 反應終了後，藉由X線繞射法確認反應生成物構造的 結果，發現至細孔的深處亦生成有以羥基方鈉石爲主體之 物質。此以羥基方鈉石爲主體之物質的陽離子交換容量爲 340 cmol ( + ) kg — 1 0 (比較例35 ) 在不施以·超音波的條件下，使用與實施例46相同的方 法進行沸石化反應。藉由X線繞射法確認所得之反應生成 物構造的結果，並沒有在細孔的深處發現沸石的轉換。此 以羥基方鈉石爲主體之物質的陽離子交換容量爲270 cmol (+ ) kg - 1 (實施例47 ) 在藉由本發明之加熱反應管接觸來製造人X沸石的製 造裝置之反應管上設置超音波振動器（股份有限公司日本 精機製作所製，MODEL旧-600T )，於原料混合物準備步驟 裝置方面’將非結晶性矽酸鋁之含有量爲95 %而矽鋁比約 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） - --------------------訂---------^ (請先閱讀背面之注意事項再填寫本頁) 491814 A7 ___ B7 五、發明說明（79) (請先閱讀背面之注意事項再填寫本頁) 2.5之飛灰（電源開發股份有限公司松浦發電所製’由飛灰 協會提供）20kg與4N的氫氧化鈉水溶液200L相互混合’ 於下述的條件下，使用人工沸石生成裝置來進行人工沸石 的合成。 鹼濃度：2N的氫氧化鈉水溶液 反應溫度：120 °C 反應時間：3小時 超音波振動的頻率：25 kHz 反應終了後，藉由X線繞射法確認反應生成物構造的 結果，發現至細孔的深處亦生成有以鈣十字沸石爲主體之 物質。此以鈣十字沸石爲主體之物質的陽離子交換容量爲 350 cmol ( + ) kg — 1 〇 (比較例3 6 .) 經濟部智慧財產局員工消費合作社印制衣 在不施以超音波的條件下，使用與實施例47相同的方 法進行沸石化反應。藉由X線繞射法確認所得之反應生成 物構造的結果，並沒有在細孔的深處發現沸石的轉換。此 以鈣十字沸石爲主體之物質的陽離子交換容量爲280 cmol (+ ) kg — 1 。 (實施例48 ) 在藉由本發明之加熱反應管接觸來製造人工沸石的製 造裝置之反應管上設置超音波振動器（股份有限公司日本 精機製作所製，MODEL US - 6GGT )，於原料混合物準備步驟 -82 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 491814 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（80) 裝置方面，將非結晶性矽酸鋁之含有量爲95 %而矽鋁比約 2.5之飛灰（電源開發股份有限公司松浦發電所製，由飛灰 協會提供）20kg，玻璃粉末（西日本環境開發協同組合製 )5kg以及4N的氫氧化鈉水溶液200L相互混合，於下述的 條件下，使用人工沸石生成裝置來進行人工沸石的合成。 鹼濃度：4 N的氫氧化鈉水溶液 反應溫度：200 °C 反應時間：5小時 超音波振動的頻率：25 kHz 反應終了後，藉由X線繞射法確認反應生成物構造的 結果，發現至細孔的深處亦生成有以八面沸石爲主體之物 質。此以八面沸石爲主體之物質的陽離子交換容量爲380 (比較例37 ) 在不施以超音波的條件下，使用與實施例4 8相同的方 法進行沸石化反應。藉由X線繞射法確認所得之反應生成 物構造的結果，並沒有在細孔的深處發現沸石的轉換。此 以八面沸石爲主體之物質的陽離子交換容量爲230 cmol ( + ) kg 1 〇 (實施例49 ) 在藉由本發明之加熱反應管接觸來製造人工沸石的製 造裝置之反應管上設置超音波振動器（股份有限公司日本 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） •83· --------------------訂---------線-41^- (請先閱讀背面之注意事項再填寫本頁) 涇齊邛，¾°¾讨i苟員11肖t合咋fi卬製 491814 A7 _ B7 五、發明說明（81) 精機製作所製，MODEL US - 6G0T )，於原料混合物準備步驟 裝置方面，將垃圾固態化燃料的焚化灰（由東京都町田市 淸掃局焚化場提供）30kg，砍藻土 70kg以及3.5N的氫氧 化鈉水溶液240L相互混合，於下述的條件下，使用人工沸 石生成裝置來進行人工沸石的合成。 鹼濃度：2N的氫氧化鈉水溶液 反應溫度：90 °C 反應時間：24小時 超音波振動的頻率：25 kHz 反應終了後，藉由X線繞射法確認反應生成物構造的 結果，發現至細孔的深處亦生成有以鈣十字沸石爲主體之 物質。此以鈣十字沸石爲主體之物質的陽離子交換容量爲 360,cmol( + )kg— 1〇 (比較例38 ) 在不施以超音波的條件下，使用與實施例49相同的方 法進行沸石化反應。藉由X線繞射法確認所得之反應生成 物構造的結果，並沒有在細孔的深處發現沸石的轉換。此 以鈣十字沸石爲主體之物質的陽離子交換容量爲230 cmol (+ ) kg 1。 (實施例50 ) 在藉由本發明之加熱反應管接觸來製造人工沸石的製 造裝置之反應管上設置超音波振動器（股份有限公司曰本 本纸張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -84- ---------til----- (請先閱讀背面之注意事項再填寫本頁) 491814 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（82) 精機製作所製，MODEL US -⑼GT )，於原料混合物準備步驟 裝置方面，將已粉碎之鹿耳島產且矽鋁比約3.2之火山玻璃 20kg，玻璃粉末（西日本環境開發協同組合製）5kg，以 及2N的氫氧化鈉水溶液200L相互混合，於下述的條件下 ，使用人工沸石生成裝置來進行人工沸石的合成。 鹼濃度：2N的氫氧化鈉水溶液 反應溫度：90 °C 反應時間：1 2小時 超音波振動的頻率·· 25 kHz 反應終了後，藉由X線繞射法確認反應生成物構造的 結果，發現至細孔的深處亦生成有以八面沸石爲主體之物 質。此以八面沸石爲主體之物質的陽離子交換容量爲300 cmpl ( + ) kg 一 】。 (比較例39 ) 在不施以超音波的條件下，使用與實施例50相同的方 法進行沸石化反應。藉由X線繞射法確認所得之反應生成 物構造的結果，並沒有在細孔的深處發現沸石的轉換。此 以八面沸石爲主體之物質的陽離子交換容量爲210 cmol .( + ) kg — 1 。 (實施例5 1 ) 在藉由本發明之加熱反應管接觸來製造人工沸石的製 造裝置之反應管上設置超音波振動器（股份有限公司曰本 --------------------訂---------線 (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） -85- 491814 經濟部智慧財產局員工消費合作社印製 A7 B7_____ 五、發明說明（83) 精機製作所製，MODEL US - 6GGT ) ’於原料混合物準備步驟 裝置方面，將已粉碎之鹿耳島產且矽鋁比約3.2之火山玻璃 2 0kg，鋁渣滓（由社團法人輕金屬協會提供）5kg，以及 2N的氫氧化鈉水溶液200L相互混合，於下述的條件下，使 用人工沸石生成裝置來進行人工沸石的合成。 鹼濃度：2N的氫氧化鈉水溶液 反應溫度：90 °C 反應時間：1 2小時 超音波振動的頻率：25 kHz 反應終了後，藉由X線繞射法確認反應生成物構造的 結果，發現至細孔的深處亦生成有以鈣十字沸石爲主體之 物質。此以鈣十字沸石爲主體之物質的陽離子交換容量爲 390,cmol ( + ) kg-1。 (比較例4 0 ) 在不施以超音波的條件下，使用與實施例5 1相同的方 法進行沸石化反應。藉由X線繞射法確認所得之反應生成 物構造的結果，並沒有在細孔的深處發現沸石的轉換。此 以鈣十字沸石爲主體之物質的陽離子交換容量爲280 cmol (+ ) kg — 1 〇 (實施例5 2 ) 在藉由本發明之加熱反應管接觸來製造人工沸石的製 造裝置之反應管上設置超音波振動器（股份有限公司曰本 --------------------訂---------線 (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） 86- 491814 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（84) 精機製作所製’ Μ 0 D E L U S - 6 G G T ) ’於原料混合物準備步驟 裝置方面’將非結晶性矽酸鋁之含有量爲8〇 %而矽鋁比約 2.0之都市垃圾的焚化灰（東京都町田市淸掃局焚化場製） 20kg，玻璃粉末（西日本環境開發協同組合製）1〇kg，以 及3.5 N的氣氧化納水溶液2 4 0 L相互混合，於下述的條件下 ，使用人工沸石生成裝置來進行人工沸石的合成。 鹼濃度：3 · 5 N的氫氧化鈉水溶液 反應溫度：90 °C 反應時間：20小時 超音波振動的頻率·· 25 kHz 反應終了後，藉由X線繞射法確認反應生成物構造的 結果，發現至細孔的深處亦生成有以鈣十字沸石爲主體之 物質。此以鈣十字沸石爲主體之物質的陽離子交換容量爲 3 70 cmol (+.) kg— 1〇 (比較例41 ) 在不施以超音波的條件下，使用與實施例52相同的方 法進行沸石化反應。藉由X線繞射法確認所得之反應生成 物構造的結果，並沒有在細孔的深處發現沸石的轉換。此 以鈣十字沸石爲主體之物質的陽離子交換容量爲210 cmol (+ ) kg 一 1。 (實施例53 ) 在藉由本發明之加熱反應管接觸來製造人工沸石的製 -丨丨丨—丨—丨——II .! — I — — I 訂---------線 (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） -87- 491814 A7 五、發明說明（85) 造裝置之反應管上設置超苜波振動器（股份有限公司日本 精機製作所製，MODEL US - 6GGT )，於原料混合物準備步驟 裝置方面’將非結晶性砂酸銘之含有量爲8 〇 %而砂銘比約 2.0之都市垃圾的焚化灰（東京都町田市淸掃局焚化場製） 2 0kg，玻璃粉末（西日本環境開發協同組合製）2〇kg，以 及3 · 5 N的氫氧化鈉水溶液240L相互混合，於下述的條件下 ，使用人工沸石生成裝置來進行人工沸石的合成。v 一 «» JI II «1 ϋ II ϋ II i I tm— emt III an _1 an ϋ nn ϋ ϋ ϋ a ^ i I ϋρ ϋ I -79 · 491814 Printed by the Consumers’ Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 i 2. Description of the invention (77) In terms of equipment, 20 kg of volcanic glass produced from Kagoshima with a silica-to-aluminum ratio of about 3.2 and 200 L of 2N sodium hydroxide aqueous solution are mixed with each other, and an artificial zeolite generating device is used under the following conditions. To carry out the synthesis of artificial zeolite. Alkali concentration: 2 N sodium hydroxide aqueous solution Reaction temperature: 200 ° C Reaction time: 1 hour Frequency of ultrasonic vibration: 25 kHz After the reaction, the structure of the reaction product was confirmed by X-ray diffraction method, and it was found that A substance mainly composed of phillipsite is also formed in the depth of the pores. The cation exchange capacity of the substance mainly composed of phillipsite was 4 2 0 cmο1 (+) kg " 1 ° (Comparative Example 34). The same method as in Example 45 was used without applying ultrasonic waves. Zeolite reaction. As a result of confirming the structure of the obtained reaction product by the X-ray diffraction method, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of the substance mainly composed of phillipsite was 300 cmol (+) kg 1 (Example 4 6) on a reaction tube of a manufacturing apparatus for manufacturing artificial zeolite by contacting the heated reaction tube of the present invention. Ultrasonic vibrator (MODEL US-6GGT, manufactured by Japan Seiki Seisakusho Co., Ltd.) is installed, and in terms of raw material mixture preparation step device, the content of amorphous aluminum silicate is 80%, and the ratio of silicon to tin is about this paper standard. China National Standard (CNS) A4 Specification (210 X 297 mm) -80- -------------------- Order --------- line ( (Please read the notes on the back before filling this page) 491814 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ___B7_______ V. Invention Description (78) 2.0 Incineration Ash of Municipal Waste (Machida City, Tokyo Metropolitan Government Incineration Plant ) 20 kg and 200 L of 2 N sodium hydroxide aqueous solution were mixed with each other, and artificial zeolite was synthesized using an artificial zeolite generating device under the following conditions. Alkali concentration: 2N sodium hydroxide aqueous solution Reaction temperature: 90 ° C Reaction time: 24 hours Frequency of ultrasonic vibration: 25 kHz After the reaction, the structure of the reaction product was confirmed by X-ray diffraction method, and it was found to be fine Substances dominated by hydroxy sodalite are also formed deep in the pores. The cation exchange capacity of the hydroxy sodalite-based substance was 340 cmol (+) kg — 10 (Comparative Example 35). The zeolite was subjected to the same method as in Example 46 without applying ultrasonic waves.化 反应。 Reaction. As a result of confirming the structure of the obtained reaction product by the X-ray diffraction method, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of the hydroxy sodalite-based substance was 270 cmol (+) kg-1 (Example 47). The reaction tube was installed on a reaction tube of a manufacturing apparatus for producing human zeolite X by contacting the heated reaction tube of the present invention. Ultrasonic vibrator (manufactured by Nippon Seiki Co., Ltd., MODEL old-600T), in terms of the raw material mixture preparation step device, the content of amorphous aluminum silicate is 95%, and the ratio of silicon to aluminum is suitable for this paper. China National Standard (CNS) A4 Specification (210 X 297 mm)--------------------- Order --------- ^ (please first Read the notes on the back and fill in this page) 491814 A7 ___ B7 V. Description of the invention (79) (Please read the notes on the back before filling this page) 2.5 Fly Ash (made by Power Development Co., Ltd. Matsuura Power Generation Co., Ltd.) (Supplied by Fly Ash Association) 20 kg and 200 L of 4N aqueous sodium hydroxide solution were mixed with each other 'Under the conditions described below, an artificial zeolite generator was used to synthesize artificial zeolite. Alkali concentration: 2N sodium hydroxide aqueous solution Reaction temperature: 120 ° C Reaction time: 3 hours Frequency of ultrasonic vibration: 25 kHz After the reaction was completed, the result of the reaction product structure was confirmed by X-ray diffraction method, and it was found to be fine A substance mainly composed of phillipsite was also formed in the depth of the pores. The cation exchange capacity of this substance, which is mainly phillipsite, is 350 cmol (+) kg — 10 (Comparative Example 36). The clothing printed by the staff consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is not subjected to ultrasonic waves. The zeolite reaction was carried out in the same manner as in Example 47. As a result of confirming the structure of the obtained reaction product by the X-ray diffraction method, no zeolite conversion was found in the depth of the pores. The cation-exchange capacity of this substance, mainly phillipsite, is 280 cmol (+) kg-1. (Example 48) An ultrasonic vibrator (MODEL US-6GGT, manufactured by Nippon Seiki Co., Ltd.) was installed on a reaction tube of a manufacturing device for manufacturing artificial zeolite by heating the reaction tube contact of the present invention, and in the preparation step of the raw material mixture -82-This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 491814 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of Invention (80) For the device, non-crystalline silicon Fly ash with a content of 95% aluminum and a silica-to-aluminum ratio of about 2.5 (manufactured by Matsuura Electric Power Development Co., Ltd., provided by the fly ash association) 20 kg, glass powder (manufactured by West Japan Environmental Development Cooperative) 5 kg and 4N 200 L of a sodium hydroxide aqueous solution were mixed with each other, and artificial zeolite was synthesized using an artificial zeolite generating apparatus under the following conditions. Alkali concentration: 4 N sodium hydroxide aqueous solution Reaction temperature: 200 ° C Reaction time: 5 hours Frequency of ultrasonic vibration: 25 kHz After the reaction was completed, the structure of the reaction product was confirmed by X-ray diffraction method. A substance mainly composed of faujasite was also formed in the depth of the pores. The cation exchange capacity of this faujasite-based material was 380 (Comparative Example 37). The zeolite reaction was carried out in the same manner as in Examples 4 to 8 without applying ultrasonic waves. As a result of confirming the structure of the obtained reaction product by the X-ray diffraction method, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this faujasite-based substance was 230 cmol (+) kg 1 0 (Example 49). An ultrasonic wave was set on a reaction tube of a manufacturing apparatus for manufacturing artificial zeolite by contacting the heated reaction tube of the present invention. Vibrator (Japan Co., Ltd. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) • 83 · -------------------- Order --------- 线 -41 ^-(Please read the notes on the back before filling out this page) 泾 泾 泾, ¾ ° ¾ t 11 t t 咋 卬 fi system 491814 A7 _ B7 V. Description of the invention (81) Made by Seiki Co., Ltd., MODEL US-6G0T), in the preparation process of the raw material mixture, the incineration ash of solid waste fuel (provided by the incineration plant of the Sweeping Bureau, Machida City, Tokyo) 30kg, chopped algae 70 kg of soil and 240 L of 3.5 N aqueous sodium hydroxide solution were mixed with each other, and artificial zeolite was synthesized using an artificial zeolite generating apparatus under the following conditions. Alkali concentration: 2N sodium hydroxide aqueous solution Reaction temperature: 90 ° C Reaction time: 24 hours Frequency of ultrasonic vibration: 25 kHz After the reaction, the structure of the reaction product was confirmed by X-ray diffraction method, and it was found to be fine A substance mainly composed of phillipsite was also formed in the depth of the pores. The cation exchange capacity of the substance mainly composed of phillipsite was 360, cmol (+) kg — 10 (Comparative Example 38). Zeolization was performed by the same method as in Example 49 without applying ultrasonic waves. reaction. As a result of confirming the structure of the obtained reaction product by the X-ray diffraction method, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this substance, mainly phillipsite, is 230 cmol (+) kg1. (Example 50) An ultrasonic vibrator is installed on a reaction tube of a manufacturing apparatus for manufacturing artificial zeolite by contacting the heated reaction tube of the present invention (the paper size of the company's paper is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -84- --------- til ----- (Please read the notes on the back before filling out this page) 491814 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 5 2. Description of the invention (82) MODEL US- 制作 GT manufactured by Seiki Seisakusho Co., Ltd., in the preparation process of the raw material mixture, 20 kg of volcanic glass produced from Kagoshima with a silica-to-aluminum ratio of about 3.2, and glass powder (Western Japan Environment Development Cooperative) 5 kg) and 200 L of 2 N aqueous sodium hydroxide solution were mixed with each other, and artificial zeolite was synthesized using an artificial zeolite generating apparatus under the following conditions. Alkali concentration: 2N sodium hydroxide aqueous solution Reaction temperature: 90 ° C Reaction time: 12 hours Frequency of ultrasonic vibration 25 kHz After the reaction was completed, the structure of the reaction product was confirmed by X-ray diffraction method and found A substance mainly composed of faujasite is also formed to the depth of the pores. The cation exchange capacity of the faujasite-based material is 300 cmpl (+) kg. (Comparative Example 39) A zeolite reaction was carried out in the same manner as in Example 50 without using ultrasonic waves. As a result of confirming the structure of the obtained reaction product by the X-ray diffraction method, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this faujasite-based substance is 210 cmol. (+) Kg-1. (Example 5 1) An ultrasonic vibrator is installed on a reaction tube of a manufacturing apparatus for manufacturing artificial zeolite by contacting the heated reaction tube of the present invention (the company's Japanese version ------------- ------- Order --------- Line (Please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -85- 491814 Printed by A7 B7_____ of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (83) Made by Seiki Co., Ltd., MODEL US-6GGT 20 kg of volcanic glass with a silica-to-aluminum ratio of 3.2, 5 kg of aluminum dross (provided by the Light Metal Association of Japan), and 200 L of 2N aqueous sodium hydroxide solution were mixed with each other, and artificial zeolite was produced using an artificial zeolite generating device under the following conditions. Synthesis. Alkali concentration: 2N sodium hydroxide aqueous solution Reaction temperature: 90 ° C Reaction time: 12 hours Frequency of ultrasonic vibration: 25 kHz After the reaction, the structure of the reaction product was confirmed by X-ray diffraction method. A substance mainly composed of phillipsite is also formed in the depth of the pores. The cation exchange capacity of this substance, mainly phillipsite, is 390, cmol (+) kg-1. (Comparative Example 40) The zeolite reaction was carried out in the same manner as in Example 51 without applying ultrasonic waves. As a result of confirming the structure of the obtained reaction product by the X-ray diffraction method, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of the substance mainly composed of phillipsite was 280 cmol (+) kg — 10 (Example 5 2). The reaction tube was installed on a reaction tube of a manufacturing apparatus for producing artificial zeolite by contacting the heated reaction tube of the present invention. Ultrasonic Vibrator (Co., Ltd. ---------------------- Order --------- Line (Please read the precautions on the back first) (Fill in this page) This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 86- 491814 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (84) Made by Seiki 0 DELUS-6 GGT) 'In the raw material mixture preparation step device', the incineration ash of municipal waste with a content of 80% of amorphous aluminum silicate and a ratio of silicon to aluminum of about 2.0 Field production) 20 kg, glass powder (manufactured by Nippon Environmental Development Co., Ltd.) 10 kg, and 3.5 N aerosol aqueous sodium oxide solution 2 40 L are mixed with each other, and artificial zeolite is produced using an artificial zeolite generating device under the following conditions. Synthesis. Alkali concentration: 3 · 5 N sodium hydroxide aqueous solution Reaction temperature: 90 ° C Reaction time: 20 hours frequency of ultrasonic vibration · 25 kHz After the reaction is completed, the result of the reaction product structure is confirmed by X-ray diffraction method It was found that to the depth of the pores, a substance mainly composed of phillipsite was also formed. The cation exchange capacity of the substance mainly composed of phillipsite was 3 70 cmol (+.) Kg—10 (Comparative Example 41). The zeolite was prepared in the same manner as in Example 52 without using ultrasonic waves.化 反应。 Reaction. As a result of confirming the structure of the obtained reaction product by the X-ray diffraction method, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this substance, mainly phillipsite, is 210 cmol (+) kg-1. (Example 53) In the production of artificial zeolite by contacting the heated reaction tube of the present invention-丨 丨 丨-丨-丨 ——II.! — I — — I Order --------- Line ( Please read the precautions on the back before filling this page) This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) -87- 491814 A7 V. Description of the invention (85) Set on the reaction tube of the device Ultra-clover wave vibrator (MODEL US-6GGT, manufactured by Nippon Seiki Seisakusho Co., Ltd.), in terms of the raw material mixture preparation step device, the content of the amorphous sand acid salt is 80% and the sand ratio is about 2.0. Waste incineration ash (manufactured by the Municipal Sweeping Bureau Incineration Plant, Machida, Tokyo) 20 kg, glass powder (manufactured by Nippon Environmental Development Co., Ltd.) 20 kg, and 240 L of a 3.5 N sodium hydroxide aqueous solution are mixed with each other in the following Under the conditions, the artificial zeolite generator is used to synthesize artificial zeolite.
鹼濃度：3.5N的氫氧化鈉水溶液 反應溫度：90 °C 反應時間：30小時 ‘ 超音波振動的頻率：25 kHz 反應終了後，藉由X線繞射法確認反應生成物構造的 結果/，發現至細孔的深處亦生成有以八面沸石爲主體之物 質。此以八面.沸石爲主體之物質的陽離子交換容量爲240 cmol ( + ) kg — 1〇 (比較例42 ) 在不施以超音波的條件下，使用與實施例53相同的方 法進行沸石化反應。藉由X線繞射法確認所得之反應生成 物構造的結果，並沒有在細孔的深處發現沸石的轉換。此 以八面沸石爲主體之物質的陽離子交換容量爲190 cmol ( + ) kg — 1 。 實施例54 ) -88- (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） 逐齋邹ti讨4苟員11.消費合阼汪卬製 491814 A7 B7 五、發明說明（86) 在藉由本發明之加熱反應管接觸來製造人工沸石的製 造裝置之反應管上設置超音波振動器（股份有限公司曰本 精機製作所製’ MODEL US -⑼0T )，於原料混合物準備步驟 裝置方面，將非結晶性矽酸鋁之含有量爲95 %而矽鋁比約 2.5之飛灰（電源開發股份有限公司松浦發電所製，由飛灰 協會提供）20kg，玻璃粉末（西日本環境開發協同組合製 )10kg，以及3·5Ν的氫氧化鈉水溶液240L相互混合，於 下述的條件下，使用人工沸石生成裝置來進行人工沸石的 合成。 鹼濃度：3.5Ν的氫氧化鈉水溶液 ^ 反應溫度：90 °C 反應時間：30小時 ，超音波振動的頻率：25 kHz 反應終了後，藉由X線繞射法確認反應生成物構造的 結果，發現至細孔的深處亦生成有以八面沸石爲主體之物 質。此以八面沸石爲主體之物質的陽離子交換容量爲360 cmol ( + ) kg — 1 〇 (比較例4 3 ) 在不施以超音波的條件下，使用與實施例54相同的方 法進行沸石化反應。藉由X線繞射法確認所得之反應生成 物構造的結果，並沒有在細孔的深處發現沸石的轉換。此 以八面沸石爲主體之物質的陽離子交換容量爲240 cmol ( + ) kg ~ 1 〇 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -89- --------— if i (請先閱讀背面之注意事項再填寫本頁) 1^·- .線- 491814 經濟部智慧財產局員工消費合作社印製 A7 B7 i、發明說明（87) (實施例55 ) 在藉由本發明之加熱反應管接觸來製造人工沸石的製 造裝置之反應管上設置超音波振動器（股份有限公司日本 精機製作所製，MODEL US - 6GGT )，於原料混合物準備步驟 裝置方面’將非結晶性矽酸鋁之含有量爲95 %而矽鋁比約 2.5之飛灰（電源開發股份有限公司松浦發電所製，由飛灰 協會提供）20kg，玻璃粉末（西日本環境開發協同組合製 )5kg，使其矽鋁比變爲大約4之物質與4N的氫氧化鈉水 溶液200L相互混合，於下述的條件下，使用人工沸石生成 裝置來進行人工沸石的合成。 鹼濃度：4N的氫氧化鈉水溶液 ，反應溫度：200 °C 反應時間：3小時 超音波振動的頻率：25 kHz 反應終了後，藉由X線繞射法確認反應生成物構造的 結果，發現至細孔的深處亦生成有以八面沸石爲主體之物 質。此以八面沸石爲主體之物質的陽離子交換容量爲300 cmol ( + ) kg 一 1 〇 (比較例44 ). 在不施以超音波的條件下，使用與實施例5 5相同的方 法進行沸石化反應。藉由X線繞射法確認所得之反應生成 物構造的結果，並沒有在細孔的深處發現沸石的轉換。此 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -90- --------------------訂---------^ IAWI (請先閱讀背面之注意事項再填寫本頁) 491814 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（88) 以八面沸石爲主體之物質的陽離子交換容量爲220 cmo丨（ + ) kg " 1 ° (實施例56 ) 在藉由本發明之加熱反應管接觸來製造人工沸石的製 造裝置之反應管上設置超音波振動器（股份有限公司曰本 精機製作所製，MODEL US - 6GGT )，於原料混合物準備步驟 裝置方面，將鹼濃度（使用氫氧化鈉水溶液）約6N、鋁濃 度約1 Og/L之鋁製窗框的廢液以水稀釋至變成爲鹼濃度約 4N之廢液後，與水玻璃混合，使其變成矽鋁比約1.5之物 質，再於下述的條件下，將前述的物質放入人工沸石生成 裝置中來進行人工沸石的合成。 .鹼濃度：4N的氫氧化鈉水溶液 反應溫度：150 °C 反應時間：20分鐘 超音波振動的頻率：25 kHz 反應終了後，藉由X線繞射法確認反應生成物構造的 結果，發現至細孔的深處亦生成有以羥基方鈉石爲主體之 純白色的物質。此以羥基方鈉石爲主體之物質的陽離子交 換容量爲 420cmol ( + ) kg—、 (比較例4 5 ) 在不施以超音波的條件下，使用與實施例56相同的方 法進行沸石化反應。藉由X線繞射法確認所得之反應生成 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -91 - -------r------------訂----K--線 (請先閱讀背面之注意事項再填寫本頁) 491814 A7 B7Alkali concentration: 3.5N sodium hydroxide aqueous solution Reaction temperature: 90 ° C Reaction time: 30 hours' Frequency of ultrasonic vibration: 25 kHz After the reaction is completed, the result of the structure of the reaction product is confirmed by X-ray diffraction method, It was found that a substance mainly composed of faujasite was formed to the depth of the pores. The cation exchange capacity of the substance mainly composed of octahedral zeolite was 240 cmol (+) kg — 10 (Comparative Example 42). Zeolization was performed by the same method as in Example 53 without applying ultrasonic waves. reaction. As a result of confirming the structure of the obtained reaction product by the X-ray diffraction method, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this faujasite-based substance is 190 cmol (+) kg-1. Example 54) -88- (Please read the notes on the back before filling out this page) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Cooperated with Wang Jian 491814 A7 B7 V. Description of the invention (86) An ultrasonic vibrator is installed on the reaction tube of the manufacturing device for manufacturing artificial zeolite by contacting the heated reaction tube of the present invention (manufactured by Japan Seiki Seiki Co., Ltd.) MODEL US -⑼0T), in the preparation process of the raw material mixture, the fly ash with an amorphous aluminum silicate content of 95% and a silicon-aluminum ratio of about 2.5 (manufactured by Matsuura Electric Power Development Co., Ltd., produced by fly ash) (Supplied by the Association) 20 kg, 10 kg of glass powder (manufactured by West Japan Environmental Development Cooperative) and 240 L of 3.5N sodium hydroxide aqueous solution were mixed with each other, and artificial zeolite was synthesized using an artificial zeolite generating device under the following conditions. Alkali concentration: 3.5N sodium hydroxide aqueous solution ^ Reaction temperature: 90 ° C Reaction time: 30 hours, frequency of ultrasonic vibration: 25 kHz After the reaction is completed, the result of the structure of the reaction product is confirmed by X-ray diffraction method, It was found that a substance mainly composed of faujasite was formed to the depth of the pores. The cation exchange capacity of this faujasite-based substance was 360 cmol (+) kg — 10 (Comparative Example 43). Zeolization was performed in the same manner as in Example 54 without applying ultrasonic waves. reaction. As a result of confirming the structure of the obtained reaction product by the X-ray diffraction method, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this faujasite-based substance is 240 cmol (+) kg ~ 1 〇 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -89- ----- ---— if i (Please read the notes on the back before filling out this page) 1 ^ ·-. Line-491814 Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 i, Invention Note (87) (Example 55 ) An ultrasonic vibrator (manufactured by Nippon Seiki Co., Ltd., MODEL US-6GGT) is installed on the reaction tube of the manufacturing device for manufacturing artificial zeolite by contacting the heated reaction tube of the present invention. Non-crystalline aluminum silicate with a content of 95% and fly ash with a silica-to-aluminum ratio of about 2.5 (manufactured by Matsuura Electric Power Development Co., Ltd., provided by the fly ash association) 20 kg, glass powder (manufactured by West Japan Environment Development Cooperative) 5 kg of a substance whose silicon-aluminum ratio was changed to about 4 was mixed with 200 L of 4N aqueous sodium hydroxide solution, and artificial zeolite was synthesized using an artificial zeolite generating apparatus under the following conditions. Alkali concentration: 4N sodium hydroxide aqueous solution, reaction temperature: 200 ° C reaction time: 3 hours frequency of ultrasonic vibration: 25 kHz After the reaction, the structure of the reaction product was confirmed by X-ray diffraction method. A substance mainly composed of faujasite was also formed in the depth of the pores. The cation exchange capacity of this faujasite-based substance was 300 cmol (+) kg-10 (Comparative Example 44). Zeolite was carried out in the same manner as in Examples 5 and 5 without applying ultrasonic waves.化 反应。 Reaction. As a result of confirming the structure of the obtained reaction product by the X-ray diffraction method, no zeolite conversion was found in the depth of the pores. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -90- -------------------- Order ------ --- ^ IAWI (Please read the notes on the back before filling out this page) 491814 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (88) Cation exchange capacity of the substance mainly composed of faujasite 220 cmo (+) kg " 1 ° (Example 56) An ultrasonic vibrator was installed on a reaction tube of a manufacturing apparatus for manufacturing artificial zeolite by contacting the heated reaction tube of the present invention (Kyomoto Seiki Co., Ltd. (MODEL US-6GGT), in the raw material mixture preparation step device, dilute the waste liquid of aluminum window frame with alkali concentration (using sodium hydroxide aqueous solution) of about 6N and aluminum concentration of about 1 Og / L with water to become After the waste liquid having an alkali concentration of about 4N, it is mixed with water glass to make it into a substance having a silicon-aluminum ratio of about 1.5. Then, under the following conditions, the aforementioned substance is put into an artificial zeolite generating device to synthesize artificial zeolite. . . Alkali concentration: 4N sodium hydroxide aqueous solution. Reaction temperature: 150 ° C. Reaction time: 20 minutes. Frequency of ultrasonic vibration: 25 kHz. After the reaction, the structure of the reaction product was confirmed by X-ray diffraction method. Pure white substance with hydroxy sodalite as the main body is also formed in the depth of the pores. The cation exchange capacity of the hydroxy sodium sodalite-based substance was 420 cmol (+) kg—, (Comparative Example 4 5). The zeolite reaction was performed using the same method as in Example 56 without applying ultrasonic waves. . The resulting reaction was confirmed by X-ray diffraction method. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -91-------- r -------- ---- Order ---- K--line (Please read the precautions on the back before filling this page) 491814 A7 B7
五、發明說明（89) 物構造的結果，並沒有在細孔的深處發現沸石的轉換。此 以羥基方鈉石爲主體之純白色物質的陽離子交換容量爲42〇 cmol ( + ) kg (實施例57 ) 在藉由本發明之加熱反應管接觸來製造人工沸石的製 造裝置之反應管上設置超音波振動器（股份有限公司日本 精機製作所製，MODEL US - 6GGT )，於原料混合物準備步驟 裝置方面，以4N的氫氧化鈉水溶液來中和耐酸鋁製造過程 中所產生之草酸的酸性廢液後，加熱乾燥所得的鋁之沉搬 凝膠，將此鋁的沉澱凝膠1 〇〇〇g溶解於氫氧化鈉水溶液 1 00L中，使其成爲鹼濃度約4N之物，再將此物質與水玻璃 混合，使其變成矽鋁比約3.0之混合物，於下述的條件下， 將此混合物放入人工沸石生成裝置中來進行人工沸石的合 成。 鹼濃度：4N的氫氧化鈉水溶液 反應溫度：150 °C 反應時間：20分鐘 超音波振動的頻率：25 kHz 反應終了後，藉由X線繞射法確認反應生成物構造的 結果，發現至細孔的深處亦生成有以八面沸石爲主體之純 白色的物質。此以八面沸石爲主體之物質的陽離子交換容 量爲 420 cmol ( + ) kg — 1。 (請先閱讀背面之注意事項再填寫本頁) -參 經濟部智慧財產局員工消費合作社印製 訂----:----I'線-iR------------------------ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -92 - 491814 A7 B7 五、發明說明（9〇) (比較例46) (請先閱讀背面之注意事項再填寫本頁) 在不施以超音波的條件下，使用與實施例57相同的方 法進行沸石化反應。藉由X線繞射法確認所得之反應生成 物構造的結果，並沒有在細孔的深處發現沸石的轉換。此 以八面沸石爲主體之純白色物質的陽離子交換容量爲420 cmol ( + ) kg — 1 〇 (實施例5 8 ) 在藉由本發明之加熱反應管接觸來製造人工沸石的製 造裝置之反應管上設置超音波振動器（股份有限公司日本 精機製作所製，MODEL US - 6G0T )，於原料混合物準備步驟 裝置方面，將已粉碎之稻的植物體1 0kg與約4N的氫氧化鈉 水溶液2 0 L混合，一邊攪拌一邊加熱，然後噴霧乾燥加熱 所得到含有矽酸鹽成分之溶解析出液，將所得到含矽之粉 末（二氧化矽含有率95重量％ ) 2kg與30L具有lOOOOppm 鋁濃度之鋁酸蘇打水的氫氧化鈉水溶液（約3 N )混合，使 其變成爲矽鋁比約3之混合物，於下述的條件下，將此混 合物放入本發明的裝置中來進行人工沸石反應。 变齊郢皆慧讨4苟員x-省費合阼fi卬製 鹼濃度：3.0N的氫氧化鈉水溶液 反應溫度：150 t 反應時間：30分鐘 超音波振動的頻率：25 kHz 反應終了後，藉由X線繞射法確認反應生成物構造的 結果，發現至細孔的深處亦生成有以沸石X爲主體之純白 -93- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 491814 A7 B7 五、發明說明（91) 色的物質。此以沸石X爲主體之物質的陽離子交換容量爲 420 cmol ( + ) kg - 1 〇 (請先閱讀背面之注意事項再填寫本頁) 產業上的可利用性 如以上說明般，藉由以天然沸石爲主到合成沸石間之 品質上的差異，沸石具有廣泛的用途。而且人工沸石不僅 能夠比合成沸石更便宜地製造，亦比天然沸石具有更優秀 的品質。本發明係以含矽酸以及鋁之物質，例如火山噴出 物之降塵、可燃性廢棄物之焚化灰、污泥之焚化灰、煤灰 、垃圾固態化燃燒之焚化灰、鋁廢液、禾本科植物等之未 利用資源爲原料來製造人工沸石之方法，或者是，藉由添 加玻璃、矽藻土、水玻璃等之矽酸富集材或鋁渣滓、鋁酸 蘇打水等之鋁富集材，能任意地調整原料的矽鋁比，以製 造合於用途之任意品質的人工沸石之方法。 又，本發明，係藉由於進行沸石化反應時倂用超音波 處理，能得到甚至到所生成之人工沸石的細孔深處亦擁有 優秀之沸石化品質的人工沸石之人工沸石製造方法。 經濟部智慧財產局員工消費合作社印製 而且，藉由採用紅外線放射、微波加熱、感應加熱等 之加熱方法來做好製造人工沸石時之預熱。 若使用藉本發明之加熱反應管接觸來製造人工沸石的 連續製造方法以及其連續製造裝置，則因藉由原料混合物 通過被加熱之反應管內時所產生之亂流的作用，可非常有 效率地攪拌原料混合物中之人工沸石原料與鹼性水溶液， 故能促進人工沸石的反應，進而謀求縮短反應時間及提昇 -94- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） 491814 A7 _ B7 五、發明說明（92 ) 製造效率之效果。此外，因能夠容易地調節原料混合物的 固液比、反應時間、反應溫度等，故相對於其供給量或生 產量之變化能容易地對應，進而使連續操作或自動操作變 成爲可能。 具有如此效果之藉由加熱反應管接觸來製造人工沸石 的連續製造方法以及其連續製造裝置’不僅能使裝置全體 小型化，亦能減低工廠建設費。更者，因能夠連續且有效 率地製造，故又能大量生產，又能使其容易對應於生產量 之增減。 (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 -95 - 本紙張尺度適用中國國家標準（CNS)A4規格（2〗0 X 297公釐）V. Description of the invention As a result of the structure of (89), no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this pure white substance with hydroxy sodalite as the main body was 42.0 cmol (+) kg (Example 57). The reaction tube was installed on a reaction tube of a manufacturing apparatus for producing artificial zeolite by contacting the heated reaction tube of the present invention. Ultrasonic vibrator (MODEL US-6GGT, manufactured by Japan Seiki Seisakusho Co., Ltd.) uses a 4N aqueous solution of sodium hydroxide to neutralize the acidic waste liquid of oxalic acid produced during the production of aluminum-resistant aluminum in the process of preparing the raw material mixture. Then, the obtained aluminum precipitation gel was dried by heating, and 1,000 g of the aluminum precipitation gel was dissolved in 100 L of an aqueous sodium hydroxide solution to make it a substance having an alkali concentration of about 4N. Water glass was mixed to make it into a mixture of silicon-aluminum ratio of about 3.0. Under the following conditions, this mixture was put into an artificial zeolite generator to synthesize artificial zeolite. Alkali concentration: 4N sodium hydroxide aqueous solution Reaction temperature: 150 ° C Reaction time: 20 minutes Frequency of ultrasonic vibration: 25 kHz After the reaction, the structure of the reaction product was confirmed by X-ray diffraction method, and it was found to be fine Deep white pores of pure faujasite were also formed in the depth of the pores. The cation exchange capacity of this faujasite-based substance is 420 cmol (+) kg — 1. (Please read the precautions on the back before filling out this page)-Participated in the work of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ----: ---- I'line-iR ----------- ------------- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -92-491814 A7 B7 V. Description of the invention (90) (Comparative Example 46) ) (Please read the precautions on the back before filling out this page.) The zeolite reaction was carried out in the same manner as in Example 57 without using ultrasonic waves. As a result of confirming the structure of the obtained reaction product by the X-ray diffraction method, no zeolite conversion was found in the depth of the pores. The cation exchange capacity of this pure white substance with faujasite as the main body was 420 cmol (+) kg — 10 (Example 5 8). The reaction tube of the manufacturing device for manufacturing artificial zeolite was contacted by the heating reaction tube of the present invention. An ultrasonic vibrator (MODEL US-6G0T, manufactured by Japan Seiki Seisakusho Co., Ltd.) is installed on the raw material mixture preparation step device. 10 kg of the crushed rice plant body and about 4 N sodium hydroxide aqueous solution 20 L Mix, heat while stirring, and then spray dry and heat to obtain the solvate containing the silicate component. The obtained silicon-containing powder (silicon dioxide content 95% by weight) 2 kg and 30 L of aluminate with an aluminum concentration of 1000 ppm An aqueous sodium hydroxide solution (about 3 N) of soda water was mixed to make a mixture of silicon and aluminum with a ratio of about 3, and the mixture was put into the apparatus of the present invention to perform an artificial zeolite reaction under the following conditions. All the changes are made. All of them are x-cost-saving. Fi-based alkali concentration: 3.0N sodium hydroxide solution. Reaction temperature: 150 t. Response time: 30 minutes. Frequency of ultrasonic vibration: 25 kHz. As a result of confirming the structure of the reaction product by the X-ray diffraction method, it was found that pure white with zeolite X as the main body was also formed to the depth of the pores. -93- This paper is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 491814 A7 B7 V. Description of the invention (91) Colored substance. The cation exchange capacity of this zeolite X-based substance is 420 cmol (+) kg-1 〇 (please read the precautions on the back before filling this page). The industrial applicability is as explained above. Zeolites are widely used because of the difference in quality between zeolite-based and synthetic zeolites. Moreover, artificial zeolite can not only be manufactured cheaper than synthetic zeolite, but also has better quality than natural zeolite. The present invention is based on substances containing silicic acid and aluminum, such as dust fall of volcanic effluent, incineration ash of combustible waste, incineration ash of sludge, coal ash, incineration ash of solid waste burning, aluminum waste, grass A method for producing artificial zeolite from unused resources of plants or the like, or by adding a silicic acid-rich material such as glass, diatomaceous earth, water glass, or the like The method can adjust the silicon-aluminum ratio of the raw materials arbitrarily to produce artificial zeolite of any quality suitable for the application. In addition, the present invention is an artificial zeolite manufacturing method capable of obtaining artificial zeolite having excellent zeolite quality even to the depth of the pores of the artificial zeolite produced by ultrasonic treatment during the zeolization reaction. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Furthermore, pre-heating for the manufacture of artificial zeolite is done by heating methods such as infrared radiation, microwave heating, and induction heating. If the continuous production method and the continuous production device for producing artificial zeolite by contacting the heated reaction tube of the present invention are used, the turbulent flow generated when the raw material mixture passes through the heated reaction tube can be very efficient. The artificial zeolite raw material and the alkaline aqueous solution in the raw material mixture are stirred, so that the reaction of artificial zeolite can be promoted, so as to shorten the reaction time and improve. -94- This paper size applies to China National Standard (CNS) A4 (210 X 297). ) 491814 A7 _ B7 V. Description of the invention (92) Effect of manufacturing efficiency. In addition, since the solid-liquid ratio, reaction time, reaction temperature, etc. of the raw material mixture can be easily adjusted, it is possible to easily cope with changes in the supply amount or production amount thereof, thereby making continuous operation or automatic operation possible. The continuous production method for producing artificial zeolite by heating the contact of the reaction tube and the continuous production apparatus' having such an effect can not only miniaturize the entire apparatus, but also reduce the construction cost of the plant. Furthermore, since it can be manufactured continuously and efficiently, it can be mass-produced and it can be easily adapted to increase or decrease in production volume. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -95-This paper size applies to China National Standard (CNS) A4 (2) 0 X 297 mm