CN101331240B - 从使用过的含氧化钌的催化剂中回收钌的方法 - Google Patents
从使用过的含氧化钌的催化剂中回收钌的方法 Download PDFInfo
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 229910001925 ruthenium oxide Inorganic materials 0.000 title claims abstract description 14
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000011084 recovery Methods 0.000 title description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 21
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 19
- 230000002829 reductive effect Effects 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 6
- 239000011707 mineral Substances 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 10
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 238000010306 acid treatment Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims 1
- 239000012876 carrier material Substances 0.000 abstract description 4
- 239000007789 gas Substances 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 239000010970 precious metal Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003570 air Substances 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 platinum metals Chemical class 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- MAZOHJVAXBNBPX-UHFFFAOYSA-N ruthenium hydrochloride Chemical compound Cl.[Ru] MAZOHJVAXBNBPX-UHFFFAOYSA-N 0.000 description 1
- VDRDGQXTSLSKKY-UHFFFAOYSA-K ruthenium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ru+3] VDRDGQXTSLSKKY-UHFFFAOYSA-K 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/048—Recovery of noble metals from waste materials from spent catalysts
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
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-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/68—Liquid treating or treating in liquid phase, e.g. dissolved or suspended including substantial dissolution or chemical precipitation of a catalyst component in the ultimate reconstitution of the catalyst
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Abstract
本发明涉及一种从使用过的含钌催化剂中回收钌的方法,所述催化剂含有负载于难以溶于无机酸中的载体材料上的作为氧化钌的钌。所述方法包括下列步骤:a)将含氧化钌的催化剂在氢气流中处理,使得载体上提供的氧化钌被还原为金属钌;b)将来自步骤a)的含有负载于载体材料上的金属钌的经还原的催化剂在含氧气的气体存在下用盐酸处理,使得载体上提供的金属钌以氯化钌(III)溶解,并因此以氯化钌(III)溶液回收;c)合适的话,将来自步骤b)的氯化钌(III)溶液进一步后处理。
Description
本发明涉及一种从使用过的含氧化钌的催化剂中回收钌的方法。
在Deacon于1868开发的催化氧化氯化氢的方法中,借助于氧气以放热的平衡反应将氯化氢氧化,形成氯气。EP-A 0 743 277公开了这样一种催化氧化氯化氢的方法,其中使用包含钌的负载催化剂。在该方法中,钌以氯化钌、氯氧化钌、氯钌酸盐(Chlorruthenat)络合物、三氢氧化钌、钌-胺络合物的形式或者以其它负载于载体上的钌络合物的形式使用。根据GB1,046,313,负载于氧化铝上的氯化钌(III)在催化氧化氯化氢的方法中用作催化剂。
经常将γ-氧化铝用作氧化铝载体。
使用过的含有负载于作为载体的γ-氧化铝上的铂族金属的贵金属催化剂通常通过湿法冶金方法处理,以回收贵金属。这里,将γ-氧化铝载体溶解于氢氧化钠溶液或硫酸中,其中贵金属仍旧作为未溶解的残余物。该回收方法要求所述使用过的催化剂具有低碳含量。具有高碳含量的贵金属催化剂和含有负载于不溶性载体如α-氧化铝、二氧化硅或沸石上的贵金属的催化剂以高温冶金方法处理,以回收贵金属。在高温冶金方法中,催化剂于>1300℃的温度下转化为熔体,并随后分离成它的元素组分,参见“烃工程(Hydrocarbon Engineering)”,2003年7月,48-53以及“烃工程”,2004年3月,31-36。从使用过的包含贵金属的催化剂中通过高温冶金法回收贵金属不仅复杂,而且昂贵。
采用基于α-氧化铝的催化剂的催化氧化氯化氢的方法的缺点是,催化剂的机械强度低。这导致高磨耗和形成细粉。出于这一原因,含有负载于α-氧化铝载体上的钌的贵金属催化剂近期也已经用于催化氧化氯化氢。由于α-氧化铝在氢氧化钠溶液和硫酸中都不溶,因此通过湿法冶金方法从使用过的包含α-氧化铝的催化剂中回收钌被排除掉。
JP 03-013531公开了一种从包含钌或氧化钌的残余物中回收钌的方法。使这些残余物与气态氯在高温下反应,形成氯化钌。随后,将挥发性氯化钌通入氯化钡溶液,并作为水溶性BaRuC15收集。
JP 58-194745公开了一种回收钌的方法,其中首先将存在于耐腐蚀载体上的氧化钌还原为金属钌,并随后转化为可溶的碱金属钌酸盐。
JP 2002-206122涉及这样一种方法,其中从包含钌的混合氧化物中回收钌,所述混合氧化物还含有其它金属。将包含钌的混合氧化物还原,使得钌和其它金属被还原。除了钌之外的其它金属随后借助于酸处理而溶解,其中钌留下为不溶性残余物,并通过过滤分离。
本发明的目的是提供一种从含钌催化剂中回收钌的方法,所述催化剂含有负载于微溶于无机酸的陶瓷载体材料上的呈氧化物形式的钌。该方法实施简便并且廉价。
上述目的通过一种从使用过的含钌催化剂中回收钌的方法得以实现,所述催化剂含有负载于微溶于无机酸的载体材料上的作为氧化钌的钌,该方法包括下列步骤:
a)将含氧化钌的催化剂在氢气流中处理,其中氧化钌被还原为金属钌;
b)将来自步骤a)的含有负载于微溶性载体材料上的金属钌的经还原的催化剂在含氧气的气体存在下用盐酸处理,其中存在于载体上的金属钌以氯化钌(III)溶解,并且以氯化钌(III)水溶液获得;
c)合适的话,将来自步骤b)的氯化钌(III)溶液进一步后处理。
可通过本发明方法处理的合适的微溶性载体材料例如是α-氧化铝、二氧化硅、二氧化钛(金红石型和锐钛矿型TiO2,优选金红石型TiO2)、二氧化锆、沸石和石墨。优选的载体是α-氧化铝。
本发明方法优选用于从这样的使用过的含钌催化剂中回收钌,所述含钌催化剂已经用于Deacon方法中并且包含合适的话,与其它载体材料混合的作为载体的α-氧化铝。通常而言,载体基本上由α-氧化铝组成,但是可以包含其它载体材料,例如石墨、二氧化硅、二氧化钛和/或二氧化锆,优选二氧化钛和/或二氧化锆。通常而言,该催化剂已经于高于200℃、优选高于350℃的温度下用于催化氧化氯化氢。该反应温度通常不超过600℃,优选不超过500℃。
通过本发明方法后处理的含钌催化剂通常通过将载体材料用钌盐的水溶液浸渍而获得,其中催化剂的成形在载体材料浸渍之后或优选浸渍之前进行。该催化剂还可以以平均粒度为10-200μm的粉末形式用作流化床催化剂。对于固定床催化剂,它们通常以催化剂成形体形式使用。在浸渍之后,通常将催化剂成形体或粉末干燥,并随后于100-400℃的温度下在空气、氮气或氩气气氛,优选在空气气氛中煅烧。
催化剂成形体或粉末优选首先于100-150℃下干燥,并且随后于200-400℃下煅烧。煅烧导致由氯化物形成氧化物。
本发明从含钌的负载催化剂中回收钌的方法的特别优点在于如下事实:钌可以以氯化钌(III)水溶液形式回收。该氯化钌(III)溶液可随后通过将其用于新鲜载体材料,之后干燥以及合适的话,煅烧经浸渍的载体而用于再生催化剂。
含氧化钌的催化剂在步骤a)中的还原通常在在氢气流中在升高的温度下,通常于50-600℃下,优选于100-300℃,特别优选于140-250℃,例如于约200℃下进行。该还原可例如通过将氢气在旋转管式炉中在使用过的催化剂上通过而进行。
钌在步骤b)中的氧化优选在氯化氢含量为20-37重量%,例如约32重量%的浓盐酸中进行。该氧化在含氧气的气体,例如空气存在下进行。例如,可以将含金属钌的微溶性载体与浓盐酸一起置于高压釜中,并将空气通入到该溶液中。为了限制溶液体积,可额外通入气态的氯化氢。金属钌的溶解经常在通常60-150℃,例如约100℃的升高的温度下发生。
所得的含氯化钌(III)的水溶液合适的话,可以包含呈氯化物形式的其它金属。这些其它金属可能来自反应器材料,并且可能由于摩蚀的结果进入到催化剂中(例如,来自含镍不锈钢的镍),或者作为除了钌之外的其它活性金属已经包含到含镍催化剂中。因此,含钌催化剂可包含例如选自如下的贵金属:钯、铂、锇、铱、铜、银、金和铼。这些其它金属可在任选的后处理步骤c)中通过常规方法部分或全部分离出来。合适的方法描述于Beck的Edelmetall-Taschenbuch,第二版,Heidelberg:Hüthig 1995和Winnacker-Küchler,Chemische Technologie,第4版,第4卷,540-572。
本发明通过下列实施例来阐述。
实施例
将300g含有负载于作为载体的α-氧化铝上的2重量%RuO2的使用过的催化剂在旋转管式炉中于200℃下在氢气流中还原3小时。此处,首先将催化剂在氮气流中加热至200℃,然后在N2/H2(5∶1)流中还原1小时,之后在纯氢气中还原3小时。将经还原的催化剂在氮气氛下分配到有氮气通入其中的容器中。随后,将经还原的催化剂在氮气氛下转移到2000ml搅拌装置中,并加入1160g的32重量%强度的盐酸。在搅拌和引入氮气的同时,将混合物加热至100℃。随后,将混合物于100℃下搅拌,同时用50L/h空气将该溶液吹洗24小时。获得深红色氯化钌溶液,将该溶液与残余物滗析分离。作为残余物剩下的载体用约1L水洗涤,直至达到中性为止。随后,将载体于120℃下干燥16小时,并测定载体的钌含量。该测定显示,钌含量为0.20重量%。作为对比,使用过的催化剂包含1.49重量%的钌。因此,原始包含的钌的约13%留在载体上。
Claims (5)
1.一种从使用过的含钌催化剂中回收钌的方法,所述使用过的含钌催化剂含有负载于微溶于无机酸的载体材料上的作为氧化钌的钌,该方法包括下列步骤:
a)将所述使用过的含钌催化剂在氢气流中处理,其中存在于载体材料上的氧化钌被还原为金属钌;
b)将来自步骤a)的含有负载于载体材料上的金属钌的经还原的催化剂于60-150℃的温度下在空气存在下用氯化氢含量为20-37重量%的盐酸处理,其中将空气通入到盐酸中,其中存在于载体材料上的金属钌以氯化钌(III)溶解,并且以氯化钌(III)水溶液获得;
c)任选将来自步骤b)的氯化钌(III)溶液进一步后处理。
2.根据权利要求1的方法,其中微溶于无机酸的载体材料包含α-氧化铝。
3.根据权利要求1的方法,其中含钌催化剂通过将微溶于无机酸的载体材料用氯化钌(III)溶液浸渍、干燥和煅烧而生产。
4.根据权利要求3的方法,其中在步骤b)中获得的氯化钌(III)溶液用于生产新鲜催化剂。
5.根据权利要求1的方法,其中将含钌催化剂用于氯化氢的催化氧化。
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DE102008006797B4 (de) * | 2008-01-30 | 2014-05-22 | Heraeus Precious Metals Gmbh & Co. Kg | Verfahren und Vorrichtungen zum Entfernen von Ruthenium durch Destillation als RuO4 aus ruthenathaltigen Lösungen |
US8057572B2 (en) | 2008-03-07 | 2011-11-15 | Exxonmobil Research And Engineering Company | Metal recovery |
DE102008039278A1 (de) | 2008-08-22 | 2010-02-25 | Bayer Materialscience Ag | Verfahren zur Gewinnung von metallischem Ruthenium oder Rutheniumverbindungen aus Ruthenium-haltigen Feststoffen |
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EP2391740B1 (de) * | 2008-12-30 | 2014-04-09 | Basf Se | Verfahren zur wiedergewinnung von ruthenium aus gebrauchten rutheniumoxidhaltigen katalysatoren |
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CN102560128B (zh) * | 2012-03-05 | 2013-10-09 | 武汉凯迪工程技术研究总院有限公司 | 氧化铝负载钌废催化剂中回收钌的方法 |
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CN111100999B (zh) * | 2018-10-26 | 2021-11-05 | 贵研资源(易门)有限公司 | 废催化剂钌的回收方法 |
KR102262496B1 (ko) * | 2018-12-21 | 2021-06-07 | 한화솔루션 주식회사 | 염소 제조용 산화루테늄 담지 촉매의 제조방법 및 이에 의해 제조된 촉매 |
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