201113478 六、發明說明： r發明所屬之技術領域:j 本發明係關於一種從實質上固態燃料來製造熱裂解氣 及/或合成氣的流體化床反應裝置，與用來加熱該流體化床 反應裝置的流體化床之電加熱工具。本發明進一步關於一 種在流體化床反應裝置（較佳為該型式）中從實質上固態燃 料製造合成氣之方法，與用來加熱該流體化床反應裝置之 流體化床的電加熱工具，該加熱工具包括一空腔及一與該 空腔毗連之經加熱的多孔及氣體可滲透區段。 L· ^tr ^ 從生質製造合成氣為未來氫經濟的關鍵技術。隨著 此，能量主要以氫運送至終端使用者。在氫經濟中，當使 用燃料電池時會產生過剩的電力。因此，在此熱控制的能 量經濟中，至今幾乎不需要電力網柵。經採集作為電力的 太陽能量則必需藉由水電解來轉換成氫。不可避免的是， 在此方法期間會形成純氧。可使用電力及氧氣二者來支持 熱化學氣化。 至今，用來對固態燃料變成合成氣之吸熱反應提供能 量的電力尚不常見，因為電力為高價值及昂貴的能量。但 是，在氫經濟中，電力的價值不會比熱高。二篇最近的發 明 DE 10 2008 014 799 Α1 及DE 10 2008 032 166 Α1利用此 來電加熱該流體化床反應裝置，而沒有擴張該電加熱器的架 構。 因為這些反應裝置約850°C的工作溫度相當接近灰渣 201113478 的炼點，使用生質、透過該喷嘴基座供應純氧將會超過灰 渣的炫點。不想要灰渣溶融，因為該灰渣則無法再使用作 為無機肥料。同樣地，流體化床反應裝置之操作不可能含 有熔融的灰渣。但是’若使用大氣的氧氣時，其操作可能 不超過灰渣熔點，然而在此情況中氮會進入該合成氣中。 藉由沙再循環系統連接的雙流體化床反應裝置找到解答。 此之一個實施例為在奥地利（Austria)的辜新（Gussing)鎮中 之8MW設施。於此，僅使用空氣來加熱該旋轉的沙床及分 別地排出。因此’未發現氮氣進入合成氣的路徑中。 因此，若欲選擇性地使用電力或氧氣時，則在每個情 況中需要分別特定設計的流體化床反應裝置° C 明内】 本發明以提議出一種流體化床反應裝置及操作其之方 法的目標為基礎’其中以簡單方式使用電力來加熱該流體 化床及其中可避免灰渣'熔融。 此目標由申請專利範圍第1及11項之特徵達成。申請專 利範圍第2至1〇及12至16項係關於本發明之進一步優良的 具體實例。 就設備而論’所提供的電加熱工具包括至少一個空腔 及一與該空腔連的多孔區段。 另一方面’就方法而論’本發明提供將氣體經由多孔 區段從外部導向空腔及/或從空腔導向外部。 因此，已提供一種具有多孔區段的電加熱器，其中該 氣體可選擇性以一種或其它方法流過。此允許在實質上與 201113478 焦炭粒子呈空間分離下於流體化床反應裝置的流體化床中 加熱該氣體’因為焦炭粒子無法渗透過該多孔區段的孔洞 系’先此避免將焦炭粒子直接加熱至溫度高於灰渣炫點。 於此，多孔區段意謂著一具有開口孔隙率…pen p〇_ty)的區段’其因此形成以便氣體可渗透。 ,該加熱工具的多孔區段可或可不直接加熱。在後者的 ft况中’该多孔區段作用為該加熱工具之實際加熱區段的 屏障’以阻擔焦炭粒子到達此加熱區段為較佳。然後，在 相對於該加純段的外面區射提供該纽區如便能夠 滿足此功能為較佳。若應該能夠滲透氣體時，則該加熱工 具的加熱區段其自身可形成如為多孔區段；或若可省掉 體渗透作_ ’討以《不錢構件提供。 、 為了簡化事件及為了避免不需要的重覆，一起描述根 康该设備及根據财法的較佳具體實例。因此 乂 技術者提供本發_較佳細微㈣之適#的各別特徵W 但是，亦可對與該空腔眺連的多孔區段提供Μ 別是，該經加熱的纽區段可騎加#具的純電阻考 之部分。於此情況巾，該加熱多㈣段形成該純工且的 加熱電阻器之至少部分。但是，該加熱工具亦可以不^ 絲電加熱⑽如，藉㈣導）。然後，魏體當流過該加教 夕孔區段時可被加熱，且焦炭粒子不能夠進人該加孔、 區段之孔洞系統。為了進一步遮擋該加熱工具的加敎、多孔 區段，可雜加熱4提供進— Μ多孔未加_段(其配 置在該已加熱的多孔區段外部）。 201113478 在該流體化床反應裝置的較佳具體實例中，該加熱工 具包括一用來將氣體供應至空腔及/或從空腔排出氣體之 埠。以此方法，可將氣體供應至該加熱工具及藉由該加熱 工具加熱且如需要經由一埠排出該氣體。對氣體來說，另 一種可能性為從流體化床反應裝置流入該空腔中。在此期 間，該氣體可被加熱，隨後從該流體化床反應裝置移出。 亦可同步或交替地應用此二方法的原理。於此情況中，最 好提供一用來供應氣體的埠及一進一步用來排出大概不同 的氣體之埠。特別是，欲供應的氣體可為含氧氣體，也就 是空氣或工藝氧氣。該含氧氣體可經由與可燃燒氣體（例 如，熱裂解氣或合成氣）氧化而促成進一步釋放出熱。 該加熱工具包括（至少在某些區域中）雙壁及該雙壁的 外壁包括一多孔區段可特別佳。因此，產生一中間空間， 其與該流體化床反應裝置的流體化床之焦炭粒子空間地分 隔開。然後，焦炭粒子可例如不到達該雙壁之經加熱的内 壁（其自身不必需多孔）。例如，可使用該中間空間將含氧氣 體或不同氣體(諸如包含焦油的熱裂解氣）引進其中。然後， 在該中間空間中或在該多孔區段的孔洞系統内，該氧氣氧 化該可燃燒氣體為較佳，因此加熱該流體化床反應裝置額 外或再者該電加熱工具。然後，在該中間空間中，該熱裂 解氣的焦油可在高溫下裂解而沒有形成熔融的灰渣。 但是，若需要時，該雙壁的内壁可包括多孔區段，特 別在欲將氣體供應至由該内壁所形成的中間空間中之情況 下，此作出貢獻。如需要的話，此可為含氧氣體、可燃燒 201113478 氣體及/或含焦油的熱裂解氣。可獲得該空腔及中間空間二 個艙，其可分別引進含氧氣體及可燃燒氣體，然後可將該 等氣體帶至一起（也就是在中間空間中），以便於此彼此反 應。在此處，該合成氣亦可視為可燃燒氣體。但是，其亦 可沒有氧氣而引進該空腔中，以便在該内壁的多孔區段中 轉換所包含的的焦油。此可觸媒地進行，諸如經由在該孔 洞系統的表面上之觸媒材料。於此，可由該額外的外壁遮 擋來自流體化床的焦炭粒子之溫度提高（其藉由内壁的多 孔區段之加熱進一步增加）。含有至少部分已移除焦油之氣 體或至少部分已氧化的氣體可經由外壁的多孔區段釋放至 流體化床中。若經由各別的埠排出各別氣體時，亦可在外 壁中不具有多孔區段。 因此，依該流體化床反應裝置之想要的操作而定，該 雙壁之内壁及/或外壁可包括經加熱的多孔區段。此外，該 内壁及/或外壁可形成一中間空間，及該加熱工具可包括一 用來將氣體供應至該中間空間及/或用來從該中間空間排 出氣體之琿。然後，該流體化床反應裝置之具體實例可各 別適應所使用之氣體或該流體化床反應裝置之想要的操 作。 若該加熱工具、内壁及/或外壁的多孔區段包含觸媒或 從觸媒材料製造時，則其特別適合於被包含在熱裂解氣或 合成氣中的焦油之觸媒性裂解。該加熱工具較佳包含該觸 媒材料的區域遵循來自該流體化床反應裝置之各別先前討 論的較佳操作。 201113478 以包含複數根輸送管（包括空腔）的加熱工具達成該流 體化床反應裝置之特別簡單及成本有效的具體實例。這些 可在合理的成本下容易地分佈在該流體化床中及各別多孔 地製造或含有多孔區段。 在雙壁的情況中，為了上述提及的理由，想要其應該 各別由内輸送管及同中心的外輸送管形成。其則由複數組 至少二根輸送管組成為較佳，其一根輸送管為内管及另一 根輸送管為同中心的外輸送管。然後，該二根輸送管之一 為多孔或包括至少一個多孔區段。但是，亦可為每根輸送 管皆為多孔或包括至少一個多孔區段，每個多孔區段不必 需電加熱。 為了在該加熱工具中轉換熱裂解氣或合成氣的焦油， 可在將各別氣體引進該空腔中前，將觸媒作用的助濾劑加 入至其。然後，將該助濾劑沉積在該加熱工具的多孔區段 處，及若需要時其可重覆使用。 為了保證所使用的氣體以想要的方式流過該加熱工具 所標出的空腔、中間空間及/或多孔區段，可在該加熱工具 之空腔及/或中間空間上強加壓力擺盪(較佳為脈動）。該壓 力擺盪提供氣體流動的驅動壓力差，且其大到能讓該氣體 在多孔區段内的流動方向隨著每次壓力擺盪翻轉為較佳。 特別是，若來自流體化床反應裝置的氣體（其可為含焦油的 熱裂解氣或含焦油的合成氣）被吸引進入加熱工具中及隨 後不被排出而是被回饋進入該流體化床反應裝置中時，此 為一種選擇。 8 201113478 根據本發明的較佳具體實例，該流體化床反應裝置裝 備一包含氣體可滲透的輸送管之電加熱器，在其中如需要 可進料氧氣而不會在該流體化床中熔融該灰渣。 本發明合適於加熱在流體化床反應裝置中之全部型式 的流體化床’特別是含或不含惰性床材料的再循環式流體 化床及固定式流體化床。亦可隨著此安排，使用焦炭粒子 來加熱氣體艙。這些氣體艙可設置在固定式流體化床上及 可藉由穿孔板或噴嘴格柵分開（串接），如此就反應而論，形 成一系列的攪拌槽。 此外’該流體化床反應裝置可再者或額外地為一種用 於固態燃料(特別是生質）之熱裂解的熱裂解反應裝置。就合 成氣反應裝置的意義來說’其亦可為一種用於從該型式之 固態燃料（諸如生質）及較佳為從該型式之熱裂解反應裝置 的熱裂解氣產生合成氣之流體化床反應裝置。但是，如需 要時其亦可為一種用於熱裂解及蒸汽重組而包含複數個 流體化床的綜合反應裝置。然後，該流體化床反應裝置包 含—熱裂解反應裝置作為該反應裝置的部分及一合成氣反 應農置作為該反應裝置的另一部分二者。 就本發明來說，採用“實質上固態燃料，，以意指為在正 中條件下呈現出完全或部分固相的燃料。使用生質作為燃 料為較佳。 5亥電加熱器包括氣體可滲透的中空主體，例如，由多 孔燒結的導電輪送管製得。適當地為了將在流體化床之輸 送皆與焦炭粒子間的溫度差保持在極限内，在流體化床中 201113478 安排大量的這些輸送管為較佳。該輸送管亦可由一在具有 穿孔(如需要）的金屬輸送管與多孔輸送管間之組合組成，在 該金屬輸送管中產生歐姆熱。 可藉由對輸送管末端施加電壓及/或藉由供應氧氣及 流過該多孔輸送管來提供加熱該流體化床（例如，以歐姆 熱）。最好該加熱工具的金屬輸送管提供作為該加熱工具之 加熱電阻器。但是，誘導加熱該輸送管亦可理解。 為了方便，下列部分僅提到輸送管，因為為了成本的 理由，該加熱工具包含複數根輸送管為較佳。該包含複數 根輸送管的加熱工具之具體實例並無強制，即使此未每次 提到。亦可使用其它結構。 為了以氧氣操作，至少一根輸送管末端包含一氣體 埠。氧氣導致包含在流體化床中的氣體氧化或部分氧化。 氧氣意謂著工藝上純氧為較佳。可在外輸送管層的孔洞中 或直接在輸送管處於界面層處發生此與氧氣之反應，因此 包含在流體化床中的焦炭不被氧氣氧化，但是輸送管被加 熱，藉由輻射、傳導及對流將其熱轉移至流體化床。當在 流體化床中的焦炭粒子轉變成氣體（例如，經由吸熱反應) 時，該焦炭粒子通常比該輸送管及/或流體化床冷。 在加熱工具之操作上，所包含的氣體之流動方向一方 面可由在空腔與流體化床間之壓力差或在空腔與中間空間 間之壓力差，及另一方面該流體化床所限定。隨著施加相 應的壓力差，氣體從流體化床反應裝置流入輸送管，然後 在内輸送管壁處由來自含氧氣體（其經由合適的槔進料至 10 201113478 該輸送管的空腔)之氧氣氧化。如需要，每根輸送管具有二 個埠，一個用來供應氧氣及其它用來排出經氧化的氣體。 對此情況來說，空氣作為該含氧氣體亦非常合適，因為合 成氣不會被氮氣稀釋，因為經氧化的氣體會被排出。此方 法在含有惰性床材料的流體化床中優良，因為該惰性床材 料然後將再次透過磨擦立即地移除任何形成的微粒狀物質 層（就濾餅而論）。 隨著提供適當設計的加熱工具，該流體化床反應裝置 可以電力、氧氣或二者並行（如需要的話)加熱。 在電操作期間，亦可使用至少一根多孔輸送管來觸媒 減少焦油。可例如在合成氣產生之上游製程（諸如熱裂解） 中產生含焦油的氣體。產生熱裂解氣的預備階段描述在DE 198 07 988 A1及DE 10 2008 032 166 A1 中。若將已經移除 粉塵的熱裂解氣引導通過該多孔輸送管時，在這些輸送管 中增加的溫度將造成多數焦油在其中裂解。當使用生質作 為進料時，輸送管的溫度必需依生質型式而不超過溫度從 700°C至120(TC。因此’對溫度敏感之任何生質材料來說， 該導電（即’經加熱)輸送管由進一步的多孔輸送管同中心地 包圍之安排優良。然後’該外多孔輸送管作用為熱電阻器。 若在輸送管間餘留小的間隙時，其效應可甚至進一步增 加。因此’該内輸送管能夠變成非常熱而沒有在外輸送管 上聚集灰渣沉積。不需要加熱各別的外輪送管，因此其不 需導電。因此，該輸送管可由陶曼製得，及可例如形成如 為推到各別的内輸送管上之套筒。 201113478 對内輸送管來說，由於碳化矽在還原性大氣氛中的高 溫穩疋性，其特別合適。配備其與焦油裂解觸媒亦有用。 例如，週期系統的第VIII族之以鎳為基礎的觸媒合適，其亦 會破壞乱。所描述的型式之内輸送管揭示例如在De 1 〇 1 〇9 9 8 3 A1中。摻雜以Mg0、Zr〇2或Zr〇2_Μα之以鎳為基礎的 觸媒亦優良。 右將熱裂解氣進料至該加熱工具例如以轉換包含在其 中的任何焦油時，則該熱裂解氣以本身已知的方式(例如， 在溫度500°C至70(TC下使用氧化鈣(CaO))先前粗脫硫可為 適當。由於該脫硫，可降低該内輸送管的溫度。氧化鈣亦 合適作為内輸送管的助濾劑（預塗層）以吸收來自熱裂解氣 之殘餘粉塵。藉由施加真空及/或壓力定期地移除該助濾劑 為較佳。此程序已知來自卡匣式過濾器之操作。同時，若 該内輸送管被分成不同群組（其每個具有自己的氣體埠） 時，其方便。此允許實際上連續操作，因為為了清潔的目 的，僅有各別獨自的輸送管曝露至有關的壓力衝擊。 因為氧化鈣支援焦油裂解，其可使用來取代内輸送管 的觸媒塗層或與其互補。氧化舞亦能夠在較高溫度下黏姅 氣及硫。但是’因為氯化物及硫醚的溶點各別為75〇〇C及772 °C，大部分生質型式必需包括上述提及的粗脫硫。其它試 劑亦合適作為助濾劑，諸如橄欖石，其可使用來取代氧化 飼或與其一起使用。 若欲將來自流體化床反應裝置的任何熱裂解上游之熱 裂解氣完全或以任何比例部分地傳導過該加熱工具的中空 12 201113478 主體時，則其潛在可能獲得不足的流體化氣體。例如，若 水洛π及重組製程所需要之可能的額外氣體不符合所需要 之流體化氣體的要求量時，則可再循環在流體化床反應裝 置中所產生的部分氣體(例如，合成氣），即，在越化床反 應裝置的頭處抽出且將其回饋至基底中。於此情況中，具 有減少式錐形㈣嘴格栅為較佳，通過其來傳導流體化氣 體及再循環氣體。 戎輸送管亦可以群組安排，如此僅有部分的輸送管提 供含焦油氣體之觸媒裂解，及其它群組的輸送管則由氧氣 加熱。此可在相同流體化床中發生，但是亦可在配置於該 製程的上游或下游之流體化床中發生。不同安排及/或操作 的輸送管群組之其它組合可理解。 若該輸送管配備有用於焦油裂解之觸媒時，以從0.1赫 茲至10,000赫茲（較佳為在5至500赫茲間）的脈動壓力擺盪 來加壓該輸送管之内部空腔是有利的。壓力擺盪促進在多 孔輸送管中物質交換。依振幅而定，它們亦可將用於觸媒 性轉換的產物氣體抽入孔洞中一段短時間。可以本身已知 的方式藉由薄膜振動產生這些壓力擺盪。 本發明能夠依暫時及局部供應而選擇性以電力及/或 氧氣加熱。此讓使用來自風及光生伏打電力的局部電力產 生波峰（其無法使用）及使用來自電解槽的氧氣(在從這些來 源之小及中規模生產期間）可能。 本發明之一個優良用途為在流體化床反應裝置中裂解 焦油或在電加熱工具中裂解一熱裂解氣（諸如上游氣化階 13 201113478 段），而不需要昂貴及招致損失的額外製程。 現在，隨著參照僅顯示出典型具體實例的圖形來進一 步解釋本發明，其中： 第1圖顯示出根據本發明之具有固定式流體化床及加 熱器之流體化床反應裝置； 第2圖顯示出第1圖之管狀加熱器的截面； 第3圖顯示出根據第1圖作為材料組合的管狀加熱器之 截面； 第4圖顯示出具有複數個用來破壞焦油的流體化床與 加熱工具之流體化床反應裝置； 第5圖顯示出用來破壞焦油的加熱輸送管之截面；及 第6圖顯示出第5圖的縱區段。 C實施方式3 第1圖顯示出具有上端7及黏合喷嘴格柵11的下端之固 定式流體化床6的流體化床反應裝置5。該流體化床外罩1〇 在其下端處包括用來散佈已引進其中的流體化氣體13之氣 體艙9。在該流體化床6上，有一排出產物氣體14的自由空 間8。依操作而定，此可為熱裂解氣或合成氣。藉由於本文 中未顯示出的輸送工具將生質12a引進該流體化床反應裝 置中。流體化床反應裝置通常内襯著耐火性水泥。 為了讓吸熱反應能夠進入合成氣中，藉由包含複數根 形成空腔30的氣體可渗透輸送管1之加熱工具29來加熱該 流體化床反應裝置。輸送管1它們本身合適於電加熱電阻器 或由與進一步輸送管la(諸如陶瓷輸送管）組合之導電輸送 201113478 管lb形成。該輸送管形成加熱工具29的多孔區段31。 根據第3圖，在二根輸送管間安排一間隔器27，以讓流 過穿孔輸送管lb的孔洞所引進之氣體能夠有較好的分佈。 輸送管1具有一埠3及一在其末端處的閉合構造4。該流體化 床6可藉由對輸送管1的末端施加電壓及/或藉由供應氧氣 15a來加熱。 在引進氧氣期間，在流體化床中的氣體被部分氧化以 供應所需要的熱。氧化發生在多孔層中或直接在輸送管1的 界面層處。氧氣不會造成焦炭粒子燃燒，因為其在到達焦 炭粒子前已耗盡。熱從輸送管1藉由輻射、傳導及對流轉移 至流體化床6。輸送管表面及熱傳遞的品質決定在輸送管與 流體化床（其可由焦炭及惰性床材料組成）間之溫度差。 在含有惰性床材料(諸如沙）的流體化床中，熱傳遞比在 焦炭及灰渣塵雲中好。該流體化床6可獨自地藉由電力、獨 自地藉由氧氣或藉由二種製程同步地加熱。 第4圖顯示出含有複數個流體化床的流體化床反應裝 置5，其中該等流體化床在彼此之上且安排在共同的外罩10 中。在下部分中，有一含有惰性床材料的固定式流體化床 6，在其中引進來自上游製程（諸如熱裂解反應裝置）的焦 炭。在流體化床中，該焦炭經細微地研磨及藉由電加熱該 輸送管1部分轉換成熱裂解氣或合成氣。殘餘的焦炭隨著氣 體昇高。在外罩10的上部分中，有二個黏合穿孔板23、24 及25的流體化床28。該流體化床由未轉換的焦炭及灰渣粒 子組成。將穿孔板安排成能避免氣體及粒子回流，從而形 15 201113478 成检塞流(plug flGW)或-系列養槽的流動圖案。 此流特別合適於在輸送管1上及中之任何殘餘在氣體 中的焦油之觸媒裂解，及減少合歧μ在輸出口處的焦油 含量。若在氧氣15a的輸入口處使用一薄膜或活塞來產生川 至500_的脈動時’ _媒效射增加。㈣化床反應裝 置H)的此上部分可獨自地藉由電力、獨自地藉由氧氣以或 藉由二者同步地操作。將氧氣…經由中間基礎⑽料至氣 密埠3。 在第4圖的下部分中顯示出含有雙壁33之電加熱器1， 其包含一呈導電且經加熱的輸送管丨之形狀的内壁丨與一環 繞該導電輸送管1且呈非導電輸送管2的形狀之外壁。該輸 送管2可例如由安排在彼此之上且由彈簧壓緊的短陶瓷套 筒組成。間隔器27在輸送管1及2間形成一環形的中間空間 34。隨著此安排，若對輸送管1末端施加電壓時，此輸送管 1變成比輸送管2(其藉由在流體化床6中之好的熱轉移而冷卻） 熱。 此雙輸送管安排特別合適於藉由熱觸媒來破壞焦油。 來自上游製程之含焦油的熱裂解氣15b引進由板16及17所 形成且導向該輸送管之空腔中。在輸送管1末端處的閉合構 造4迫使熱裂解氣流過多孔輸送管1及2。二輸送管亦可具有 觸媒性塗層來支撐焦油裂解。若熱裂解氣15b不完全無粉塵 時，已推薦如卡匣式過濾器般操作該安排，其中藉由短暫 逆轉該壓力梯度來從輸送管中移除粉塵，及於此情況中其 會落入安排如為中空主體的噴嘴格栅中。該粉塵藉由由氣 16 201113478 體31驅動之氣流式振動裝備20輸送至板17的最低部分。從 此，經由鎖閘工具22從該製程移除粉塵。為了讓伴隨著清 潔操作之干擾達到最小’應該分割在板16與17間之空炉且 具有複數個用來引進熱裂解氣15b的埠。使用助濾劑（預涂 層）(諸如氧化鈣，其自身也具有好的焦油裂解致應）亦優 良。可將氧化妈加入至熱裂解氣15b。此輔助亦抑制炫融的 灰渣沉積積聚。在此安排中，該等噴嘴18必需每根皆途^ 二個板16與17。噴嘴18通常提供止回器19。 I：圖式簡單說明3 第1圖顯示出根據本發明之具有固定式流體化床ϋ 熱器的流體化床反應裝置。 第2圖顯示出第1圖之管狀加熱器的截面。 第3圖顯示出根據第1圖作為材料組合的管狀加熱器之 截面。 第4圖顯示出具有複數個用來破壞焦油的流體化床與 加熱工具之流體化床反應裝置。 第5圖顯示出用來破壞焦油的加熱輸送管之截面。 第6圖顯示出第5圖的縱區段。 【主要元件符號說明】 l··加熱輸送管 4...閉合栓 la·••導電加熱輸送管 5···流體化床反應裝置 lb··.非導電加熱輸送管 2··.加熱電阻器輸送管 3...蜂 6.. .流體化床 7.. .流體化床的上端 8.. .在流體化床上之自由空間 17 201113478 9.. .用於流體化氣體之散佈的 氣體搶 10.. .流體化床外罩 11.. .喷嘴格栅 12a.··生質 12b...來自部分轉換的生質之焦炭 13.. .流體化氣體 14.. .合成氣 15a...氧氣 15b...熱裂解氣 16.. .喷嘴格柵的上板 17.. .喷嘴格柵的下板 18.. .喷嘴輸送管 19.. .噴嘴輸送管的止回器 20.. .氣流式振動器 21.. .供應給振動器的氣體 22.. .用於粉塵的排出裝置 23.. .下穿孔板 24.. .中央穿孔板 25…上穿孔板 26.. .中間基礎 27.. .間隔器 28.. .焦炭塵雲流體化床 29…加熱工具 30.. .空腔 31.. .多孔區段 33.. .雙壁 34.. .中間空間 18201113478 VI. Description of the invention: Technical field in which the invention belongs: j The present invention relates to a fluidized bed reactor for producing pyrolysis gas and/or syngas from substantially solid fuel, and for reacting the fluidized bed An electric heating tool for a fluidized bed of the device. The invention further relates to a method of producing a syngas from a substantially solid fuel in a fluidized bed reactor, preferably in the form, and an electric heating tool for heating a fluidized bed of the fluidized bed reactor The heating tool includes a cavity and a heated porous and gas permeable section adjacent the cavity. L· ^tr ^ Synthetic gas from biomass is the key technology for the future hydrogen economy. As a result, energy is primarily delivered to the end user as hydrogen. In the hydrogen economy, excess power is generated when a fuel cell is used. Therefore, in this energy-controlled economy of heat control, power grids have hardly been needed so far. The amount of solar energy collected as electricity must be converted to hydrogen by electrolysis of water. Inevitably, pure oxygen is formed during this process. Both thermal and oxygen can be used to support thermochemical gasification. To date, the power used to provide energy for the endothermic reaction of solid fuels to syngas is not yet common because electricity is a high value and expensive energy. However, in the hydrogen economy, the value of electricity is not higher than heat. The two recent inventions DE 10 2008 014 799 Α 1 and DE 10 2008 032 166 Α 1 use this call to heat the fluidized bed reactor without the expansion of the electric heater. Since the operating temperature of these reactors is approximately 850 ° C close to the refining point of ash 201113478, the use of biomass, the supply of pure oxygen through the nozzle base will exceed the scum of the ash. It is not desirable to melt the ash because the ash can no longer be used as an inorganic fertilizer. Likewise, the operation of a fluidized bed reactor is unlikely to contain molten ash. However, if atmospheric oxygen is used, its operation may not exceed the melting point of the ash, however in this case nitrogen will enter the syngas. The solution was found by a two fluidized bed reactor connected by a sand recirculation system. One such embodiment is an 8 MW facility in the town of Gussing, Austria. Here, only the air is used to heat the rotating sand bed and to discharge it separately. Therefore, no nitrogen was found to enter the path of the syngas. Therefore, if electricity or oxygen is to be selectively used, a fluidized bed reactor of a specific design is required in each case. The present invention proposes a fluidized bed reactor and a method of operating the same. The goal is based on 'the use of electricity in a simple manner to heat the fluidized bed and its avoidance of ash' melting. This goal is achieved by the characteristics of items 1 and 11 of the scope of application for patents. Items 2 to 1 and 12 to 16 of the patent application range are further excellent specific examples of the present invention. The electrical heating tool provided in terms of equipment includes at least one cavity and a porous section associated with the cavity. Another aspect, in terms of method, provides for directing gas from the exterior to the cavity via the porous section and/or from the cavity to the exterior. Accordingly, an electric heater having a porous section has been provided in which the gas can selectively flow in one or other manner. This allows the gas to be heated in a fluidized bed of a fluidized bed reactor in substantial separation from the 201113478 coke particles 'because coke particles cannot penetrate the pore system of the porous section'. This avoids direct heating of the coke particles. The temperature is higher than the ash residue. Here, the porous section means a section having an open porosity ... pen p〇_ty) which is thus formed so that the gas is permeable. The porous section of the heating tool may or may not be heated directly. In the latter case, it is preferred that the porous section acts as a barrier to the actual heating section of the heating tool to prevent the coke particles from reaching the heating section. Then, it is preferable to provide the button area with respect to the outer area of the pure section to satisfy the function. If it is possible to permeate the gas, then the heating section of the heating tool itself can be formed as a porous section; or if the penetration of the body can be omitted, it is provided by the "no money component." In order to simplify the incident and to avoid unnecessary duplication, together describe the equipment and the better specific examples according to the financial law. Therefore, the technologist provides the individual features of the present invention, but it is also possible to provide a distinction between the porous section that is connected to the cavity, and the heated section can be ridden. # has a pure resistance test part. In this case, the heating plurality (four) segments form at least a portion of the purely heated resistor. However, the heating tool can also be electrically heated (10), for example, by (four). Then, the Wei body can be heated while flowing through the teaching hole section, and the coke particles cannot enter the hole system of the hole and section. To further obscure the twisted, porous section of the heating tool, the hybrid heating 4 provides a feed-through porous un-segment (which is disposed outside of the heated porous section). In a preferred embodiment of the fluidized bed reactor, the heating tool includes a crucible for supplying gas to and/or exhausting gas from the cavity. In this way, gas can be supplied to the heating tool and heated by the heating tool and discharged as needed via a stack. Another possibility for the gas to flow from the fluidized bed reactor into the cavity. During this time, the gas can be heated and subsequently removed from the fluidized bed reactor. The principles of the two methods can also be applied synchronously or alternately. In this case, it is preferable to provide a crucible for supplying a gas and a crucible for further discharging a substantially different gas. In particular, the gas to be supplied may be an oxygen-containing gas, that is, air or process oxygen. The oxygen-containing gas can be promoted to further release heat via oxidation with a combustible gas (e.g., pyrolysis gas or syngas). The heating means comprising (at least in certain areas) the double wall and the outer wall of the double wall comprising a porous section may be particularly preferred. Thus, an intermediate space is created which is spatially separated from the coke particles of the fluidized bed of the fluidized bed reactor. The coke particles can then, for example, not reach the heated inner wall of the double wall (which is not necessarily porous by itself). For example, the intermediate space can be used to introduce an oxygen-containing gas or a different gas such as a pyrolysis gas containing tar. Then, in the intermediate space or in the pore system of the porous section, the oxygen oxidizes the combustible gas preferably, thereby heating the fluidized bed reactor or additionally the electric heating tool. Then, in the intermediate space, the hot cracked tar can be cracked at a high temperature without forming molten ash. However, if necessary, the inner wall of the double wall may include a porous section, particularly in the case where gas is to be supplied to the intermediate space formed by the inner wall. If desired, this can be an oxygen-containing gas that burns 201113478 gas and/or tar-containing pyrolysis gas. Two chambers of the cavity and the intermediate space are available, which can respectively introduce an oxygen-containing gas and a combustible gas, which can then be brought together (i.e., in the intermediate space) to react with each other. Here, the syngas can also be regarded as a combustible gas. However, it may also be introduced into the cavity without oxygen to convert the contained tar in the porous section of the inner wall. This is done catalytically, such as via a catalytic material on the surface of the hole system. Here, the additional outer wall may obstruct the temperature increase of the coke particles from the fluidized bed (which is further increased by the heating of the porous section of the inner wall). A gas containing at least a portion of the removed tar or at least a portion of the oxidized gas may be released into the fluidized bed via the porous section of the outer wall. When the respective gases are discharged through the respective crucibles, there is no porous section in the outer wall. Thus, depending on the desired operation of the fluidized bed reactor, the inner and/or outer walls of the double wall may comprise heated porous sections. Further, the inner wall and/or the outer wall may define an intermediate space, and the heating means may include a weir for supplying gas to the intermediate space and/or for discharging gas from the intermediate space. The specific examples of the fluidized bed reactor may then each be adapted to the gas used or the desired operation of the fluidized bed reactor. If the porous section of the heating tool, the inner wall and/or the outer wall contains or is made of a catalytic material, it is particularly suitable for the catalytic cracking of tar contained in the pyrolysis gas or syngas. Preferably, the heating tool comprises a region of the catalytic material that follows the preferred operation previously discussed from the fluidized bed reactor. 201113478 A particularly simple and cost effective embodiment of the fluidized bed reactor is achieved with a heating tool comprising a plurality of conduits (including cavities). These can be easily distributed in the fluidized bed at a reasonable cost and individually made or contain porous sections. In the case of double walls, for the reasons mentioned above, it is intended that they should be formed by the inner duct and the concentric outer duct. It is preferably composed of a plurality of at least two conveying pipes, one of which is an inner pipe and the other of which is a concentric outer conveying pipe. One of the two delivery tubes is then porous or comprises at least one porous section. However, it is also possible for each of the tubes to be porous or to comprise at least one porous section, each of which does not require electrical heating. In order to convert the tar of the pyrolysis gas or syngas in the heating tool, a catalyst-assisted filter aid may be added thereto before introducing the respective gases into the cavity. The filter aid is then deposited at the porous section of the heating tool and can be reused if desired. In order to ensure that the gas used flows through the cavity, intermediate space and/or porous section indicated by the heating tool in a desired manner, pressure swings can be imposed on the cavity and/or intermediate space of the heating tool ( It is preferably pulsating). The pressure swing provides a drive pressure differential for the gas flow and is large enough to allow the flow direction of the gas within the porous section to be reversed with each pressure swing. In particular, if a gas from a fluidized bed reactor (which may be a tar-containing pyrolysis gas or a tar-containing syngas) is drawn into the heating tool and subsequently not discharged, it is fed back into the fluidized bed reaction. This is an option when in the device. 8 201113478 According to a preferred embodiment of the invention, the fluidized bed reactor is equipped with an electric heater comprising a gas permeable duct, wherein oxygen can be fed if desired without melting in the fluidized bed Ash residue. The present invention is suitable for heating all types of fluidized beds in fluidized bed reactors, particularly recirculating fluidized beds and stationary fluidized beds with or without inert bed materials. With this arrangement, coke particles can also be used to heat the gas compartment. These gas compartments can be placed on a stationary fluidized bed and can be separated (series) by a perforated plate or nozzle grid, thus reacting to form a series of agitation tanks. Further, the fluidized bed reactor may be additionally or additionally a thermal cracking reactor for thermal cracking of solid fuels, particularly biomass. In the sense of a syngas reactor, it may also be a fluidization process for producing syngas from a solid fuel of this type, such as biomass, and preferably from a pyrolysis gas of the type of thermal cracking reactor. Bed reaction unit. However, it may also be a comprehensive reaction apparatus comprising a plurality of fluidized beds for thermal cracking and steam reforming, if desired. Then, the fluidized bed reactor comprises a thermal cracking reactor as part of the reactor and a syngas reactor as the other part of the reactor. For the purposes of the present invention, "substantially solid fuel," is meant to mean a fuel that exhibits a complete or partial solid phase under medium conditions. It is preferred to use biomass as a fuel. The hollow body, for example, is controlled by a porous sintered conductive wheel. Suitably, in order to keep the temperature difference between the delivery of the fluidized bed and the coke particles within the limits, a large number of these are arranged in the fluidized bed in 201113478. Preferably, the delivery tube is comprised of a combination of a metal delivery tube having a perforation (if desired) and a porous delivery tube, in which ohmic heat is generated in the metal delivery tube. The fluidization bed (eg, in ohmic heat) is supplied with a voltage and/or by supplying oxygen and flowing through the porous delivery tube. Preferably, the metal delivery tube of the heating tool provides a heating resistor as the heating means. Induction heating of the delivery tube is also understood. For convenience, the following sections only refer to the delivery tube, because for heating reasons, the heating tool contains a plurality of roots. The tube is preferred. The specific example of the heating means comprising a plurality of tubes is not mandatory, even though it is not mentioned every other. Other structures may be used. For operation with oxygen, at least one end of the tube contains a gas 埠Oxygen causes oxidation or partial oxidation of the gas contained in the fluidized bed. Oxygen means that pure oxygen is preferred in the process. This can occur in the pores of the outer conveying pipe layer or directly at the interface layer of the conveying pipe. The reaction, therefore, the coke contained in the fluidized bed is not oxidized by oxygen, but the transfer tube is heated and transferred to the fluidized bed by radiation, conduction and convection. When the coke particles in the fluidized bed are converted into gas (eg, via an endothermic reaction), the coke particles are typically cooler than the delivery tube and/or the fluidized bed. In the operation of the heating tool, the flow direction of the contained gas may be between the cavity and the fluidized bed on the one hand. The pressure difference or the pressure difference between the cavity and the intermediate space, and on the other hand, the fluidized bed is defined. As the corresponding pressure difference is applied, the gas is from the fluidized bed. The device shall flow into the transfer tube and then be oxidized by oxygen from an oxygen-containing gas (which is fed through a suitable helium feed to the cavity of the 10 201113478). If necessary, each transfer tube has two Helium, one is used to supply oxygen and the other is used to discharge the oxidized gas. In this case, air is also very suitable as the oxygen-containing gas because the synthesis gas is not diluted by nitrogen because the oxidized gas is discharged. This method is preferred in a fluidized bed containing an inert bed material, as the inert bed material will then again pass through the friction to remove any layer of particulate matter formed (as far as the filter cake is concerned). a heating tool that can be heated in parallel with electricity, oxygen, or both, if desired. During electrical operation, at least one porous delivery tube can also be used to reduce tar by the catalyst. For example, in syngas generation A tar-containing gas is produced in an upstream process such as thermal cracking. The preparation of the pyrolysis gas is described in DE 198 07 988 A1 and DE 10 2008 032 166 A1. If the hot cracked gas from which the dust has been removed is directed through the porous transfer tube, the increased temperature in these transfer tubes will cause most of the tar to crack therein. When using raw biomass as the feed, the temperature of the transfer tube must be in the form of the raw material without exceeding the temperature from 700 ° C to 120 (TC. Therefore, for any raw material sensitive to temperature, the conductive (ie The heating tube is preferably arranged in a concentric manner by a further porous delivery tube. The outer porous delivery tube then acts as a thermal resistor. The effect can be even further increased if a small gap remains between the delivery tubes. Therefore, the inner conveying pipe can be made very hot without collecting ash deposits on the outer conveying pipe. It is not necessary to heat the respective outer wheel feeding pipes, so that it does not need to conduct electricity. Therefore, the conveying pipe can be made by Taman and can be obtained. For example, a sleeve is formed which is pushed onto the respective inner conveying pipe. 201113478 For the inner conveying pipe, it is particularly suitable because of the high temperature stability of the cerium carbide in a large reducing atmosphere. The medium is also useful. For example, a nickel-based catalyst of Group VIII of the periodic system is suitable, which also disrupts the chaos. The inner tube of the type described is disclosed, for example, in De 1 〇1 〇9 9 8 3 A1. . The nickel-based catalyst doped with Mg0, Zr〇2 or Zr〇2_Μα is also excellent. When the hot cracking gas is fed to the heating tool, for example, to convert any tar contained therein, the pyrolysis gas is used. It may be appropriate to previously crude desulfurization in a manner known per se (for example, using calcium oxide (CaO) at a temperature of 500 ° C to 70 (TC). Due to the desulfurization, the temperature of the inner transfer tube can be lowered. Calcium oxide Also suitable as a filter aid (precoat) for the inner transfer tube to absorb residual dust from the pyrolysis gas. It is preferred to periodically remove the filter aid by applying vacuum and/or pressure. This procedure is known to come from The operation of the cassette filter. At the same time, if the inner tube is divided into different groups (each of which has its own gas 埠), it is convenient. This allows practical continuous operation, because for the purpose of cleaning, only Individually separate tubes are exposed to the associated pressure shocks. Because calcium oxide supports tar cracking, it can be used to complement or complement the catalyst coating used to replace the inner tube. Oxidation dance can also stick to argon at higher temperatures. Sulfur. But 'because of chlorine The melting point of the substance and thioether is 75 ° C and 772 ° C, respectively. Most of the raw type must include the above-mentioned crude desulfurization. Other reagents are also suitable as filter aids, such as olivine, which can be used. To replace or use with the oxidizing feed. If any pyrolysis gas upstream of any thermal cracking from the fluidized bed reactor is to be partially or partially conducted in any proportion through the hollow body of the heating tool, then its potential Obtaining insufficient fluidizing gas. For example, if the water π and the possible additional gas required for the recombination process do not meet the required amount of fluidizing gas required, the portion produced in the fluidized bed reactor may be recycled. A gas (e.g., syngas), i.e., is withdrawn at the head of the chemical bed reactor and fed back into the substrate. In this case, it is preferred to have a reduced conical (four) nozzle grid through which the fluidizing gas and the recirculating gas are conducted. The 戎 ducts can also be arranged in groups such that only a portion of the ducts provide catalyzed cracking of the tar-containing gas, and other groups of ducts are heated by oxygen. This can occur in the same fluidized bed, but can also occur in a fluidized bed disposed upstream or downstream of the process. Other combinations of differently arranged and/or operated transport tube groups are understood. If the transfer tube is equipped with a catalyst for tar cracking, it is advantageous to pressurize the internal cavity of the transfer tube with a pulsating pressure swing from 0.1 Hz to 10,000 Hz, preferably between 5 and 500 Hz. Pressure swings facilitate material exchange in a multi-hole delivery tube. Depending on the amplitude, they can also draw product gases for catalytic conversion into the holes for a short period of time. These pressure swings can be generated by film vibration in a manner known per se. The present invention is capable of selectively heating with electricity and/or oxygen depending on temporary and local supply. This allows the use of local power from wind and photovoltaic power to generate peaks (which are not available) and the use of oxygen from the cells (during small and medium scale production from these sources). One of the preferred uses of the present invention is to crack tar in a fluidized bed reactor or to crack a pyrolysis gas in an electric heating tool (such as the upstream gasification stage 13 201113478) without the need for an expensive and inadvertent additional process. The invention will now be further explained with reference to the drawings showing only typical embodiments, in which: Figure 1 shows a fluidized bed reactor with a fixed fluidized bed and heater according to the invention; A section of the tubular heater of Fig. 1; Fig. 3 shows a section of a tubular heater as a material combination according to Fig. 1; Fig. 4 shows a fluidized bed and a heating tool having a plurality of tars for destroying tar Fluidized bed reactor; Figure 5 shows a section of a heated transfer tube for destroying tar; and Figure 6 shows a vertical section of Figure 5. C. Embodiment 3 Fig. 1 shows a fluidized bed reactor 5 having a fixed fluidized bed 6 having an upper end 7 and a lower end of a bonded nozzle grid 11. The fluidized bed housing 1 包括 includes a gas chamber 9 at its lower end for dispersing the fluidizing gas 13 introduced therein. On the fluidized bed 6, there is a free space 8 for discharging product gas 14. Depending on the operation, this can be thermal cracking gas or syngas. The biomass 12a is introduced into the fluidized bed reactor by means of a transport tool not shown herein. Fluidized bed reactors are typically lined with refractory cement. In order to allow the endothermic reaction to enter the syngas, the fluidized bed reactor is heated by a heating tool 29 comprising a plurality of gases forming a cavity 30 permeable to the delivery tube 1. The transfer tubes 1 themselves are suitable for electrical heating resistors or are formed by electrically conductive delivery 201113478 tubes lb in combination with further delivery tubes la (such as ceramic delivery tubes). The delivery tube forms a porous section 31 of the heating tool 29. According to Fig. 3, a spacer 27 is arranged between the two ducts to allow a better distribution of the gas introduced through the holes of the perforated duct lb. The delivery tube 1 has a crucible 3 and a closed configuration 4 at its end. The fluidized bed 6 can be heated by applying a voltage to the end of the delivery tube 1 and/or by supplying oxygen 15a. During the introduction of oxygen, the gas in the fluidized bed is partially oxidized to supply the required heat. Oxidation occurs in the porous layer or directly at the interface layer of the transfer tube 1. Oxygen does not cause coke particles to burn because it is depleted before it reaches the coke particles. Heat is transferred from the delivery tube 1 to the fluidized bed 6 by radiation, conduction and convection. The quality of the surface of the duct and the heat transfer determines the temperature difference between the duct and the fluidized bed which may consist of coke and inert bed material. In fluidized beds containing inert bed materials such as sand, heat transfer is better than in coke and ash dust clouds. The fluidized bed 6 can be heated on its own by means of electricity, independently by oxygen or by two processes. Figure 4 shows a fluidized bed reactor 5 containing a plurality of fluidized beds, wherein the fluidized beds are on top of one another and are arranged in a common housing 10. In the lower section, there is a stationary fluidized bed 6 containing an inert bed material into which coke from an upstream process, such as a thermal cracking reactor, is introduced. In a fluidized bed, the coke is finely ground and partially converted into pyrolysis gas or syngas by electrically heating the transfer tube 1. The residual coke rises with the gas. In the upper portion of the outer cover 10, there are two fluidized beds 28 that bond the perforated plates 23, 24 and 25. The fluidized bed consists of unconverted coke and ash particles. The perforated plate is arranged to avoid gas and particle reflow, thereby shaping the flow pattern of the plug flGW or the series of tanks. This flow is particularly suitable for catalyst cracking of any tar remaining in the gas on and in the transfer line 1, and to reduce the tar content of the ambiguity μ at the outlet. If a film or piston is used at the input of the oxygen 15a to generate a pulsation of 500 to _, the mediation increases. (d) The upper portion of the chemical bed reactor H) can be operated by itself by electricity, by oxygen alone or by both. Oxygen is supplied to the airtight crucible 3 via the intermediate foundation (10). In the lower part of Fig. 4, an electric heater 1 comprising a double wall 33 comprising an inner wall 呈 in the shape of a conductive and heated transfer tube and a non-conductive transport around the conductive tube 1 is shown. The outer wall of the shape of the tube 2. The delivery tube 2 can for example consist of a short ceramic sleeve arranged on top of one another and pressed by a spring. The spacer 27 forms an annular intermediate space 34 between the tubes 1 and 2. With this arrangement, if a voltage is applied to the end of the delivery pipe 1, the delivery pipe 1 becomes hotter than the delivery pipe 2 which is cooled by good heat transfer in the fluidized bed 6. This dual duct arrangement is particularly suitable for destroying tar by thermal catalyst. The tar-containing pyrolysis gas 15b from the upstream process is introduced into the cavity formed by the plates 16 and 17 and directed to the transfer pipe. The closed configuration 4 at the end of the delivery tube 1 forces the pyrolysis gas stream through the porous delivery tubes 1 and 2. The second delivery tube can also have a catalytic coating to support tar cracking. If the pyrolysis gas 15b is not completely dust-free, it has been recommended to operate the arrangement as a cartridge filter, wherein the pressure gradient is briefly reversed to remove dust from the delivery tube, and in this case it will fall into the dust. Arrange in the nozzle grille as a hollow body. The dust is delivered to the lowest portion of the panel 17 by the airflow vibrating device 20 driven by the gas 31 201113478 body 31. From then on, the dust is removed from the process via the lock tool 22. In order to minimize the interference accompanying the cleaning operation, the furnace should be divided between the plates 16 and 17 and have a plurality of crucibles for introducing the pyrolysis gas 15b. The use of filter aids (precoats) such as calcium oxide, which itself also has good tar cracking requirements, is also preferred. Oxidation mother can be added to the pyrolysis gas 15b. This assist also inhibits the accumulation of ash deposits. In this arrangement, the nozzles 18 must each have two plates 16 and 17. Nozzle 18 typically provides a backstop 19. I: Schematic description of the drawings 3 Fig. 1 shows a fluidized bed reactor having a fixed fluidized bed heat exchanger according to the present invention. Figure 2 shows a cross section of the tubular heater of Figure 1. Fig. 3 shows a section of a tubular heater as a material combination according to Fig. 1. Figure 4 shows a fluidized bed reactor with a plurality of fluidized beds and heating tools for destroying tar. Figure 5 shows a section of a heated transfer tube used to destroy tar. Figure 6 shows the vertical section of Figure 5. [Description of main component symbols] l··heating duct 4...closed plug la·••conducting heating duct 5···fluidized bed reactor lb··.non-conductive heating duct 2··.heating resistor Conveyor tube 3...Bee 6.. Fluidized bed 7.. Upper end of fluidized bed 8. Free space on fluidized bed 17 201113478 9.. Dispersed gas for fluidized gas Grab 10.. Fluidized bed cover 11.. Nozzle grille 12a.· Biomass 12b...Coke from partially converted biomass 13.. Fluidizing gas 14.. Syngas 15a.. . Oxygen 15b... Thermal cracking gas 16.. Upper plate of nozzle grille 17.. Lower plate of nozzle grille 18.. Nozzle duct 19. End nozzle of nozzle duct 20.. Airflow vibrator 21. Gas supplied to the vibrator 22. Discharge device for dust 23.. Lower perforated plate 24. Central perforated plate 25... Perforated plate 26.. Intermediate foundation 27.. spacer spacer 28.. coke dust cloud fluidized bed 29... heating tool 30.. cavity 31.. porous section 33.. double wall 34.. intermediate space 18