567097 Μ ____ Β7 五、發明説明（1 ) 〔發明之所屬技術領域〕 (請先閲讀背面之注意事項再填寫本頁) 本發明係關於石油系燃燒灰之濕式處理方法，詳加說 明，其爲關於藉由設置在使用石油系燃料之鍋爐等排廢氣 管道中的集塵器捕集至少含有釩之燃燒灰之濕式處理方法 ’特別是，適合使用在當需處理之燃燒灰量爲較少時，或 是當燃燒灰中之碳爲少且釩之含量高時，以簡單之工序就 可容易回收釩之有利工業性方法。 〔習知技術〕 於使用石油系燃料（例如，重油、「ORIMULSION」 等）之各種燃燒爐（燃燒裝置）中，例如，於火力發電所 之鍋爐及垃圾焚化爐等鍋爐中，爲防止燃燒氣體中所產生 之硫酸氣體（S〇3 ) ‘造成之腐蝕，在該當燃燒氣體中添 加阿摩尼亞（氨）。此外，取代阿摩尼亞（氨）亦有使用 氧化鎂。 經濟部智慧財產局員工消費合作社印製 另，上述之「ORIMULSION」，係爲天然瀝 青藉由界面活性劑分散在水中形成之ORIMULSION燃料 ，且其天然瀝青爲來自南美委內瑞拉之歐利農各（ Orinoco)河流域生產之天然瀝青，其爲委內瑞拉之 BIT OR公司之登錄商標。 / 因此，於藉由配置在其煙道後流側之電力集塵器所捕 集回收之燃燒灰中，除了含有以未燃碳及重金屬（N i 、 V、M g等）爲主體之灰成份外，尙含有硫酸銨等。特別 是「〇R I M U L S I〇N」之燃燒灰，所含有之碳較少 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） -4- 567097 A7 B7五、發明説明（2 ) 而所含有之硫酸錢（或是硫酸鍾）及釩較多。例如，從「 ◦ R I Μ U L S I〇N」焚化爐中回收之燃燒灰的組成分 析（乾粉狀態）一例如表1所示。 (表1 ) 成份 C ΝΗ4 S〇4 V Ni Mg 重量％ 1〜5 12 〜20 50 〜65 4〜9 0.5〜2 0.1 〜2 經濟部智慧財產局員工消費合作社印製 做爲上述之燃燒灰的濕式處理方法，以在回收釩等之 有價成份的同時藉由閉合系統化謀求公害防止對策之被稱 爲濕式工序之技術有多數之提案。具體而言，例如，有由 本案申請人既已提案之日本專利特開昭6 0 - 1 9 0 8 6 號、特開昭6 0 — 4 6 9 3 0號、特公平4 一 6 1 7 0 9 號、特公平5 - 1 3 7 1 8號之各公報記載之濕式工序。 做爲上述之濕式工序的具體例，例如，於上述之特公 平5 — 1 3 7 1 8號公報中，記載有如以下之石油系燃燒 灰之濕式處理工序。即，上述之濕式工序，係包括：（1 )將燃燒灰與水進行混合，視需要添加硫酸調整成Ρ Η爲 3以下砂漿狀態之第1工程；（2 )將固體成份（碳等） 進行分離之第2工程；將液體部加溫至7 0 °C以上，然後 供給阿摩尼亞（氨）與氧化劑漸漸將ρ Η調整成7〜9使 金屬氧化之第3工程；（4 )將析出物（鐵泥漿）進行分 離之第4工程；（5 )將液體部冷卻成4 0 °C以下析出fL 化合物（偏釩酸銨）之第5工程；（6 )將被析出之釩化 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） (請先閲讀背面之注意事項再填寫本頁) 567097 A7 B7 五、發明説明（3 ) (請先閲讀背面之注意事項再填寫本頁) 合物進行分離之第6工程；（7 )在液體部中添加氫氧化 鈣或氧化鈣後析出石膏及金屬（鎳及鎂）氫氧化物，同時 使阿摩尼亞（氨）游離之第7工程；從游離之阿摩尼亞（ 氨）中將阿摩尼亞（氨）脫離後進行回收之第8工程及將 石膏進行分離之第9工程。 然而，如上述般大工程之工序，於需處理之燃燒灰量 爲較少時，或者是，燃燒灰中之碳含量少且釩含量較高時 就談不上具經濟性。 本發明，係有鑑上述實情而爲者，其目的，係爲提供 一種特別適合使用在需處理之燃燒灰量爲較少時，或者是 ，燃燒灰中之碳含量少且釩含量較高時，以簡單之工序就 可容易回收釩之有利工業性方法。 〔發明之開示〕 經濟部智慧財產局員工消費合作社印製 本發明者們，爲達成上述目的進行銳意改革之重覆檢 討結果，獲得以下之想法與知識。即，若能濃縮燃燒灰中 之有價金屬成份，就可在處理還原劑之未燃碳的同時適用 眾所周知之有價金屬回收技術。例如，從上述表1所示之 燃燒灰中去除硫酸錢之大部份後與未燃碳同時將有價金屬 成份進行濃縮時所得之組成分析（乾粉狀態）之一例如表 2所示。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 567097 A7 ______B7 五、發明説明（4 ) (表2 ) 成份 C NH4 S〇4 V Ni Mg 重量％ 5〜10 0.5〜1.5 2〜3.5 25 〜38 2〜5 1〜2 (請先閲讀背面之注意事項再填寫本頁) 接著，若在上述習知技術之第2工程分離固體成份（ 碳等）之1處可回收實質全量之有價金屬成份時，燃燒灰 中之有價金屬成份就會被濃縮。此外，藉此、，使工序變簡 單，於需處理之燃燒灰量較少時，或者是，燃燒灰中之碳 含量少且釩含量較多時變得較有利。 根據上述想法再次重覆檢討之結果，在回收釩時所需 要之酸反應，因在高濃度硫酸銨之存在條件下可容易進行 故即使是在較低溫之狀態仍要進行。其結果，持續採用爲 回收實質全量之有價金屬成份時所需之低溫是可進行固體 成份（碳等）及有價金屬成份之分離·回收。 經濟部智慧財產局員工消費合作社印製 本發明，係爲根據上述之想法與知識來完成燃燒灰之 濕式處理方法，其主旨如下，其爲藉由設置在使用石油系 燃料之鍋爐等排廢氣管道中的集塵器捕集至少含有釩之燃 燒灰的濕式處理方法，其特徵爲包括：將上述石油系燃燒 灰中之釩溶解在水中之燃燒灰砂漿調製工程；在硫酸銨之 存在條件下，對燃燒灰砂漿供給阿摩尼亞（氨）及氧化氣 體使釩進行氧化而調製成含有偏釩酸銨（ammoniom metavanadate) 之砂漿的金屬氧化工程； 將含有偏釩酸銨 （ ammoniom meta-vanadate)之砂漿中去除固體成份之固液 本紙張尺度適用中周國家標準（CNS ) A4規格（21〇><297公釐) " ' 567097 A7 __ B7 五、發明説明（5 ) (請先閲讀背面之注意事項再填寫本頁) 分離工程；對從該當固液分離工程中回收之硫酸銨水溶液 添加使水溶性硫酸鹽形成之金屬化合物之硫酸銨複分解工 程；從該當複分解工程中所回收之複分解液中將阿摩尼亞 (氨）進行回收之阿摩尼亞（氨）回收工程；接著，上述 之金屬氧化工程係在水溶液中之硫酸錶濃度爲2 0〜4 0 重量％且溫度爲5 0°C以下之條件下進行，而上述之固液 分離工程係在使用過濾型固液分離裝置且砂漿溫度爲4 0 °C以下之條件下進行。 以下，根據所附圖面對本發明進行詳細說明。 於本發明之處理方法中，成爲處理對象之石油系燃燒 灰，係爲藉由設置在使用石油系燃料之鍋爐等排廢氣管道 中的集塵器捕集至少含有釩之燃燒灰。如此之燃燒灰，如 ,上述般，係由在燃燒氣體中添加阿摩尼亞（氨）或是氧化 鎂進行運轉之各種燃燒爐（燃燒裝置）之電力集塵器來回 收。特別是，本發明，係最佳適用在釩含量高之> ◦RIMULSION」燃燒灰。 經濟部智慧財產局員工消費合作社印製 本發明之濕式處理方法，依順序係包括：燃燒灰砂漿 調製工程（A );金屬氧化工程（C );固液分離工程（ E ):硫酸銨複分解工程（F ):阿摩尼亞（氨）回收工 程（G )。 接著，於本發明之最佳形態中，係包括：在燃燒灰砂 漿調製工程（A )與金屬氧化工程（C )之間配置P Η調 整工程（Β):在金屬氧化工程（C)與固液分離工程（ Ε )之間配置結晶工程（（D ):在硫酸銨複分解工程（ 1紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐] "" -8- 567097 A7 B7 五、發明説明（6 ) F )之後依序配置溫排水冷卻工程（Η )及排水處理工程 (I ) 〇 (請先閱讀背面之注意事項再填寫本頁) 於燃燒灰砂漿調製工程（A )中，將燃燒灰與水進行 混合而調製燃燒灰砂漿。此時所使用之水量，係需視後述 金屬氧化工程（C )所要求之硫酸銨濃度（2 0〜4 5重 量％ )再決定。 於P Η調整工程（B )中，對上述燃燒灰砂漿之P Η 進行調整。即，後述金屬氧化工程（C )，係在中性或鹼 性之條件下進行。因此，於Ρ Η調整工程（Β )中，燃燒 灰砂漿之Ρ Η値，通常調整爲7以上，最佳爲調整成7〜 9。ρ Η之調整，亦可藉由供給有反應成份之阿摩尼亞（ 氨）水或銨化合物來進行調整。僅以調整Ρ Η本身爲目的 時雖亦可使用苛性蘇打等之苛性鹼，但爲避免帶進反應系 中新的化學種，最好是使用阿摩尼亞（氨）水或銨化合物 來進行調整。 另，燃燒灰砂漿之Ρ Η調整，亦可在金屬氧化工程（ C )之氧化槽中，於氧化反應前進行調整。 經濟部智慧財產局員工消費合作社印製 於金屬氧化工程（C )中，在硫酸銨之存在條件下， 對燃燒灰砂漿供給阿摩尼亞（氨）及氧化性氣體使釩進行 氧化而調製成含有偏釩酸鏡（ammoniom meta-vanadate) 之砂漿。做爲阿摩尼亞（氨），例如可使用在後述之阿摩 尼亞（氨）回收工程所得之阿摩尼亞（氨）。做爲氧化性 氣體，例如有空氣、氧氣、臭氧，但從實用性之觀點來看 最好是使用空氣。 本紙張尺度適用中國國家標準（ CNS ) A4規格（210X297公釐） 567097 A7 B7 五、發明説明（7 ) (請先閲讀背面之注意事項再填寫本頁) 於本發明中，上述之金屬氧化工程（C)，重要的是 要在水溶液中之硫酸銨濃度爲2 0〜4 0重量％且溫度爲 5 0 °C以下之條件下進行。於此所謂水溶液中之濃度是表 示去除構成砂漿之固體成份後之水溶液中之濃度。硫酸銨 濃度未滿2 0重量％時於5 0 °C以下反應溫度之反應速度 會降低使反應時間變長，硫酸銨濃度超過4 0重量％時硫 酸銨會被析出。另一方面，若反應溫度超過5 0 °C時，會 使要將在下個工程之結晶工程（D )或固液分離工程（E )所要求之砂漿冷卻爲溫度（4 0 °C )以下之能源成本變 大。硫酸銨濃度最佳爲3 0〜4 0重量％，反應溫度最佳 爲2 0〜4 0 t。硫酸銨濃度之調整，除了燃燒灰砂漿之 調製時所使用之水量外，亦可藉由從固液分離工程（E ) 回收之硫酸銨水溶液的添加來進行調整。 經濟部智慧財產局員工消費合作社印製 於結晶工程（D )中，係對在金屬氧化工程（C )所 得之砂漿進行冷卻，而析出偏釩酸銨（a m m ο n i 〇 m m e t a -vanadate )之結晶。於本發明中，偏釩酸銨之結晶，雖係 於下個工程之固液分離工程（E )中，與碳等同時被固液 分離，但藉由在結晶工程（D )事先析出偏釩酸銨之結晶 ，故可使固液分離工程（E )中之偏釩酸銨的回收率變高 〇 做爲結晶工程（D )中之冷卻手段，最好是採用對含 有偏釩酸銨（ammoniom meta-vanadate)之砂漿導入冷卻 用空氣之直接冷卻手段。於利用熱交換器之間接冷卻手段 時，會招惹傳熱面之起鱗皮（scaling)問題，但藉由上述 本紙張尺度適用中國國家標準（CNS ) A4規格（21〇Χ；297公釐） -10- 567097 A7 B7 五、發明説明（8 ) 之直接冷卻手段可消除如此之問題。含有偏釩酸銨之砂漿 ’通常是冷卻爲4 0°C以下，最好市冷卻爲2 0〜3 〇 (請先閲讀背面之注意事項再填寫本頁) 爲要將其中所含之阿摩尼亞（氨）進行回收，故從結 晶工程（D )所排出之上述空氣，最好是導入砂漿調製工 程（A )之燃燒灰砂漿中。 於固液分離工程（E )中，係從上述含有偏釩酸銨（ ammoniom meta-vanadate)之砂漿中將固體成份（偏釩酸 銨結晶、碳等）進行去除。此時，於本發明中，係使用過 濾型固液分離裝置。 經濟部智慧財產局員工消費合作社印製 做爲過濾型固液分離裝置，通常以使用壓濾機（ filter press)爲最佳，可使用平槽型壓濾機（flush plate press)或凹槽型壓瀘機。此外，亦可使用離心式過濾器 。過濾型固液分離裝置最好是使用壓瀘機（filter press ) 。於本發明中，過瀘型固液分離裝置之使用結果，係與使 用沉澱濃縮裝置不同，在能有效率進行處理的同時又能達 成高之容積減少率。此外，過濾型固液分離裝置，即使與 離心沉降型固液分離裝置（例如傾析器）相比其固液分離 之效率仍爲高。 又，於本發明中，上述固液分離工程（E )，若省略 結晶工程（D )時，重要的是要在砂漿溫度4 0 °C以下之 條件下進行。砂漿溫度若超過4 0 °C時，就無法充分析出 偏釩酸銨（ammoniom meta-vanadate )。砂漿溫度最佳爲 2 0〜3 0°C。另，若在上述金屬氧化工程（C)副產生 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) ~ -11 - 567097 Α7 Β7 五、發明説明（9 ) 以鐵之氧化物爲主成份之鐵泥漿等固體成份時，這些固體 成份也會被上述之固液分離工程（E )分離。 (請先閱讀背面之注意事項再填寫本頁) 此外，於固液分離工程（E )中，爲要去除回收之塊 狀物中所含有之硫酸銨，最好進行塊狀物之洗淨處理。其 理由如下。即，在固液分離工程（E )所回收之含有偏釩 酸銨結晶、碳等的塊狀物，雖可利用在與還原劑之碳同時 處理之眾所周知之有價金屬成份回收工序，但於該時，成 爲硫酸成份（S ◦ 4 )之硫酸銨的含量最好是較少。此外 ，附著在塊狀物中之硫酸銨，係藉由回收做爲洗淨後之排 水，可有效利用做爲砂漿調製工程（A )之用水。 上述之洗淨處理，例如藉由從壓瀘機之砂漿供給部供 給塊狀物洗淨水之方法就可容易進行洗淨處理。洗淨後之 塊狀物（以乾燥狀態爲基準）的硫酸銨含有率，最好是在 5重量％以下。 經濟部智慧財產局員工消費合作社印製 於硫酸銨複分解工程（F )中，對從上述固液分離工 程（E )所回收之濾出液（硫酸銨水溶液）添加可形成水 溶性硫酸鹽之金屬化合物。做爲可形成水溶性硫酸鹽之金 屬化合物代表者有氧化鎂或氫氣化鎂。藉由它們使硫酸銨 分解成阿摩尼亞（氨）和硫酸鎂（M g S〇4 )。由於硫 酸鎂爲水溶性不同於硫酸鈣（C a S〇4 )，故其不會造 成排水中產生浮游固體成份。 於複分解所使用之氧化鎂或氫氣化鎂的量，通常針對 硫酸根爲化學量論或是較其若干多餘之量。複分解後之液 體的p Η値，根據所含有之阿摩尼亞（氨）與未反應氫氣 本紙張尺度適用中國國家標準（CNS ) Α4規格（210><297公釐） ~ ~ -12 - 567097 A7 _ B7 五、發明説明（10) 化鎂等，通常爲8 · 5〜1 1，較多時爲9〜10。 (請先閲讀背面之注意事項再填寫本頁) 於阿摩尼亞（氨）回收工程（G )中，係將阿摩尼亞 (氨）從上述複分解液中進行回收。對於做爲阿摩尼亞（ 氨）分離裝置，雖並無特別限制，但通常是使用分離效率 佳之對流接觸分離裝置，其中，又以對流接觸塡充塔爲佳 ，再者，對分離媒體以使用水蒸氣爲更佳。對於做爲對流 接觸塡充塔，並無限制故可使用眾所周知者。於該塡充塔 內部，通常多量塡充有Rashihiring(音譯）、Gooshing ring(音譯）、馬鞍型塡料等表面積大之塡料。 圖示之阿摩尼亞（氨）回收工程（G )，係採用對分 離媒體使用水蒸氣之方法，其係由對流接觸分離裝置 (G 1 )、冷凝器（G 2 )、儲存槽（G 3 )形成。從流接 觸分離裝置（G i )回收之含有阿摩尼亞（氨）的水蒸氣 ，在冷凝器（G2)轉換成阿摩尼亞（氨）水，然後導入 儲存槽（G 3 )。 經濟部智慧財產局員工消費合作社印製 所回收之阿摩尼亞（氨）水，係利用在上述金屬氧化 工程（C )，又，阿摩尼亞（氨）氣體係供給在上述排廢 氣管道內，亦可做爲排廢氣中所含之硫酸氣體（S 〇3) 之中和劑來使用。 於溫排水冷卻工程（Η )中，對從阿摩尼亞（氨）回 收工程（G )排出之溫排水導入冷卻用空氣。溫排水冷卻 工程（Η )，係特別於採用對阿摩尼亞（氨）回收工程（ G )之分離媒體使用水蒸氣之方法時具有意義。 即，從阿摩尼亞（氨）回收工程（G )排出之溫排水 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） 567097 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（11 ) 的溫度通常是接近1 〇 °c。因此，於做爲最佳形態所設置 之下個工程得排水處理工程（I )(沉澱濃縮裝置）中， 若不處理如上述之溫排水時，會因液體之對流現象而使固 體成份之沉降速度降低。所以，於本發明中，爲要抑制溫 排水冷卻後之液體的對流現象，而設有溫排水冷卻工程（ Η )。從阿摩尼亞（氨）回收工程（G )排出之溫排水， 係於溫排水冷卻工程（Η )中被冷卻至2 5〜5 0 °C。 從溫排水冷卻工程（Η )排出之上述空氣，爲要回收 其中所含之阿摩尼亞（氨），最好方法是導入砂漿調製工 程（A )之燃灰砂漿中。 於排水處理工程（I )中，將從阿摩尼亞（氨）回收 工程（G )中回收之排水以沉澱濃縮裝置進行處理，並將 回收之砂漿供給在固液分離工程（E )。途示之排水處理 工程（I )，係由沉澱濃縮裝置（I ^ )和儲存槽（I 2 )形成。做爲沉澱濃縮裝置（I ^ )，雖有濃縮槽、沉降 槽、沉降圓錐等，但以使用濃縮槽爲佳。 排水中之浮游固體（S S )，係以鎂或鎳之氫氣化物 爲主要成份。由於這些之氫氣化物爲微粒子，故在過濾型 固液分離裝置容易造成阻塞，此外，於離心沉降型固液分 離裝置中也不容易分離。因此，於本發明中，並不藉由沉 澱濃縮裝置（I i )對濃厚之砂漿進行回收，而將回收之 砂漿供給在固液分離工程（E )，與碳、偏釩酸銨（ ammoniom meta-vanadate )、鐵泥漿等之固體成份同時一 起整合進行回收。 (請先閲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（210X297公釐） -14- 567097 Α7 Β7 五、發明説明（12) (請先閲讀背面之注意事項再填寫本頁) 從排水處理工程之儲存槽（I 2 )排出之廢液，由於 實質上並不含有浮游固體（SS)，只含有些許量之阿摩 尼亞（氨），故可依其原狀放流，或者是，以活性污泥進 行處理後放流。 於本發明中，將容積減少率高之固液分離工程（E ) 配置在金屬氧化工程之後，藉由如此唯一之固液分離工程 (E )對有價成份之釩的實質全量進行回收。因此，將固 液分離工程（E )之溫度限制成低，再者，藉由將做爲其 前之工程的金屬氧化工程（C )之溫度限制成低來降低能 源成本。然後，對於如此之金屬氧化工程（C )中反應速 度之降低則藉由提高硫酸銨之濃度來補救。接著，燃燒灰 中之釩，雖被濃縮且與還原劑之未燃碳同時由上述固液分 離工程（E )進行回收，但此時，成爲浮游固體（S S ) 之其他金屬成份也同時被回收。 〔發明之最佳實施形態〕 經濟部智慧財產局員工消費合作社印製 以下，根據實施例對本發明進行更加詳細之說明’但 本發明在不超過其主旨範圍，並不限定於以下之實施例。 實施例1 做爲石油系燃燒灰，係對使用燃料爲^ ◦ R I M U L S I ◦ Ν」之鍋爐燃燒爐排廢氣管道內持續供給阿摩尼亞 (氨）且藉由配置在管道末端之電力集塵器所補集，並且 使用以下表3所示組成（乾粉狀態）之石油系燃燒灰。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X297公釐） -15- 567097 A7 B7 五、發明説明（13 ) (表3 ) 成份 C NH4 S〇4 V Ni Mg 重量％ 1.0 18.0 60.0 4.5 1.0 0.3 (請先閲讀背面之注意事項再填寫本頁) 首先，於燃燒灰砂漿調製工程（A )中，將石油系燃 燒灰與水進行混合，接著加熱至5 0 °C調製成燃燒灰砂漿 。燃燒灰水溶液中之硫酸銨的濃度爲3 0重量％。然後， 於P Η調整工程（B )中對上述燃燒灰砂漿內供給後述阿 摩尼亞（氨）回收工程（G )所分離之阿摩尼亞（氨）水 使燃燒灰之Ρ Η値調整爲9。 經濟部智慧財產局員工消費合作社印製 其次，於金屬氧化工程（C )中，將上述砂漿以4 m 3 / h r之比率供給在配置有攪拌翼及加溫裝置之容量 1 0 m 3的密閉型金屬氧化槽內，將空氣以6 0 N m 3 / hr及3氣壓之加熱水蒸氣以0 · 1〜0 · 2Ton/ h r之比率，從金屬氧化槽所具備之氣體供給管導入在砂 漿中，使砂漿持續氧化，以獲得含有偏釩酸銨（ am moniom meta-vanadate)之燃燒灰砂漿。金屬氧化槽內 之溫度爲5 0 t：。 接著，於結晶工程（D )中，以冷卻用空氣對含有偏 釩酸銨（a m m ο n i 〇 m m e t a - v a n a d a t e )之燃燒灰砂漿進行吹 送將砂漿溫度冷卻成3 0 °C以析出偏釩酸銨（ammoniom meta-vanadate)之結晶。然後，於固液分離工程（E )中 ，使用壓濾機，對上述砂漿進行處理。接著從壓濾機之砂 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -16 - 567097 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明説明（14 ) 漿供給部供給洗淨水進行塊狀物之洗淨。其結果，回收了 以碳爲主要成份且釩濃度（乾粉狀態）高達約1 7重量％ 之塊狀物。又，乾燥後塊狀物中之硫酸銨含有率爲1重量 %。 其次，於複分解工程（F )中，將從上述固液分離工 程（E )所回收之硫酸銨水溶液供給在反應器然後添加氧 化鎂使硫酸銨進行複分解。 接著，於阿摩尼亞（氨）回收工程（G )中，將上述 複分解液供給在對流接觸塡充塔，使阿摩尼亞（氨）與水 蒸氣同時被分離回收。即，將上述之複分解液加溫成8 0 °C後，以5，0 0 0 K g /小時之比率供給在塡充塔上部 。此外，並行作業，將做爲分離媒體之1 6 0 °C的水蒸氣 以1，5 0 0 K g /小時之比率供給在塡充塔下部。另， 對流接觸塡充塔之塡料收容室的容積爲1 · 0 m 3，塡料 爲SUS304製凹型塡料（lOOKg)。 其次，於溫排水冷卻工程（Η )中，將冷卻用空氣導 入在從上述阿摩尼亞（氨）回收工程中所回收之溫度約 9 5 °C之排水中，冷卻至約4 0 t。然後，於排水處理工 程（I )中，使用濃縮器，對從上述溫排水冷卻工程（Η )所回收之排水進行處理。以濃縮器處理後之排水，係含 有阿摩尼亞（氣）150ppm、釩lOppm、鎳10 p p m。又，被濃縮之砂漿係供給在上述固液分離工程與 含有偏釩酸鏡（ammoniom meta-vanadate)之燃燒灰砂漿 同時一起進行處理。 (請先閲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（210X297公釐） -17- 567097 A7 B7 五、發明説明（15) 根據以上所說明之本發明，可提供一種特別適合使用 在需處理之燃燒灰量較少時，或者是’燃燒灰中之碳含量 少且釩含量高時，以簡單之工序就容易回收釩之有利工業 性之方法。 〔圖式之簡單說明〕 第1圖爲表示本發明相關之石油系燃燒灰處理方法的 最佳一例之前段工程說明圖。 第2圖爲表示本發明相關之石油系燃燒灰處理方法的 最佳一例之後段工程說明圖。 (請先閲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 主要元件對照表 A 砂漿調製工程 B P Η調整工程 C 金屬氧化工程 D 結晶工程 E 固液分離工程 F 複分解工程 G Ν Η 3回收工程 Gi 對流接觸分離裝置 G 2 冷凝器 G 3 儲存槽 Η 溫排水冷卻工程 I 排水處理工程 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -18- 567097 A7 B7 五、發明説明（16 ) 11 沈澱濃縮裝置 12 儲存槽 (請先閲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 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）567097 Μ ____ Β7 V. Description of the invention (1) [Technical field to which the invention belongs] (Please read the precautions on the back before filling out this page) This invention relates to the wet treatment method for petroleum-based combustion ash. The wet treatment method for capturing combustion ash containing at least vanadium by a dust collector installed in an exhaust gas pipe such as a boiler using petroleum-based fuel is particularly suitable for use when the amount of combustion ash to be treated is relatively small. When there is less, or when the carbon in the combustion ash is small and the vanadium content is high, the vanadium is an advantageous industrial method that can be easily recovered with a simple process. [Know-how] In various combustion furnaces (combustion devices) that use petroleum-based fuels (for example, heavy oil, "ORIMULSION", etc.), for example, in boilers such as thermal power plants and waste incinerators, to prevent burning gas Corrosion caused by the sulfuric acid gas (S03) generated in the process, Ammonium (ammonia) is added to the gas. In addition, magnesium oxide is used in place of Armonia (ammonia). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In addition, the above-mentioned "ORIMULSION" is an ORIMULSION fuel formed by natural asphalt dispersed in water with a surfactant, and the natural asphalt is Orinoco from Venezuela, South America ) Natural bitumen produced in the river basin is a registered trademark of BIT OR in Venezuela. / Therefore, in the combustion ash collected and recovered by the electric dust collector disposed on the rear stream side of the flue, in addition to the ash components mainly containing unburned carbon and heavy metals (N i, V, M g, etc.) In addition, thallium contains ammonium sulfate and the like. In particular, the combustion ash of "〇RIMULSION" contains less carbon. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) -4- 567097 A7 B7 V. Description of the invention (2) Contains more sulfuric acid (or sulfuric acid bell) and vanadium. For example, Table 1 shows the composition analysis (dry powder state) of the combustion ash recovered from the "◦ UM UL S ION" incinerator. (Table 1) Ingredient C ΝΗ4 S〇4 V Ni Mg Weight% 1 ～ 5 12 ～ 20 50 ～ 65 4 ～ 9 0.5 ～ 2 0.1 ～ 2 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs as the above-mentioned combustion ash. There are many proposals for a wet processing method, a technology called a wet process that recovers valuable components such as vanadium and seeks to prevent pollution by closing the system. Specifically, for example, there are Japanese Patent Laid-Open Nos. 6 0-1 9 0 8 6 which have been proposed by the applicant of the present case, Japanese Patent Laid-Open Nos. 6 0-4 6 9 3 0, and Special Fair 4 1 6 1 7 Wet process as described in each of Gazette No. 0-9, JP 5-1 3 7 1 8. As a specific example of the above-mentioned wet process, for example, the above-mentioned Japanese Patent Publication No. 5-1 3 7 18 describes a wet process of a petroleum-based combustion ash as described below. That is, the above wet process includes: (1) the first process of mixing combustion ash with water, adding sulfuric acid as needed to adjust the pH to a mortar state of 3 or less; (2) changing the solid content (carbon, etc.) The second project of separation; the third project of heating the liquid part to more than 70 ° C, and then supplying ammonium (ammonia) and oxidant to gradually adjust ρ Η to 7-9 to oxidize the metal; (4) The fourth process of separating the precipitate (iron slurry); (5) The fifth process of cooling the liquid part to below 40 ° C to precipitate fL compounds (ammonium metavanadate); (6) the vanadium to be precipitated This paper size applies to Chinese National Standard (CNS) A4 specifications (210 × 297 mm) (Please read the precautions on the back before filling this page) 567097 A7 B7 V. Description of the invention (3) (Please read the precautions on the back before filling (This page) The 6th process of separating compounds; (7) Adding calcium hydroxide or calcium oxide to the liquid part to precipitate gypsum and metal (nickel and magnesium) hydroxides, while freeing Armonia (ammonia) Project No. 7; Admiral Amo from the Free Amogna (Ammonia) The recovered after 8 alkylene Engineering (ammonia), and from the gypsum separation of Engineering 9. However, in the case of a large project like the above, it is not economical when the amount of combustion ash to be treated is small, or when the carbon content in the combustion ash is small and the vanadium content is high. The present invention is based on the above facts, and its purpose is to provide a method that is particularly suitable for use when the amount of combustion ash to be treated is small, or when the carbon content in the combustion ash is small and the vanadium content is high. An advantageous industrial method that can easily recover vanadium with a simple process. [Invention of Invention] Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The inventors obtained the results of repeated deliberate reforms to achieve the above-mentioned goals, and obtained the following ideas and knowledge. That is, if the valuable metal component in the combustion ash can be concentrated, the well-known valuable metal recovery technology can be applied while processing the unburned carbon of the reducing agent. For example, as shown in Table 2, one of the composition analysis (dry powder state) obtained when a large part of the sulfuric acid is removed from the combustion ash shown in Table 1 above and the valuable metal components are concentrated with unburned carbon at the same time. This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 567097 A7 ______B7 V. Description of the invention (4) (Table 2) Composition C NH4 S〇4 V Ni Mg Weight% 5 ~ 10 0.5 ~ 1.5 2 ～ 3.5 25 ～ 38 2 ～ 5 1 ～ 2 (Please read the precautions on the back before filling this page) Then, if you separate the solid components (carbon, etc.) in the second process of the above-mentioned conventional technology, you can recover substantially the entire amount When the valuable metal component is contained, the valuable metal component in the combustion ash is concentrated. In addition, by this, the process is simplified, and it becomes more advantageous when the amount of combustion ash to be treated is small, or when the carbon content in the combustion ash is small and the vanadium content is large. As a result of repeated review based on the above ideas, the acid reaction required when recovering vanadium can be easily carried out in the presence of a high concentration of ammonium sulfate, so it must be carried out even at a lower temperature. As a result, it is possible to separate and recover solid components (carbon, etc.) and valuable metal components at the low temperature required to continuously recover substantially all of the valuable metal components. The present invention is printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to complete the wet treatment method of burning ash based on the above-mentioned ideas and knowledge. The main purpose is as follows. The wet treatment method for the dust collector in the pipeline to capture combustion ash containing at least vanadium, which is characterized by: a combustion ash mortar preparation project in which vanadium in the petroleum-based combustion ash is dissolved in water; the presence conditions of ammonium sulfate Next, the combustion ash mortar is supplied with ammonium (ammonia) and an oxidizing gas to oxidize vanadium to prepare a metal oxidation process containing ammoniom metavanadate; ammoniom meta- vanadate) solid-liquid removal of solid components in mortar. The paper size is applicable to the China National Standards (CNS) A4 specification (21〇 > < 297 mm) " '567097 A7 __ B7 V. Description of the invention (5) ( Please read the precautions on the back before filling in this page) Separation project; add ammonium sulfate aqueous solution recovered from the solid-liquid separation project to add water-soluble sulfate Belongs to the compound ammonium sulfate metathesis project; the ammonium (ammonia) recovery project that recovers amonia (ammonia) from the metathesis liquid recovered in the current metathesis project; then, the above metal oxidation project is in an aqueous solution The concentration of sulfuric acid in the table is 20 to 40% by weight and the temperature is below 50 ° C. The above-mentioned solid-liquid separation process is a filtration-type solid-liquid separation device and the mortar temperature is 40 ° C. Performed under the following conditions. Hereinafter, the present invention will be described in detail based on the drawings. In the processing method of the present invention, the petroleum-based combustion ash to be treated is to capture the combustion ash containing at least vanadium by a dust collector installed in an exhaust gas pipe such as a boiler using petroleum-based fuel. Such combustion ash, as described above, is collected by electric dust collectors of various combustion furnaces (combustion devices) operated by adding ammonium (ammonia) or magnesium oxide to the combustion gas. In particular, the present invention is best suited for "> RIMULSION" combustion ash with high vanadium content. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the wet processing method of the present invention, which, in order, includes: combustion ash mortar preparation project (A); metal oxidation project (C); solid-liquid separation project (E): ammonium sulfate metathesis Project (F): Ammonia (Ammonia) Recovery Project (G). Next, in the best form of the present invention, it includes: disposing PP between the combustion ash mortar preparation process (A) and the metal oxidation process (C); the adjustment process (B): between the metal oxidation process (C) and the solid state Liquid separation project (E), crystallization project ((D)): ammonium sulfate metathesis project (1 paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) " " -8- 567097 A7 B7 five 1. Description of the invention (6) F) After that, the warm drainage cooling project (Η) and drainage treatment project (I) will be arranged in sequence (please read the precautions on the back before filling this page) in the combustion ash mortar preparation project (A) The combustion ash and water are mixed to prepare a combustion ash mortar. The amount of water used at this time depends on the ammonium sulfate concentration (20 to 45% by weight) required by the metal oxidation process (C) described later. In the P Η adjusting process (B), the P Η of the above-mentioned burning mortar is adjusted. That is, the metal oxidation process (C) described below is performed under neutral or alkaline conditions. Therefore, the P 于 adjusting process ( Β), P 燃烧 of the burning mortar, It is usually adjusted to 7 or more, and the best is adjusted to 7 to 9. The adjustment of ρ Η can also be adjusted by supplying ammonium (ammonia) water or ammonium compounds with reaction components. Only by adjusting ρ Η itself Although caustic soda such as caustic soda can also be used for this purpose, in order to avoid bringing new chemical species into the reaction system, it is best to use ammonium (ammonia) water or ammonium compounds for adjustment. In addition, combustion ash The adjustment of the mortar's pH can also be adjusted in the oxidation tank of the metal oxidation project (C) before the oxidation reaction. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the metal oxidation project (C) in the ammonium sulfate Under the existing conditions, the combustion ash mortar is supplied with Armonia (ammonia) and oxidizing gas to oxidize vanadium to prepare a mortar containing ammoniom meta-vanadate. As the ammonia (ammonia) For example, Ammonia (ammonia) obtained in the later-mentioned amonia (ammonia) recovery project can be used. As the oxidizing gas, for example, air, oxygen, and ozone, it is best from a practical point of view. Use air. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 567097 A7 B7 V. Description of the invention (7) (Please read the notes on the back before filling this page) In the present invention, the above-mentioned metal oxidation project ( C), it is important to carry out under the condition that the concentration of ammonium sulfate in the aqueous solution is 20 to 40% by weight and the temperature is below 50 ° C. Here, the concentration in the aqueous solution refers to the removal of the solid components constituting the mortar. The concentration in the subsequent aqueous solution. When the ammonium sulfate concentration is less than 20% by weight, the reaction speed at a reaction temperature below 50 ° C will decrease and the reaction time will be longer. When the ammonium sulfate concentration exceeds 40% by weight, ammonium sulfate will be precipitated. . On the other hand, if the reaction temperature exceeds 50 ° C, the mortar required for the crystallization process (D) or solid-liquid separation process (E) of the next process will be cooled to a temperature below 40 ° C. Energy costs have increased. The optimum concentration of ammonium sulfate is 30 to 40% by weight, and the optimum reaction temperature is 20 to 40 t. The adjustment of the ammonium sulfate concentration can be adjusted by adding the ammonium sulfate aqueous solution recovered from the solid-liquid separation process (E) in addition to the amount of water used in the preparation of the ash mortar. Printed in the Crystallization Project (D) by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the mortar obtained in the metal oxidation project (C) is cooled to precipitate the crystals of ammonium metavanadate (amm ο ni 〇mmeta-vanadate). . In the present invention, although the crystallization of ammonium metavanadate is in the solid-liquid separation process (E) of the next process, it is simultaneously solid-liquid separated with carbon, etc., but the vanadium vanadium is precipitated in advance in the crystallization process (D). The crystallization of ammonium acid can increase the recovery rate of ammonium metavanadate in the solid-liquid separation process (E). As a cooling means in the crystallization process (D), it is best to use ammonium metavanadate ( ammoniom meta-vanadate) direct cooling means of introducing air for cooling. When using the cooling means connected between the heat exchangers, it will cause scaling problems on the heat transfer surface, but with the above paper size, the Chinese National Standard (CNS) A4 specification (21〇 ×; 297 mm) is applied. -10- 567097 A7 B7 5. The direct cooling means of the invention description (8) can eliminate such problems. The mortar containing ammonium metavanadate is usually cooled below 40 ° C, and the best city cooling is 20 ~ 3 0 (please read the precautions on the back before filling this page). Nitrogen (ammonia) is recovered, so the above air discharged from the crystallization process (D) is preferably introduced into the combustion ash mortar of the mortar preparation process (A). In the solid-liquid separation process (E), solid components (crystals of ammonium metavanadate, carbon, etc.) are removed from the mortar containing ammoniom meta-vanadate as described above. In this case, in the present invention, a filtration-type solid-liquid separation device is used. Printed as a filter-type solid-liquid separation device by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, usually using a filter press is best. A flat plate filter or a groove type can be used. Press machine. Alternatively, a centrifugal filter can be used. The filter-type solid-liquid separation device preferably uses a filter press. In the present invention, the result of using the over-type solid-liquid separation device is different from the use of a precipitation concentration device, which can efficiently process while achieving a high volume reduction rate. In addition, the filtration-type solid-liquid separation device has a higher solid-liquid separation efficiency than the centrifugal sedimentation type solid-liquid separation device (such as a decanter). In the present invention, if the solid-liquid separation process (E) is omitted, if the crystallization process (D) is omitted, it is important to perform the process at a mortar temperature of 40 ° C or lower. If the mortar temperature exceeds 40 ° C, ammoniom meta-vanadate cannot be fully analyzed. The optimum mortar temperature is 20 ~ 30 ° C. In addition, if the paper size produced in the above-mentioned metal oxidation project (C) is applied to the paper size of China National Standard (CNS) A4 (210X297 mm) ~ -11-567097 Α7 B7 V. Description of the invention (9) Take iron oxide as In the case of solid components such as iron mud, which are the main components, these solid components are also separated by the solid-liquid separation process (E) described above. (Please read the precautions on the back before filling this page.) In addition, in the solid-liquid separation project (E), in order to remove the ammonium sulfate contained in the recovered block, it is best to clean the block. . The reason is as follows. That is, the masses containing ammonium metavanadate crystals, carbon, and the like recovered in the solid-liquid separation project (E) can be used in a well-known valuable metal component recovery process that is treated simultaneously with the carbon of the reducing agent. In this case, it is preferable that the content of ammonium sulfate which is a sulfuric acid component (S ◦ 4) is less. In addition, the ammonium sulfate attached to the block is recovered as the discharged water after washing, which can be effectively used as the water for the mortar preparation process (A). The above-mentioned washing treatment can be easily performed by, for example, supplying a block washing water from the mortar supply section of the press. The ammonium sulfate content of the washed mass (based on the dry state) is preferably 5% by weight or less. Printed in the Ammonium Sulfate Metathesis Project (F) by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the filtrate (ammonium sulfate aqueous solution) recovered from the above-mentioned solid-liquid separation project (E) is added with a metal that can form water-soluble sulfate Compound. Representative examples of metal compounds capable of forming water-soluble sulfates are magnesium oxide or magnesium hydride. With them, ammonium sulfate is decomposed into ammonium (ammonia) and magnesium sulfate (M g S04). Because magnesium sulfate is different from calcium sulfate (Ca S04) in water solubility, it does not cause floating solids in the wastewater. The amount of magnesium oxide or magnesium hydride used for metathesis is usually stoichiometric or a superfluous amount for sulfate. The p Η 値 of the metathesized liquid is based on the ammonium (ammonia) and unreacted hydrogen contained in the paper. The Chinese paper standard (CNS) A4 specification (210 > < 297 mm) is applicable to this paper size ~ ~ -12- 567097 A7 _ B7 V. Description of the invention (10) Magnesium etc. are usually 8 · 5 ~ 1 1 and more often 9 ~ 10. (Please read the notes on the back before filling this page.) In the Ammonium (Ammonia) Recovery Project (G), Amonia (Ammonia) is recovered from the above metathesis solution. Although it is not particularly limited as an ammonia (ammonia) separation device, it is usually a convection contact separation device with good separation efficiency. Among them, a convection contact charging tower is better. Furthermore, the separation medium is It is better to use water vapor. For convection contact charging towers, there are no restrictions and well-known ones can be used. Inside the concrete charging tower, a large amount of concrete is usually filled with materials having a large surface area, such as Rashihiring, Gooshing ring, and saddle materials. The illustrated ammonia (ammonia) recovery project (G) in the picture uses the method of using water vapor for the separation medium, which is made by convection contacting the separation device (G 1), the condenser (G 2), and the storage tank (G 3) Formation. The water vapor containing Armonia (ammonia) recovered from the stream contact separation device (G i) is converted into the Armonia (ammonia) water by the condenser (G2) and then introduced into the storage tank (G 3). The Ammonia (ammonia) water recovered by the employees ’cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs is used in the above-mentioned metal oxidation project (C), and the Ammonia (ammonia) gas system is supplied to the above-mentioned exhaust gas pipelines. It can also be used as a neutralizing agent for sulfuric acid gas (SO3) contained in exhaust gas. In the warm water drainage cooling project (Η), the warm water discharged from the Ammonia (ammonia) recovery process (G) is introduced into the cooling air. The warm drainage cooling project (Η) is particularly meaningful when the method of using water vapor for the separation medium of the Ammonium (Ammonia) Recovery Project (G) is used. That is, the paper used for the warm drainage from the Ammonium (Ammonia) Recycling Project (G) applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 567097 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The temperature of the invention (11) is usually close to 10 ° C. Therefore, in the drainage treatment project (I) (precipitation and concentration device), which is set as the best form, if the temperature drainage is not treated as described above, the solid components will settle due to the convection of the liquid. Reduced speed. Therefore, in the present invention, in order to suppress the convection phenomenon of the liquid after the hot-water drainage is cooled, a hot-water drainage cooling project (工程) is provided. The warm water discharged from the Ammonia (ammonia) recovery project (G) is cooled to 25 ~ 50 ° C in the warm water cooling project (Η). The best way to recover the above-mentioned air discharged from the warm drainage cooling project (Η) is to introduce it into the ash mortar of the mortar preparation process (A). In the drainage treatment process (I), the wastewater recovered from the Armonia (ammonia) recovery process (G) is processed by a sedimentation and concentration device, and the recovered mortar is supplied to the solid-liquid separation process (E). Tuxiu's drainage treatment project (I) is formed by a sedimentation and concentration device (I ^) and a storage tank (I2). As a precipitation concentration device (I ^), although there are concentration tanks, sedimentation tanks, and sedimentation cones, it is better to use a concentration tank. The suspended solids (S S) in the drainage are mainly composed of magnesium or nickel hydrides. Since these hydrides are fine particles, they are liable to cause clogging in a filtration type solid-liquid separation device, and they are not easily separated in a centrifugal sedimentation type solid-liquid separation device. Therefore, in the present invention, the thick mortar is not recovered by the precipitation and concentration device (I i), but the recovered mortar is supplied to the solid-liquid separation project (E), and the carbon and ammonium metavanadate (ammoniom meta) -vanadate), iron mud and other solid components are integrated together for recycling. (Please read the precautions on the back before filling this page) This paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -14- 567097 Α7 Β7 V. Description of the invention (12) (Please read the notes on the back first Please fill in this page again for details) The waste liquid discharged from the storage tank (I 2) of the drainage treatment project does not substantially contain suspended solids (SS) and contains only a small amount of Armonia (ammonia). It is discharged as it is, or it is discharged after being treated with activated sludge. In the present invention, the solid-liquid separation project (E) with a high volume reduction rate is arranged after the metal oxidation project, and the substantially entire amount of the vanadium with a valuable component is recovered by the only solid-liquid separation project (E). Therefore, the temperature of the solid-liquid separation process (E) is limited to low, and further, the energy cost is reduced by limiting the temperature of the metal oxidation process (C), which is the previous process, to low. Then, the reduction of the reaction speed in such a metal oxidation process (C) is remedied by increasing the ammonium sulfate concentration. Next, the vanadium in the combustion ash is concentrated and recovered with the unburned carbon of the reducing agent at the same time as the solid-liquid separation project (E), but at this time, other metal components that become floating solids (SS) are also recovered at the same time . [Best Embodiment of Invention] Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the following examples without exceeding the scope of the gist thereof. Example 1 As a petroleum-based combustion ash, Amonia (ammonia) is continuously supplied to an exhaust gas pipe of a boiler combustion grate using a fuel of ^ RIMULSI ◦ N, and an electric dust collector disposed at the end of the pipe is used. For the supplementary set, petroleum-based combustion ash having the composition (dry powder state) shown in Table 3 below was used. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -15- 567097 A7 B7 V. Description of the invention (13) (Table 3) Composition C NH4 S〇4 V Ni Mg wt% 1.0 18.0 60.0 4.5 1.0 0.3 (Please read the notes on the back before filling this page) First, in the combustion ash mortar preparation process (A), mix petroleum-based combustion ash with water, and then heat to 50 ° C to prepare a combustion ash mortar. The concentration of ammonium sulfate in the aqueous combustion ash solution was 30% by weight. Then, in the PΗ adjustment process (B), the above-mentioned combustion ash mortar is supplied with the Amonia (ammonia) water separated from the later-mentioned Amonia (ammonia) recovery process (G) to adjust the P 燃烧 of the combustion ash. Is 9. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Secondly, in the metal oxidation project (C), the mortar was supplied at a ratio of 4 m 3 / hr in a hermetically sealed container with a capacity of 10 m 3 equipped with stirring wings and a heating device. In the type metal oxidation tank, air is heated at 60 N m 3 / hr and 3 atmospheres of steam at a ratio of 0 · 1 ~ 0 · 2Ton / hr, and is introduced into the mortar from the gas supply pipe provided in the metal oxidation tank. To continuously oxidize the mortar to obtain a burning gray mortar containing ammonio meta-vanadate. The temperature in the metal oxidation tank is 50 t :. Next, in the crystallization process (D), the combustion ash mortar containing ammonium metavanadate (amm ο ni 〇mmeta-vanadate) is blown with cooling air, and the temperature of the mortar is cooled to 30 ° C to precipitate ammonium metavanadate. (Ammoniom meta-vanadate). Then, in the solid-liquid separation process (E), the above-mentioned mortar is processed using a filter press. From the sand paper size of the filter press, the Chinese National Standard (CNS) A4 specification (210X297 mm) is applied. -16-567097 A7 B7 Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs 5. Description of the invention (14) Pulp supply department Supply the washing water to wash the lumps. As a result, a block containing carbon as a main component and having a vanadium concentration (dry powder state) as high as about 17% by weight was recovered. The ammonium sulfate content in the dried mass was 1% by weight. Next, in the metathesis process (F), the ammonium sulfate aqueous solution recovered from the solid-liquid separation process (E) is supplied to a reactor, and magnesium oxide is added to metathesize the ammonium sulfate. Next, in the Armonia (ammonia) recovery project (G), the above-mentioned metathesis liquid is supplied to a convection contact filling tower, so that the ammonia (ammonia) and water vapor are separated and recovered at the same time. That is, the above-mentioned metathesis liquid is heated to 80 ° C, and then supplied to the upper part of the charging tower at a rate of 5, 000 Kg / hour. In addition, in parallel operation, water vapor at 160 ° C, which is the separation medium, is supplied to the lower part of the charging tower at a rate of 1,500 Kg / hour. In addition, the volume of the concrete receiving chamber of the convection contact concrete filling tower was 1.0 m 3, and the material was a concave type material (10OKg) made of SUS304. Secondly, in the warm drainage cooling project (Η), the cooling air is led into the wastewater recovered at the temperature of about 95 ° C from the above-mentioned Armonia (ammonia) recovery project and cooled to about 40 t. Then, in the drainage treatment process (I), the condensate is used to treat the wastewater recovered from the above-mentioned warm drainage cooling process (Η). The drainage after treatment with the concentrator contains 150 ppm of Armonia (gas), 10 ppm of vanadium, and 10 p p of nickel. The concentrated mortar is supplied to the above-mentioned solid-liquid separation process and processed together with a combustion ash mortar containing an ammoniom meta-vanadate. (Please read the precautions on the back before filling this page) This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -17- 567097 A7 B7 V. Description of the invention (15) According to the invention described above It can provide a favorable industrial method that is particularly suitable for use when the amount of combustion ash to be treated is small, or when the carbon content in the combustion ash is small and the vanadium content is high, and the vanadium is easily recovered in a simple process. [Brief description of the drawings] Fig. 1 is an engineering explanatory diagram of the first stage showing a preferred example of a method for treating a petroleum-based combustion ash according to the present invention. Fig. 2 is an explanatory diagram of the latter stage showing a preferred example of a petroleum-based combustion ash treatment method according to the present invention. (Please read the precautions on the back before filling out this page.) The comparison table of the main components printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A Mortar preparation project BP Η Adjustment project C Metal oxidation project D Crystallization project E Solid-liquid separation project F Metathesis G Ν Η 3 Recycling project Gi Convection contact separation device G 2 Condenser G 3 Storage tank Η Warm water drainage cooling project I Drainage treatment project This paper applies the Chinese national standard (CNS) A4 specification (210X 297 mm) -18- 567097 A7 B7 V. Description of the invention (16) 11 Precipitation and concentration device 12 Storage tank (please read the notes on the back before filling out this page) Printed on the paper by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The Chinese standard (CNS) A4 Specifications (210X297 mm)