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所製得之顆粒可具有(例如) 3 µm至500 µm範圍內之絕對粒徑。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)中所提供之粒狀含貴金屬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，且藉助向上氣流提供為流化床之粒狀含貴金屬耐火材料與氯、氣態氯化鋁及惰性氣體(若適用)在於200℃至650℃、較佳250℃至600℃、尤其300℃至500℃溫度下之熱流化床中接觸。 粒狀含貴金屬耐火材料係藉助向上氣流以流化床形式提供，即其經流化。用於形成由粒狀固體所製得之流化床之方法及裝置為熟習此項技術者已知且不需要特別措施，包括在粒狀含貴金屬耐火材料之情況下。具體而言，粒狀含貴金屬耐火材料之流化可在常見流化床反應器中實現。方便地，在此情況下所用之裝置或流化床反應器具有內壁及/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。 流化床係反應區或至少一個反應區。 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。 將粒狀含貴金屬耐火材料加熱至200℃至650℃，並將其轉移至亦藉助向上氣流形成反應區之流化床中。此可以任何時間順序發生或在時間上重疊。具體而言，加熱粒狀含貴金屬耐火材料之方法可藉助經加熱至相應溫度之向上氣流發生。 氯、可選惰性氣體及氣態氯化鋁可各自個別地及/或或者經供應至流化床中。具體而言，氣體及/或至少一種氣體混合物在供應時可經預加熱。氣態氯化鋁亦可在流化床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。 向上氣流可包含氯、氣態氯化鋁、可選惰性氣體或該等組分中之兩者或每一者之混合物或由其組成。 在本發明方法之較佳實施例中，用於形成呈流化床形式之粒狀含貴金屬耐火材料之向上氣流係包含氣態氯化鋁、氯及惰性氣體(若適用)或基本上由其組成之氣體混合物之流。因此，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熱流化床，其在200℃至650℃、較佳250℃至600℃、尤其300℃至500℃之溫度下。較佳地，經供應至於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，即其經大概預加熱至200℃至650℃、較佳250℃至600℃、尤其300℃至500℃之溫度。藉由此方式，氣體混合物亦可實現粒狀含貴金屬耐火材料之加熱。氣體混合物可單獨產生。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。 流化床及/或反應區係熱的，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。提供且流經流化床及/或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) 1 m3
至2.5 m3
範圍內之體積流量。 一般而言，超壓在流化床及/或反應區中不佔優，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℃範圍內之粒狀含貴金屬耐火材料與氯及氣態氯化鋁在於200℃至650℃、較佳250℃至600℃、尤其300℃至500℃溫度下之熱流化床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。 通常適當選擇粒狀含貴金屬耐火材料與氯及氣態氯化鋁在熱流化床中之接觸時間及/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流化床中之停留時間。 本發明方法可以分批方法或以連續方式實施，但在後一情形中較佳使得可使用粒狀含貴金屬耐火材料經過形成反應區之流化床之進料速率來調整與氯及氣態氯化鋁接觸及/或用氯及氣態氯化鋁處理之時間。 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，即在流化床中及/或由流化床所填充之區域中加熱粒狀含貴金屬耐火材料。因此，上文所提及由流化床所填充之流化床反應器之區域係較佳反應區。 以流化床形式所提供之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。流經流化床之氣流流經流化含特定貴金屬之耐火材料。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)中以向上方向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。 提供粒狀含貴金屬耐火材料作為流化床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，即正流經或已流經形成反應區之流化床之氣流在其離開流化床時自流化床引導離開。氣流在相應溫度下離開在200℃至650℃、較佳250℃至600℃、尤其300℃至500℃溫度下之熱流化床及/或反應區，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流化床，以形成再循環系統。在流化床上游，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以不同貴金屬氯化物之混合物形式存在。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
使用流經反應區之氣體混合物(67重量%氣態氯化鋁，18重量%氯，15重量%氮)，使總計6,000 g研磨觸媒(多孔氧化鋁載劑，鉑含量0.15重量%)在流化床反應器(長60 cm、在500℃之溫度下、具有15 cm內徑之圓柱形熱流化床及/或反應區)中流化60分鐘。氣體混合物之體積流量係9.4 m3
/h。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76%之最初含於研磨觸媒中之鉑(藉助ICP-OES測定)；24%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
使用流經反應區之氣體混合物(67重量%氣態氯化鋁，18重量%氯，15重量%氮)，在靜態管式爐(長75 cm、在500℃溫度下、具有12 cm內徑之圓柱形熱反應區)中處理總計6,000 g研磨觸媒(多孔氧化鋁載劑，鉑含量0.15重量%)。氣體混合物之體積流量係70公升/h。在200℃溫度下之熱區中，自離開反應區之氣體以PtCl2
之形式回收總及34%之最初含於研磨觸媒中之鉑(藉助ICP-OES測定)；66%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)。實例 3
使用流經反應區之氣體混合物(67重量%氣態氯化鋁，18重量%氯，15重量%氮)，將總計6,000 g研磨觸媒(多孔氧化鋁載劑，鈀含量0.15重量%)在流化床反應器(長60 cm、在400℃溫度下、具有15 cm內徑之圓柱形熱流化床及/或反應區)中流化60分鐘。氣體混合物之體積流量係9.4 m3
/h。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92%最初含於研磨觸媒中之鈀(藉助ICP-OES測定)；8%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
使用流經反應區之氣體混合物(67重量%氣態氯化鋁，18重量%氯，15重量%氮)，在靜態管式爐(長75 cm、在400℃溫度下、具有12 cm內徑之圓柱形熱反應區)中處理總計6,000 g研磨觸媒(多孔氧化鋁載劑，鈀含量0.1重量%)。氣體混合物之體積流量係70公升/h。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81%最初含於研磨觸媒中之鈀(藉助ICP-OES測定)；19%最初含於研磨觸媒中之鈀留在觸媒材料(在濕法化學消化鈀耗盡之觸媒後，藉助ICP-MS測定)中。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. The particles produced from the noble metal-containing refractory material may have an absolute particle diameter in the range of, for example, 3 μm to 500 μm. Examples of such granules include disintegrated (waste) heterogeneous catalysts, disintegrated slag, precious metal slag, dried and disintegrated sludge, disintegrated waste electrical and electronic equipment, disintegrated mining concentrates and Disintegrated mining waste. The precious metal content in the granular noble metal-containing 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-containing precious metal refractory material. Within, or preferably in the range of from 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 the step (2) of the process of the invention, the temperature is provided in the step (1) and the temperature is in the range of 200 ° C to 650 ° C, preferably 250 ° C to 600 ° C, especially 300 ° C to 500 ° C, and with the upward gas flow The granular noble metal-containing refractory material provided as a fluidized bed and chlorine, gaseous aluminum chloride and an inert gas (if applicable) are 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 a hot fluidized bed. The granulated noble metal-containing refractory material is supplied in the form of a fluidized bed by means of an upward gas flow, that is, it is fluidized. Methods and apparatus for forming a fluidized bed made from a particulate solid are known to those skilled in the art and do not require special measures, including in the case of granular precious metal-containing refractories. In particular, fluidization of particulate noble metal-containing refractories can be accomplished in conventional fluidized bed reactors. Conveniently, the apparatus or fluidized bed reactor used in this case 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 Base alloys (such as Hastelloy® C) or suitable inorganic non-metallic refractories (eg, graphite). A fluidized bed reaction zone or at least one reaction zone. In particular, examples of suitable inert gases are nitrogen and noble gases such as argon. Chlorine and aluminum chloride are the active components. The granulated noble metal-containing refractory material is heated to a temperature between 200 ° C and 650 ° C and transferred to a fluidized bed which also forms a reaction zone by means of an upward gas flow. This can occur in any time order or overlap in time. In particular, the method of heating the particulate noble metal-containing refractory material can occur by means of an upward gas stream heated to a corresponding temperature. The chlorine, the optional inert gas and the gaseous aluminum chloride can each be supplied individually and/or or to the fluidized bed. In particular, the gas and/or the at least one gas mixture can be preheated upon supply. Gaseous aluminum chloride can also be formed in situ from a solid aluminum chloride mixed with a particulate noble metal-containing refractory material in a fluidized bed. The upward gas stream may comprise or consist of chlorine, gaseous aluminum chloride, an optional inert gas, or a mixture of two or each of the components. In a preferred embodiment of the process of the invention, the upward gas stream for forming a particulate noble metal-containing refractory material in the form of a fluidized bed comprises or consists essentially of gaseous aluminum chloride, chlorine and an inert gas (if applicable). The flow of the gas mixture. Thus, a stream comprising gaseous aluminum chloride, chlorine and an inert gas (if applicable) or a gas mixture consisting essentially of it is passed through a hot fluidized bed at a temperature of from 200 ° C to 650 ° C, preferably from 250 ° C to 600 ° C. Especially at temperatures between 300 ° C and 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 preheated to about 200 ° C to A temperature of 650 ° C, preferably 250 ° C to 600 ° C, especially 300 ° C to 500 ° C. In this way, the gas mixture can also be heated by the granular noble metal-containing refractory. 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 fluidized bed and/or 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 particulate precious metal-containing refractories, and optional inert gases and reaction products produced in the reaction zone are at the same temperature prevailing in the reaction zone, at 200 From °C to 650 ° C, preferably from 250 ° C to 600 ° C, especially from 300 ° C to 500 ° C, or withstand this temperature. The gas stream provided and flowing through the fluidized bed and/or reaction zone may comprise, for example, hourly and per kilogram of granular precious metal-containing refractory material (ie, granular precious metal-containing refractory material per kilogram of reaction zone) from 1 m 3 to 2.5 Volume flow within the range of m 3 . In general, the overpressure is not dominant in the fluidized bed and/or reaction zone, and typically the pressure can range from atmospheric to about 1.5 times atmospheric. The granular noble metal-containing refractory material and chlorine and gaseous aluminum chloride provided in the 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 are at 200 ° C The contact in a hot fluidized bed at a temperature of 650 ° C, preferably 250 ° C to 600 ° C, especially 300 ° C to 500 ° C may begin when heating the particulate precious metal-containing refractory material, or may only be in the granular precious metal-containing refractory material Occurs when the desired temperature is reached. The contact time and/or treatment time of the granular precious metal-containing refractory material with chlorine and gaseous aluminum chloride in the hot fluidized bed is usually appropriately selected to ensure separation of the precious metal from the granular noble metal-containing refractory material until the desired residual content or until the precious metal Does not exist (see the definition of “no precious metals” 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, the contact time and/or treatment time of the particulate noble metal-containing refractory material corresponds to its residence time in the fluidized bed forming the reaction zone. The process of the invention may be carried out in a batch process or in a continuous manner, but in the latter case it is preferred to adjust the chlorine and gaseous chlorination using a feed rate of the granular noble metal-containing refractory material through the fluidized bed forming the reaction zone. The time during which aluminum is contacted and/or treated with chlorine and gaseous aluminum chloride. 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, i.e., in the fluidized bed and/or in the region filled by the fluidized bed. Therefore, the area of the fluidized bed reactor filled with a fluidized bed as mentioned above is a preferred reaction zone. The reaction zone provided in the form of a fluidized bed 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 fluidized bed flows through a fluidized refractory material containing a specific precious metal. 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 from the reaction zone in the upward direction in step (3). The provision of a granular noble metal-containing refractory material as a fluidized bed allows the achievement of the above-mentioned objectives, namely the efficient separation of precious metals from granular precious metal-containing refractories, and not only for the treatment of a large number of granular precious metal-containing refractories in a short period of time The aim, and with regard to achieving a uniform low residual precious metal content in the granular precious metal-containing refractories treated according to the invention (when considered on the level of individual particles) achieves the goal. 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 flowing or has flowed through the fluidized bed forming the reaction zone, is directed away from the fluidized bed as it exits the fluidized bed. The gas stream exits the hot fluidized bed and/or 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 formation and deposition In the cooler regions of the solid precious metal chloride, for example, it is conducted to a region having an inner surface resistant to the gas stream 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, the gas stream that has been removed and/or depleted of precious metal and/or precious metal chloride can be directed back to the fluidized bed to form a recycle system. In a fluidized bed, 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 exist 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 gas mixture (67 wt% gaseous aluminum chloride, 18 wt% chlorine, 15 wt% nitrogen) flowing through a reaction zone was used to make a total of 6,000 g of grinding catalyst (porous alumina carrier, platinum content 0.15 wt%). The fluidized bed reactor (60 cm long, at a temperature of 500 ° C, a cylindrical hot fluidized bed having a 15 cm inner diameter and/or a reaction zone) was fluidized for 60 minutes. The volume flow of the gas mixture is 9.4 m 3 /h. In the hot zone at a temperature of 200 ° C, a total of 76% of the platinum originally contained in the grinding catalyst (determined by means of ICP-OES) is recovered as PtCl 2 from the gas leaving the reaction zone; 24% 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). Reference Example 2 used 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) in a static tube furnace (75 cm long, at a temperature of 500 ° C, with 12 cm) A total of 6,000 g of grinding catalyst (porous alumina carrier, platinum content 0.15 wt%) was treated in a cylindrical thermal reaction zone of inner diameter. The volumetric flow rate of the gas mixture is 70 liters/h. In the hot zone at a temperature of 200 ° C, the gas leaving the reaction zone recovers a total of 34% of the platinum originally contained in the grinding catalyst (determined by means of ICP-OES) in the form of PtCl 2 ; 66% originally contained in The platinum in the grinding catalyst remains in the catalyst material (determined by ICP-MS after wet chemical digestion of the platinum depleted catalyst). Example 3 uses a gas mixture (67% by weight gaseous aluminum chloride, 18% by weight chlorine, 15% by weight nitrogen) flowing through the reaction zone, and a total of 6,000 g of grinding catalyst (porous alumina carrier, palladium content 0.15 wt%) The fluidized bed reactor (60 cm long, at a temperature of 400 ° C, a cylindrical hot fluidized bed having a 15 cm inner diameter and/or a reaction zone) was fluidized for 60 minutes. The volume flow of the gas mixture is 9.4 m 3 /h. In the hot zone at a temperature of 200 ℃, the gas leaving the reaction zone from a total of 92% recovery in the form of PdCl 2 originally contained in the polishing of palladium catalyst (measured by means of ICP-OES); 8% catalyst originally contained in the polishing The palladium is left in the catalyst material (determined by ICP-MS after wet chemical digestion of the palladium depleted catalyst). Reference Example 4 used 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) in a static tube furnace (75 cm long, at a temperature of 400 ° C, with 12 cm) A total of 6,000 g of grinding catalyst (porous alumina carrier, palladium content 0.1% by weight) was treated in a cylindrical thermal reaction zone of inner diameter. The volumetric flow rate of the gas mixture is 70 liters/h. In the hot zone at a temperature of 200 ° C, a total of 81% of the palladium initially contained in the grinding catalyst (determined by ICP-OES) was recovered as PdCl 2 from the gas leaving the reaction zone; 19% was originally contained in the grinding catalyst. The palladium is left in the catalyst material (measured by ICP-MS after wet chemical digestion of the palladium depleted catalyst).