本文所用術語「永久混合之」係關於在步驟(2)中所處理之粒狀含貴金屬耐火材料。其意指至少一部分存在於反應區中之粒狀含貴金屬耐火材料在步驟(2)期間一直在移動中。較佳地，在步驟(2)期間存在於反應區中之粒狀含貴金屬耐火材料之總量在移動中及/或正在移動，且在方法中經混合或循環。 在本發明方法之較佳實施例中，實現在步驟(2)期間將粒狀含貴金屬耐火材料與氯及氣態氯化鋁接觸及/或用氯及氣態氯化鋁處理，其中流經反應區之氣體係包含氣態氯化鋁、氯及惰性氣體(若適用)或基本上由其組成之氣體混合物。然後本發明方法包含以下步驟： (1) 提供粒狀含貴金屬耐火材料； (2) 使在步驟(1)中所提供且溫度在200℃至650℃、較佳250℃至600℃、尤其300℃至500℃範圍內之永久混合之粒狀含貴金屬耐火材料與包含氣態氯化鋁、氯及惰性氣體(若適用)或基本上由其組成之氣體混合物之流在於200℃至650℃、較佳250℃至600℃、尤其300℃至500℃溫度下之熱反應區中接觸；及 (3) 將氣流引導出反應區。 本文使用術語「粒狀含貴金屬耐火材料」。該術語代表其表面及/或孔隙表面提供有貴金屬及/或以包括貴金屬顆粒之混合物形式存在之粒狀耐火材料。換言之，粒狀含貴金屬耐火材料中之粒狀耐火材料用作貴金屬載體材料及/或其係該混合物之組分。 本文使用術語「貴金屬」及/或「含貴金屬」。除非另有說明，否則該等術語係指單一貴金屬或不同貴金屬之組合，其各選自由以下各項組成之群：銀、金、錸、釕、鋨、銥、鉑、鈀及銠，尤其選自由以下各項組成之群：鉑、鈀及銠。 本文使用術語「粒狀耐火材料」。由耐火材料所製得之粒狀耐火材料及/或顆粒(耐火顆粒)應理解為由無機非金屬材料所製得之顆粒，該無機非金屬材料在高溫(例如，在200℃至650℃範圍內)下抵抗氯及氯化鋁的作用，即其在此情況下在物理上及化學上不改變或基本上不改變。舉例而言，此可係陶瓷耐火材料。適宜耐火材料可選自(例如)由以下各項組成之群：氧化鋁(例如，α-氧化鋁或γ-氧化鋁)、二氧化鈦、二氧化矽、氧化鎂、氧化鋯、混合氧化物(例如，鈰/鋯混合氧化物)，矽酸鹽(例如，矽酸鋁(例如、堇青石、富鋁紅柱石、沸石))、鈦酸鹽(例如，鈦酸鋁、鋯鈦酸鉛及鈦酸鋇)、碳化矽及氮化矽。耐火材料可經(例如)非貴金屬摻雜。因此耐火材料不含貴金屬。耐火材料可單獨或以組合形式存在，例如以不同粒狀耐火材料之混合物及/或以粒內組合形式存在。一般而言，由耐火材料所製得之顆粒為多孔的。 熟習此項技術者將本文所用術語「無貴金屬」理解為意指不含貴金屬，但貴金屬含量及/或殘餘貴金屬含量以重量計在(例如) ＞0 ppm至10 ppm範圍內，其出於技術原因對於相應材料而言基本上係不可避免的。 在本發明方法之步驟(1)中，舉例而言，以一種類型或多種不同類型之含貴金屬耐火顆粒之混合物之形式，或以無貴金屬耐火顆粒與含貴金屬耐火顆粒之混合物之形式，或以貴金屬顆粒與無貴金屬及/或含貴金屬耐火顆粒之混合物之形式提供粒狀含貴金屬耐火材料。無貴金屬耐火顆粒與含貴金屬耐火顆粒之混合物、或貴金屬顆粒與無貴金屬及/或含貴金屬耐火顆粒之混合物可係有意生產之混合物；但一般而言情況並非如此，且出於技術原因可能已生產出此類型之混合物。 由含貴金屬耐火材料製得之顆粒可係常見成形體(例如，顆粒體、丸粒或擠出物，例如圓柱體、環、球、立方體、小板)。該等成形體之直徑或大小可在(例如) 1毫米至30毫米、較佳1毫米至20毫米、尤其1毫米至15毫米之範圍內。較佳地，直徑及/或大小之下限係4毫米。舉例而言，成形體在其最厚位點之直徑可在1毫米至30毫米、較佳1毫米至20毫米、尤其1毫米至15毫米之範圍內；較佳地，直徑之下限亦係4毫米。 關於除該等成形體以外之含貴金屬耐火材料之顆粒，絕對粒徑可在(例如) 3 µm至500 µm之範圍內。不同於成形體之含貴金屬耐火材料之該等顆粒之實例包括崩解之(廢)異相觸媒、崩解之熔渣、貴金屬撇渣、乾燥及崩解之污泥、崩解之廢棄電及電子設備、崩解之採礦濃縮物及崩解之採礦廢棄物。 步驟(1)中所提供之粒狀耐火材料中之貴金屬含量各自相對於總粒狀含貴金屬耐火材料，在(例如) 0.01重量%至10重量%或0.01重量%至5重量%之範圍內，或較佳在0.1重量%至5重量%之範圍內。 粒狀含貴金屬耐火材料可係選自由以下各項組成之群之一種材料或不同材料之組合：崩解之熔渣、貴金屬撇渣、乾燥及崩解之污泥、崩解之廢棄電及電子設備、崩解之採礦濃縮物、崩解之採礦廢棄物及含貴金屬異相觸媒。 在一個實施例中，粒狀含貴金屬耐火材料可為經崩解、例如經研磨之熔渣。實例包括來自高溫冶金貴金屬精製方法之含貴金屬熔渣。 在另一實施例中，粒狀含貴金屬耐火材料可係貴金屬撇渣，例如來自珠寶或牙科行業之貴金屬撇渣。貴金屬撇渣可經預處理。舉例而言，其可經受灰化及/或用硝酸萃取及/或崩解，例如藉由研磨。灰化容許去除有機組分，例如藉助熱解及/或燃燒。硝酸萃取容許去除硝酸可溶性物質、尤其硝酸可溶性金屬，例如銅及銀。 在另一實施例中，粒狀含貴金屬耐火材料可為(例如)來自濕法冶金貴金屬精製方法之經乾燥並崩解、例如經研磨之污泥。此外，可使污泥退火。 在另一實施例中，粒狀含貴金屬耐火材料可係經崩解、例如經研磨之廢棄電及電子設備。此外，廢棄電及電子設備可經灰化或退火。退火或灰化容許去除有機組分，例如藉助熱解及/或燃燒。 在另一實施例中，粒狀含貴金屬耐火材料可係經崩解、例如經研磨之採礦濃縮物。採礦濃縮物之實例包括源自貴金屬礦、含有天然貴金屬且貴金屬部分濃度增加之材料。濃縮方法之實例係熟習此項技術者已知之常見物理及/或化學方法，例如浮選、高溫冶金熔融方法及濕法冶金方法。 在另一實施例中，粒狀含貴金屬耐火材料可係經崩解、例如經研磨之採礦廢棄物。實例包括來自貴金屬礦之天然含貴金屬採礦廢棄物。 具體而言，粒狀含貴金屬耐火材料係含貴金屬異相觸媒，尤其廢含貴金屬異相觸媒。含貴金屬異相觸媒可源自廣泛範圍之來源。舉例而言，廢含貴金屬異相觸媒可係(例如)來自化學、醫藥及石油化學工業之廢排出空氣淨化觸媒；廢排出氣體淨化觸媒；廢燃燒排出氣體淨化觸媒；廢柴油顆粒過濾器；用於生產純氣體之廢觸媒；及/或廢製程觸媒。製程觸媒之實例包括Fischer-Tropsch (費希爾-特羅普希)觸媒、重整觸媒、用於生產環氧乙烷之觸媒及氫化觸媒。 異相觸媒可以(例如)以下形式存在：(i)含有貴金屬但不經載體塗料塗佈之耐火載體材料之形式，(ii)經提供有載體塗料之含貴金屬塗層但自身不含貴金屬之耐火載體材料之形式，或(iii)經提供有載體塗料之含貴金屬塗層且自身亦含有貴金屬之耐火載體材料之形式。載體塗料塗層為熟習此項技術者已知；其係含有由耐火材料所製得之含貴金屬顆粒或由其組成之塗層，該耐火材料在自所謂的載體塗料漿液施加後經煅燒。 廢含貴金屬異相觸媒可固有地係粒狀且充分地不含干擾雜質，使得其可根據本發明方法之步驟(2)直接經處理。若情況並非如此，則其可首先經崩解(例如研磨)，及/或不期望之雜質可藉助熟習此項技術者已知之適宜方法(例如，藉由添加或不添加空氣之煅燒)自其去除。若適用，可實施還原處理(例如在還原氣氛中熱處理)，以將不以元素形式而(例如)以貴金屬氧化物形式存在於粒狀含貴金屬耐火材料中之貴金屬轉化為元素貴金屬。 在本發明方法之步驟(2)中，使在步驟(1)中所提供且溫度在200℃至650℃、較佳250℃至600℃、尤其300℃至500℃範圍內之永久混合之粒狀含貴金屬耐火材料與氯及氣態氯化鋁及惰性氣體(若適用)在氣體流經且於200℃至650℃、較佳250℃至600℃、尤其300℃至500℃溫度下之熱反應區中接觸。 具體而言，適宜惰性氣體之實例係氮及稀有氣體，例如氬。 氯及態氯化鋁共同係活性組分。 氯、可選惰性氣體及氣態氯化鋁可各自個別地及/或混合經供應至反應區中。特定而言，氣體及/或至少一種氣體混合物可在其進給至反應區時經預加熱。氣態氯化鋁亦可在反應區中自與粒狀含貴金屬耐火材料混合之固體氯化鋁原位形成。 在本發明方法之較佳實施例之步驟(2)中，使包含氣態氯化鋁、氯及惰性氣體(若適用)或基本上由其組成之氣體混合物之流流經於200℃至650℃、較佳250℃至600℃、尤其300℃至500℃溫度下之熱反應區。較佳地，供應至於200℃至650℃、較佳250℃至600℃、尤其300℃至500℃溫度下之熱反應區之氣體混合物係熱的，即其經適當預加熱至200℃至650℃、較佳250℃至600℃、尤其300℃至500℃之溫度。氣體混合物可經單獨產生。氣體混合物包含氣態氯化鋁、氯及惰性氣體(若適用)，較佳地其基本上由氣態氯化鋁、氯化物及惰性氣體(若適用)組成。較佳地，氣體混合物含有惰性氣體。氣態氯化鋁在氣體混合物中之重量分數在(例如) 10重量%至80重量%、較佳30重量%至70重量%之範圍內，氯之重量分數在(例如) 10重量%至40重量%、較佳15重量%至30重量%之範圍內，且惰性氣體之重量分數在(例如) 0重量%至80重量%、較佳10重量%至50重量%之範圍內。 反應區係熱的，其溫度為200℃至650℃、較佳250℃至600℃、尤其300℃至500℃。存在於其中之所有物質，即氯、氣態氯化鋁及永久混合之粒狀含貴金屬耐火材料，以及可選惰性氣體及在反應區中所產生之反應產物處於反應區中佔優之相同溫度下，在200℃至650℃、較佳250℃至600℃、尤其300℃至500℃範圍內，或承受此溫度。流經反應區之氣流可包含(例如)每小時且每公斤粒狀含貴金屬耐火材料(即每公斤反應區內之粒狀含貴金屬耐火材料) 5公升至15公升範圍內之體積流量。 一般而言，超壓在反應區中不佔優，通常壓力可在大氣壓至約1.5倍大氣壓之範圍內。 在步驟(1)中所提供且溫度在200℃至650℃、較佳250℃至600℃、尤其300℃至500℃範圍內之永久混合之粒狀含貴金屬耐火材料與氯及氣態氯化鋁在氣體流經且於200℃至650℃、較佳250℃至600℃、尤其300℃至500℃溫度下之熱反應區中之接觸可在加熱粒狀含貴金屬耐火材料時開始，或可僅在粒狀含貴金屬耐火材料達到期望溫度後發生。可將相同程序應用於對本發明至關重要之特定含貴金屬耐火材料之永久混合。因此，加熱粒狀含貴金屬耐火材料之方法可藉由永久混合支持，或永久混合可僅在粒狀含貴金屬耐火材料中達到期望溫度後開始。永久混合藉由機械方式發生。較佳地，在此情況中防止使粒狀含貴金屬耐火材料流化。 在一個實施例中，永久混合係藉助使用基本上已知之旋轉爐作為工作設備來實現。旋轉爐顯然地亦用於將粒狀含貴金屬耐火材料加熱至及/或維持在200℃至650℃、較佳250℃至600℃、尤其300℃至500℃之該範圍內之期望溫度。方便地，旋轉爐具有內壁及/或內襯，其在200℃至650℃下抵抗氯及氯化鋁，其係(例如)由石英玻璃、鎳基合金(例如Hastelloy® C)或適宜無機非金屬耐火材料(例如，石墨)製得。旋轉爐可水平或傾斜操作，例如以相對於水平高達12°之傾斜度操作。熟習此項技術者將適當選擇旋轉爐及/或旋轉爐之尺寸，(例如)以良好適應於欲處理之粒狀含貴金屬耐火材料之量。旋轉爐空間之長度及直徑可分別在(例如) 0.5米至10米及10 cm至100 cm之範圍內。旋轉爐空間可係圓柱形反應區。適當選擇內徑與圓周速度之函數(旋轉爐空間內壁之圓周速度)，使得旋轉運動確保對本發明至關重要之粒狀含貴金屬耐火材料之永久混合，但不對粒狀含貴金屬耐火材料施加將導致材料黏附至旋轉內壁之顯著離心力。對於反應區之內徑(例如，40 cm)而言，圓周速度可在(例如) 1 cm/s至25 cm/s之範圍內。 通常適當選擇永久混合之粒狀含貴金屬耐火材料與氯及氣態氯化鋁在氣體流經之熱反應區中之接觸時間及/或處理時間，使得確保貴金屬自粒狀含貴金屬耐火材料中分離直至期望殘餘含量或直至貴金屬不存在(參見上文所提及之「不含貴金屬」之定義)。通常，必需接觸時間及/或處理時間在(例如) 10分鐘至240分鐘、尤其15分鐘至120分鐘之範圍內。為防止關於使用旋轉爐之任何混淆，粒狀含貴金屬耐火材料之接觸時間及/或處理時間對應於其在形成反應區之實際旋轉爐空間中之停留時間。 方便地，亦使用粒狀含貴金屬耐火材料在其中經加熱之空間作為反應區。換言之，較佳在反應區中加熱粒狀含貴金屬耐火材料。因此，較佳反應區在上文所揭示為可能設備之旋轉爐、換言之旋轉爐空間內係(例如)圓柱形。若旋轉爐在傾斜位置上操作及/或若輸送設施(例如，螺旋輸送機)在旋轉爐內使用，則本發明之方法亦可作為持續方法實施，較佳使得粒狀含貴金屬耐火材料與氯及氣態氯化鋁之接觸時間及/或處理時間可藉助粒狀含貴金屬耐火材料經過反應區之輸送速率來調整。 反應區具有固有簡單的反應系統，其包含反應物、貴金屬、氯及氣態氯化鋁及/或基本上由其組成。流經反應區之氣流流過且部分地亦流經永久混合之粒狀含貴金屬耐火材料，此支持粒狀含貴金屬耐火材料與氯及氣態氯化鋁之接觸。在於反應區中佔優之200℃至650℃、較佳250℃至600℃、尤其300℃至500℃範圍內之溫度下，產生含氣態鋁、氯及貴金屬之化合物，假定產生含鋁及貴金屬之氯化複合物。用在步驟(3)中自反應區引導離開之熱氣流將含氣態鋁、氯及貴金屬之化合物一起攜帶離開。 對本發明至關重要之特定而言藉助旋轉爐所實施之粒狀含貴金屬耐火材料之永久混合容許達成上文所表述之目標，即自粒狀含貴金屬耐火材料中有效分離貴金屬，且不僅關於在短時間段內處理大量粒狀含貴金屬耐火材料達成目標，而且關於在根據本發明所處理之粒狀含貴金屬耐火材料中達到均勻低殘餘貴金屬含量(當在個別顆粒之層面上考慮時)達成目標。本發明方法容許去除大於99重量%之貴金屬，該貴金屬最初存在於粒狀含貴金屬耐火材料上及/或其中。 在步驟(3)中，將氣流，即正流經或已流經反應區之氣流在其離開反應區時自反應區引導離開。氣流在相應溫度下離開於200℃至650℃、較佳250℃至600℃、尤其300℃至500℃溫度下之熱反應區，且可經導離至允許形成並沈積固體貴金屬氯化物之較冷區域中，例如導離至具有抵抗氣流組分之內表面且溫度低於反應區中所佔優彼等之區域中。舉例而言，該等較低溫度可在(例如) 180℃至＜ 300℃之範圍內。在該等較低溫度下，由氣流一起隨同攜帶之含鋁、氯及貴金屬之化合物崩解，同時釋放沈積貴金屬氯化物，而惰性氣體、未使用的氯及氣態氯化鋁經進一步引導至(例如)氣體洗滌器中。或者，經去除及/或耗盡貴金屬及/或貴金屬氯化物之氣流可經引導回至反應區，以形成再循環系統。在反應區上游，可藉助添加因消耗氯而丟失之氯部分以及氯化鋁(若適用)來調整期望之氣體組成。 特別依賴於步驟(1)中所提供之粒狀含貴金屬耐火材料之類型，沈積貴金屬氯化物可係單一類型之物質或可作為不同貴金屬氯化物之混合物存在。貴金屬氯化物之實例包括PtCl2
、PdCl2
及RhCl3
。可使經分離之貴金屬氯化物經受常見再處理方法，例如濕法化學再處理。實例 實例 1
在以3°之水平傾斜度操作之旋轉爐(長75 cm、在500℃下、具有12 cm之內徑、反應區內壁之圓周速度為7.5 cm/s之圓柱形熱反應區)中，在流經其反應區之氣體混合物(67重量%之氣態氯化鋁、18重量%之氯、15重量之%氮、體積流量為70公升/h)下處理總計6,000 g之研磨觸媒(多孔氧化鋁載體，鉑含量為0.15重量%) (在500℃下觸媒材料之接觸時間為1小時)。在200℃溫度下之熱區中，自離開反應區之氣體以PtCl2
之形式回收總計92%之最初含於研磨觸媒中之鉑(藉助ICP-OES測定)；8%之最初含於研磨觸媒中之鉑留在觸媒材料中(在濕法化學消化鉑耗盡之觸媒後，藉助ICP-MS測定)。參考實例 2
重複實例1，其中唯一差異即旋轉爐在處理期間停滯。以PtCl2
之形式自離開反應區之氣體回收總計34%之最初含於研磨觸媒中之鉑；66%之最初含於研磨觸媒中之鉑留在觸媒材料中。實例 3
在以3°之水平傾斜度操作之旋轉爐(長75 cm、在400℃下、具有12 cm之內徑、反應區內壁之圓周速度為7.5 cm/s之圓柱形熱反應區)中，用流經其反應區之氣體混合物(67重量%之氣態氯化鋁、18重量%之氯、15重量%之氮、體積流量為70公升/h)處理總計6,000 g之研磨觸媒(多孔氧化鋁載體，鉑含量為0.1重量%) (在400℃下觸媒材料之接觸時間為1小時)。在200℃溫度下之熱區中，自離開反應區之氣體以PdCl2
之形式回收總計95%之最初含於研磨觸媒中之鈀(藉助ICP-OES測定)；5%之最初含於研磨觸媒中之鈀留在觸媒材料中(在濕法化學消化鈀耗盡之觸媒後，藉助ICP-MS測定)。參考實例 4
重複實例3，其中唯一差異即旋轉爐在處理期間停滯。以PdCl2
之形式自離開反應區之氣體回收總計81%之最初含於研磨觸媒中之鉑；19%之最初含於研磨觸媒中之鉑留在觸媒材料中。The term "permanently mixed" as used herein relates to a particulate noble metal-containing refractory material treated in step (2). It means that at least a portion of the particulate noble metal-containing refractory present in the reaction zone is constantly moving during step (2). Preferably, the total amount of particulate noble metal-containing refractory material present in the reaction zone during step (2) is moving and/or moving and is mixed or recycled in the process. In a preferred embodiment of the process of the invention, it is achieved during the step (2) that the particulate noble metal-containing refractory material is contacted with chlorine and gaseous aluminum chloride and/or treated with chlorine and gaseous aluminum chloride, wherein the reaction zone is passed through the reaction zone. The gas system comprises gaseous aluminum chloride, chlorine and an inert gas (if applicable) or a gas mixture consisting essentially of it. The method of the invention then comprises the steps of: (1) providing a granulated precious metal-containing refractory material; (2) providing the temperature in the step (1) and at a temperature of from 200 ° C to 650 ° C, preferably from 250 ° C to 600 ° C, especially 300 The flow of permanently mixed granular precious metal-containing refractories in the range of °C to 500 °C with a gaseous mixture comprising or consisting essentially of gaseous aluminum chloride, chlorine and an inert gas (if applicable) is between 200 ° C and 650 ° C. Contacting in a thermal reaction zone at a temperature of from 250 ° C to 600 ° C, especially from 300 ° C to 500 ° C; and (3) directing the gas stream out of the reaction zone. The term "granular precious metal-containing refractory" is used herein. The term refers to a particulate refractory material whose surface and/or pore surface is provided with a precious metal and/or in the form of a mixture comprising precious metal particles. In other words, the particulate refractory material in the granular noble metal-containing refractory material is used as a precious metal support material and/or as a component of the mixture. The term "precious metal" and / or "containing precious metals" is used herein. Unless otherwise stated, the terms mean a single precious metal or a combination of different precious metals, each selected from the group consisting of silver, gold, ruthenium, rhodium, iridium, osmium, platinum, palladium and rhodium, especially selected Free group of the following components: platinum, palladium and rhodium. The term "granular refractory" is used herein. Granular refractories and/or granules (refractory granules) produced from refractory materials are understood to be granules made from inorganic non-metallic materials which are at elevated temperatures (for example, in the range of 200 ° C to 650 ° C). Internally, it acts against chlorine and aluminum chloride, ie it does not change or substantially does not change in this case physically and chemically. For example, this can be a ceramic refractory material. Suitable refractory materials may be selected, for example, from the group consisting of alumina (eg, alpha-alumina or gamma-alumina), titanium dioxide, ceria, magnesia, zirconia, mixed oxides (eg, , cerium/zirconium mixed oxides, cerium salts (eg, aluminum citrate (eg, cordierite, mullite, zeolite)), titanates (eg, aluminum titanate, lead zirconate titanate, and titanic acid)钡), tantalum carbide and tantalum nitride. The refractory material can be doped, for example, by a non-noble metal. Therefore the refractory material does not contain precious metals. The refractory material may be present singly or in combination, for example in a mixture of different particulate refractory materials and/or in an intragranular combination. In general, the particles made from the refractory material are porous. The term "no precious metal" as used herein is understood to mean that no precious metal is present, but the precious metal content and/or residual precious metal content is in the range of, for example, >0 ppm to 10 ppm by weight, due to the technology. The reason is basically inevitable for the corresponding material. In the step (1) of the method of the present invention, for example, in the form of a mixture of one or more types of precious metal-containing refractory particles, or in the form of a mixture of noble metal-free refractory particles and precious metal-containing refractory particles, or A granular precious metal-containing refractory material is provided in the form of a mixture of precious metal particles and no precious metal and/or precious metal-containing refractory particles. Mixtures of precious metal-free refractory particles with precious metal-containing refractory particles, or mixtures of precious metal particles with non-precious metals and/or precious metal-containing refractory particles may be intentionally produced; however, this is generally not the case and may have been produced for technical reasons. A mixture of this type. Particles made from noble metal-containing refractories may be conventional shaped bodies (e.g., granules, pellets or extrudates such as cylinders, rings, spheres, cubes, small plates). The shaped bodies may have a diameter or size in the range of, for example, 1 mm to 30 mm, preferably 1 mm to 20 mm, especially 1 mm to 15 mm. Preferably, the lower limit of the diameter and/or size is 4 mm. For example, the diameter of the shaped body at its thickest point may be in the range of 1 mm to 30 mm, preferably 1 mm to 20 mm, especially 1 mm to 15 mm; preferably, the lower limit of the diameter is also 4 Millimeter. Regarding the particles of the noble metal-containing refractory material other than the shaped bodies, the absolute particle diameter may be in the range of, for example, 3 μm to 500 μm. Examples of the particles of the noble metal-containing refractory material different from the shaped body include disintegrated (waste) heterogeneous catalyst, disintegrated slag, precious metal slag, dried and disintegrated sludge, disintegrated waste electricity, and Electronic equipment, disintegrating mining concentrates and disintegrating mining waste. The precious metal content in the particulate refractory material provided in the step (1) is each in the range of, for example, 0.01% by weight to 10% by weight or 0.01% by weight to 5% by weight, based on the total particulate precious metal-containing refractory material, Or preferably in the range of 0.1% by weight to 5% by weight. The granulated precious metal-containing refractory material may be selected from a group consisting of a material or a combination of different materials: disintegrated slag, precious metal slag, dried and disintegrated sludge, disintegrated waste electricity and electronics Equipment, disintegrating mining concentrates, disintegrating mining waste and precious metal-containing heterogeneous catalysts. In one embodiment, the particulate noble metal-containing refractory material can be a disintegrated, for example ground, slag. Examples include precious metal-containing slags from pyrometallurgical precious metal refining processes. In another embodiment, the granular precious metal-containing refractory material may be a precious metal slag, such as precious metal slag from the jewelry or dental industry. The precious metal slag can be pretreated. For example, it can be subjected to ashing and/or extraction and/or disintegration with nitric acid, for example by grinding. Ashing allows removal of organic components, for example by means of pyrolysis and/or combustion. Nitric acid extraction allows the removal of nitric acid soluble substances, especially nitric acid soluble metals such as copper and silver. In another embodiment, the particulate noble metal-containing refractory material can be, for example, dried and disintegrated, such as ground, sludge from a hydrometallurgical precious metal refining process. In addition, the sludge can be annealed. In another embodiment, the particulate noble metal-containing refractory material can be disintegrated, such as ground waste electrical and electronic equipment. In addition, waste electrical and electronic equipment can be ashed or annealed. Annealing or ashing allows removal of organic components, for example by means of pyrolysis and/or combustion. In another embodiment, the particulate precious metal-containing refractory material can be a disintegrated, for example ground, mining concentrate. Examples of mining concentrates include materials derived from precious metal ores, containing natural precious metals and having an increased concentration of precious metal portions. Examples of concentration methods are those well known to those skilled in the art, such as flotation, pyrometallurgical melting processes, and hydrometallurgical processes. In another embodiment, the particulate noble metal-containing refractory material can be disintegrated, such as ground mining waste. Examples include natural precious metal-containing mining waste from precious metal ore. Specifically, the granular noble metal-containing refractory material contains a noble metal heterogeneous catalyst, especially a noble metal heterogeneous catalyst. The noble metal-containing heterogeneous catalyst can be derived from a wide range of sources. For example, waste precious metal heterogeneous catalysts can be, for example, waste exhaust air purification catalysts from the chemical, pharmaceutical, and petrochemical industries; waste exhaust gas purification catalysts; waste combustion exhaust gas purification catalysts; waste diesel particulate filtration a waste catalyst for the production of pure gases; and/or a waste process catalyst. Examples of process catalysts include Fischer-Tropsch catalysts, reforming catalysts, catalysts for the production of ethylene oxide, and hydrogenation catalysts. Heterogeneous catalysts may, for example, be present in the form of (i) a refractory support material containing a precious metal but not coated with a washcoat, (ii) a refractory support containing a noble metal coating provided with a washcoat but without its own precious metal In the form of a carrier material, or (iii) in the form of a refractory support material which is provided with a carrier coating and which contains a precious metal coating and which itself also contains a precious metal. Carrier coatings are known to those skilled in the art; they contain a coating comprising or consisting of precious metal-containing particles made from a refractory material which is calcined after application from a so-called carrier coating slurry. The spent precious metal heterogeneous catalyst can be inherently granulated and sufficiently free of interfering impurities such that it can be directly treated according to step (2) of the process of the invention. If this is not the case, it may first be disintegrated (e.g., ground), and/or the undesirable impurities may be obtained from a suitable method known to those skilled in the art (e.g., by calcination with or without the addition of air). Remove. If applicable, a reduction treatment (for example, heat treatment in a reducing atmosphere) may be carried out to convert a noble metal which is not in elemental form, for example, in the form of a noble metal oxide in the particulate noble metal-containing refractory into an elemental noble metal. In step (2) of the process of the invention, the permanently mixed granules provided in step (1) and having a temperature in the range of from 200 ° C to 650 ° C, preferably from 250 ° C to 600 ° C, especially from 300 ° C to 500 ° C Thermal reaction of a noble metal-containing refractory material with chlorine and gaseous aluminum chloride and an inert gas (if applicable) in a gas flowing at a temperature of from 200 ° C to 650 ° C, preferably from 250 ° C to 600 ° C, especially from 300 ° C to 500 ° C Contact in the area. In particular, examples of suitable inert gases are nitrogen and noble gases such as argon. Chlorine and aluminum chloride are the active components. Chlorine, an optional inert gas, and gaseous aluminum chloride may each be supplied to the reaction zone individually and/or in combination. In particular, the gas and/or at least one gas mixture may be preheated as it is fed to the reaction zone. Gaseous aluminum chloride can also be formed in situ from the solid aluminum chloride mixed with the particulate noble metal-containing refractory material in the reaction zone. In step (2) of the preferred embodiment of the process of the invention, a stream comprising gaseous aluminum chloride, chlorine and an inert gas (if applicable) or a gas mixture consisting essentially thereof is passed through a temperature between 200 ° C and 650 ° C Preferably, the thermal reaction zone is at a temperature of from 250 ° C to 600 ° C, especially from 300 ° C to 500 ° C. Preferably, the gas mixture supplied to the thermal reaction zone at a temperature of from 200 ° C to 650 ° C, preferably from 250 ° C to 600 ° C, especially from 300 ° C to 500 ° C, is hot, ie it is suitably preheated to 200 ° C to 650 °C, preferably 250 ° C to 600 ° C, especially 300 ° C to 500 ° C temperature. The gas mixture can be produced separately. The gas mixture comprises gaseous aluminum chloride, chlorine and an inert gas (if applicable), preferably consisting essentially of gaseous aluminum chloride, chloride and an inert gas, if applicable. Preferably, the gas mixture contains an inert gas. The weight fraction of gaseous aluminum chloride in the gas mixture is, for example, in the range of 10% by weight to 80% by weight, preferably 30% by weight to 70% by weight, and the weight fraction of chlorine is, for example, 10% by weight to 40% by weight. %, preferably in the range of 15% by weight to 30% by weight, and the weight fraction of the inert gas is, for example, in the range of 0% by weight to 80% by weight, preferably 10% by weight to 50% by weight. The reaction zone is hot and has a temperature of from 200 ° C to 650 ° C, preferably from 250 ° C to 600 ° C, especially from 300 ° C to 500 ° C. All of the substances present in it, namely chlorine, gaseous aluminum chloride and permanently mixed granular noble metal-containing refractories, and optionally inert gases and reaction products produced in the reaction zone are at the same temperature prevailing in the reaction zone It is in the range of 200 ° C to 650 ° C, preferably 250 ° C to 600 ° C, especially 300 ° C to 500 ° C, or withstand this temperature. The gas stream flowing through the reaction zone may comprise, for example, a volumetric flow rate in the range of 5 liters to 15 liters per hour per kilogram of granular precious metal-containing refractory material (i.e., granular precious metal-containing refractory material per kilogram of reaction zone). In general, the overpressure is not dominant in the reaction zone, and typically the pressure can range from atmospheric to about 1.5 times atmospheric. Permanently mixed granular precious metal-containing refractories and chlorine and gaseous aluminum chlorides provided in step (1) and having a temperature in the range of 200 ° C to 650 ° C, preferably 250 ° C to 600 ° C, especially 300 ° C to 500 ° C The contacting in the thermal reaction zone where the gas flows and is at a temperature of from 200 ° C to 650 ° C, preferably from 250 ° C to 600 ° C, especially from 300 ° C to 500 ° C, may begin when heating the particulate precious metal-containing refractory material, or may only Occurs after the granular precious metal-containing refractory material reaches the desired temperature. The same procedure can be applied to the permanent mixing of particular noble metal-containing refractories that are critical to the invention. Thus, the method of heating the particulate noble metal-containing refractory material can be initiated by permanent mixing, or permanent mixing can be initiated only after the desired temperature has been reached in the particulate noble metal-containing refractory. Permanent mixing occurs mechanically. Preferably, fluidization of the particulate noble metal-containing refractory material is prevented in this case. In one embodiment, the permanent mixing is achieved by using a substantially known rotary furnace as the working equipment. The rotary furnace is obviously also used to heat the particulate noble metal-containing refractory material to and/or to maintain a desired temperature in the range of from 200 ° C to 650 ° C, preferably from 250 ° C to 600 ° C, especially from 300 ° C to 500 ° C. Conveniently, the rotary furnace has an inner wall and/or an inner liner which is resistant to chlorine and aluminum chloride at 200 ° C to 650 ° C, for example from quartz glass, nickel based alloys (eg Hastelloy® C) or suitable inorganic Made of a non-metallic refractory material (for example, graphite). The rotary furnace can be operated horizontally or tilted, for example at an inclination of up to 12° with respect to the horizontal. Those skilled in the art will suitably select the size of the rotary furnace and/or rotary furnace, for example, to accommodate the amount of particulate precious metal-containing refractory material to be treated. The length and diameter of the rotary furnace space can be, for example, in the range of 0.5 m to 10 m and 10 cm to 100 cm, respectively. The rotary furnace space can be a cylindrical reaction zone. The function of the inner diameter and the peripheral speed (circumferential speed of the inner wall of the rotary furnace space) is appropriately selected so that the rotational movement ensures permanent mixing of the granular noble metal-containing refractory material which is essential to the invention, but does not apply to the granular noble metal-containing refractory material. A significant centrifugal force that causes the material to adhere to the rotating inner wall. For the inner diameter of the reaction zone (for example, 40 cm), the peripheral speed may be in the range of, for example, 1 cm/s to 25 cm/s. The contact time and/or treatment time of the permanently mixed granular noble metal-containing refractory material and the chlorine and gaseous aluminum chloride in the thermal reaction zone through which the gas flows is generally selected as appropriate to ensure separation of the precious metal from the granular noble metal-containing refractory material until The residual content is expected or until the precious metal is not present (see the definition of "no precious metal" mentioned above). Typically, the necessary contact time and/or treatment time is in the range of, for example, 10 minutes to 240 minutes, especially 15 minutes to 120 minutes. To prevent any confusion with respect to the use of a rotary furnace, the contact time and/or treatment time of the particulate noble metal-containing refractory material corresponds to the residence time of the actual rotary furnace space in which the reaction zone is formed. Conveniently, a space in which a granular noble metal-containing refractory material is heated is also used as a reaction zone. In other words, it is preferred to heat the particulate noble metal-containing refractory material in the reaction zone. Thus, the preferred reaction zone is, for example, cylindrical in the rotary furnace of the possible apparatus disclosed above, in other words in the space of the rotary furnace. If the rotary furnace is operated in an inclined position and/or if a conveying facility (for example, a screw conveyor) is used in a rotary furnace, the method of the present invention can also be carried out as a continuous method, preferably in the form of a granular noble metal-containing refractory material and chlorine. The contact time and/or treatment time of the gaseous aluminum chloride can be adjusted by the rate of transport of the particulate noble metal-containing refractory material through the reaction zone. The reaction zone has an inherently simple reaction system comprising and consisting essentially of reactants, precious metals, chlorine and gaseous aluminum chloride. The gas stream flowing through the reaction zone flows through and partially through the permanently mixed particulate noble metal-containing refractory material, which supports the contact of the particulate noble metal-containing refractory material with chlorine and gaseous aluminum chloride. Producing a compound containing gaseous aluminum, chlorine and a noble metal at a temperature in the range of from 200 ° C to 650 ° C, preferably from 250 ° C to 600 ° C, especially from 300 ° C to 500 ° C in the reaction zone, assuming that aluminum and precious metals are produced Chlorinated complex. The gaseous gas containing gaseous aluminum, chlorine and precious metals is carried away together with the hot gas stream directed away from the reaction zone in step (3). For the particularity of the invention, the permanent mixing of the granulated precious metal-containing refractory material by means of a rotary furnace allows the achievement of the above-mentioned object of efficient separation of precious metals from granular noble metal-containing refractories, and not only Achieving the goal of treating a large number of granular precious metal-containing refractories in a short period of time, and achieving a goal of achieving a uniform low residual precious metal content (when considered at the level of individual particles) in the granular precious metal-containing refractories treated according to the invention . The process of the invention permits removal of greater than 99% by weight of precious metals initially present on and/or in the particulate noble metal-containing refractory. In step (3), the gas stream, i.e., the gas stream that is or has flowed through the reaction zone, is directed away from the reaction zone as it exits the reaction zone. The gas stream leaves the thermal reaction zone at a temperature of from 200 ° C to 650 ° C, preferably from 250 ° C to 600 ° C, especially from 300 ° C to 500 ° C, and can be conducted to allow for the formation and deposition of solid precious metal chlorides. In the cold zone, for example, it is conducted to a region having an inner surface resistant to the gas flow component and having a temperature lower than that in the reaction zone. For example, the lower temperatures can range, for example, from 180 °C to <300 °C. At these lower temperatures, the aluminum, chlorine and noble metal-containing compounds carried together by the gas stream disintegrate while releasing the deposited precious metal chloride, while the inert gas, unused chlorine and gaseous aluminum chloride are further guided to ( For example) in a gas scrubber. Alternatively, a gas stream that has been removed and/or depleted of precious metal and/or precious metal chloride can be directed back to the reaction zone to form a recycle system. Upstream of the reaction zone, the desired gas composition can be adjusted by adding a chlorine fraction that is lost due to the consumption of chlorine and aluminum chloride (if applicable). Depending in particular on the type of particulate noble metal-containing refractory material provided in step (1), the deposited noble metal chloride may be of a single type or may be present as a mixture of different precious metal chlorides. Examples of noble metal chlorides include PtCl 2 , PdCl 2 and RhCl 3 . The separated precious metal chloride can be subjected to conventional reprocessing methods such as wet chemical reprocessing. EXAMPLES Example 1 A rotary furnace operating at a horizontal inclination of 3° (75 cm long, an internal diameter of 12 cm at 500 ° C, and a cylindrical thermal reaction zone of 7.5 cm/s at a peripheral velocity of the wall in the reaction zone) In the case of a gas mixture flowing through the reaction zone (67% by weight of gaseous aluminum chloride, 18% by weight of chlorine, 15% by weight of nitrogen, volumetric flow rate of 70 liters/h), a total of 6,000 g of abrasive contact is treated. Medium (porous alumina support, platinum content 0.15 wt%) (contact time of the catalyst material at 500 ° C was 1 hour). In the hot zone at a temperature of 200 ° C, a total of 92% of the platinum initially contained in the grinding catalyst (determined by means of ICP-OES) is recovered as a PtCl 2 from the gas leaving the reaction zone; 8% is initially contained in the grinding The platinum in the catalyst is left in the catalyst material (determined by ICP-MS after wet chemical digestion of the platinum depleted catalyst). Example 1 was repeated with reference to Example 2 , with the only difference that the rotary furnace was stagnant during processing. A total of 34% of the platinum initially contained in the grinding catalyst was recovered from the gas leaving the reaction zone in the form of PtCl 2 ; 66% of the platinum originally contained in the grinding catalyst remained in the catalytic material. Example 3 A rotary furnace operating at a horizontal inclination of 3° (75 cm long, an inner diameter of 12 cm at 400 ° C, and a cylindrical thermal reaction zone with a peripheral velocity of 7.5 cm/s in the reaction zone) A total of 6,000 g of grinding catalyst was treated with a gas mixture (67% by weight of gaseous aluminum chloride, 18% by weight of chlorine, 15% by weight of nitrogen, and a volume flow rate of 70 liters/h) flowing through the reaction zone ( The porous alumina carrier had a platinum content of 0.1% by weight) (the contact time of the catalyst material at 400 ° C was 1 hour). In the hot zone at a temperature of 200 ° C, a total of 95% of the palladium initially contained in the grinding catalyst (determined by ICP-OES) is recovered as PdCl 2 from the gas leaving the reaction zone; 5% is initially contained in the grinding The palladium in the catalyst remains in the catalyst material (determined by ICP-MS after wet chemical digestion of the palladium depleted catalyst). Example 3 was repeated with reference to Example 4 , with the only difference that the rotary furnace was stagnant during processing. A total of 81% of the platinum initially contained in the grinding catalyst was recovered from the gas leaving the reaction zone in the form of PdCl 2 ; 19% of the platinum originally contained in the grinding catalyst remained in the catalytic material.