K.A. Rasmussen 2024-07-19 LIG-001PCT2 Process for the capture of a noble metal, especially rhodium, lost by volatilization from a catalyst to a high heated gas stream by using an oxide FIELD OF THE INVENTION: The present invention relates to a process for the capture of a noble metal, especially of rhodium, lost by volatilization from a catalyst to a high heated gas stream (including local heating due to a highly exothermic reaction) by contacting the highly heated gas stream containing the volatilized noble metal with a first oxide element comprising at least one oxide, preferably being selected from of formula ABO3 (especially in form of a perovskite or its RP phases/An+1BnO3n+1 (n = integer, preferably n = 1, 3)). This process is especially useful in relation to the industrial processes like the Ostwald process (showing a highly exothermic reaction) where a catalyst containing rhodium (and platinum) is used. In selected circumstances these oxides may also act on the decomposition/conversion of unwanted N2O arising in said Ostwald process. Other aspects of this invention relate to the use of said oxide for the capture of rhodium or devices comprising this oxide that are used in the capture of rhodium. BACKGROUND OF THE INVENTION: Chemical processes on an industrial scale often rely on catalysts of noble metals. One of the metals used in this way is rhodium, a highly precious metal that is lost from the catalyst over time, especially if the process is proceeding at high temperatures and/or is highly exothermic. One of these industrial processes is the Ostwald process. Nitrogen-based inorganic fertilizers are produced from nitric acid obtained in the Ostwald process. In the first step, ammonia is oxidized over a Pt-Rh (typically 95:5 wt%) catalytic gauze at high temperature and moderate pressure to produce nitric oxide (NO). Under industrial conditions the yields achieved with the catalytic gauzes are 95–97 % depending on pressure and temperature. The strong greenhouse gas nitrous oxide (N2O) is an unwanted byproduct. Due to the highly exothermic nature of the oxidation reaction, Pt and
K.A. Rasmussen 2024-07-19 LIG-001PCT2 Rh are lost as PtO2 and RhO2 into the gas phase, with Pt being the dominating loss. Along with the cost of the ammonia feedstock, metal loss causes the largest costs in the production of nitric acid. Capturing and recycling of the precious metals is therefore a key problem that needs to be solved. There are different Pt catchment systems that have been utilized industrially to reduce the Pt loss including glass wool filters, Raschig rings, marble chips and Pd-X alloys (X = Au, Cu, Co, Ni). The most common technology used today is woven Pd-Ni (95:5 wt%) catchment gauzes installed downstream of the Pt-Rh catalyst gauzes; capturing the formed gaseous PtO2 and incorporate Pt into the Pd based alloy. Unfortunately, there are a few drawbacks with the Pd-Ni catchment system. Complete reconstruction of the Pd-Ni wire give rise to swelling and significant blockage of the gauzes; which in turn creates an undesired pressure drop. In addition, Pd is lost into gas phase, affecting the cost-benefit of the process. One other path of Pt catchment that was explored was the identification of CaO to be suited for Pt catchment due to the possible formation of CaxPt3O4 (0 ≤ x ≤ 1) (“N.I. Zakharchenko, Recovery of platinum with calcium oxide sorbent in ammonia oxidation, Russ. J. Appl. Chem.75 (2002) 402–407”). Still, it remains an important task to find alternative and improved ways for the capture of noble metals, especially rhodium, that get lost from catalysts during high temperature industrial processes. SUMMARY OF THE INVENTION: This task is solved by the present invention. The present invention discloses a process for the capture of a noble metal, especially of rhodium, lost by volatilization from a catalyst to a high heated gas stream by contacting the highly heated gas stream containing the volatilized noble metal with a first oxide element comprising at least one oxide, preferably being selected from of formula ABO3 (especially in form of a perovskite or its RP phases/An+1BnO3n+1 (n = integer, preferably n
K.A. Rasmussen 2024-07-19 LIG-001PCT2 = 1, 3)), as well as the use of these oxides for capture of such a noble metal or catchment devices comprising such an oxide. The invention is directed in a main aspect to a process for the capture of rhodium lost by volatilization from a catalyst comprising rhodium to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains the volatilized rhodium while such volatilized rhodium is still essentially in the vapor phase and at a temperature of at least 700 °C with a first oxide element comprising at least one oxide being selected from - an oxide of formula ABO3, especially as a perovskite, with A being selected from alkali earth, alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, Sr, Ca and Ba, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Fe, Co and ; optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement; or - an oxide of formula An+1BnO3n+1, with n being 1 or 3, with A being selected from alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Pr, Nd, Sr and Ca, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga; optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement. It is preferred if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, preferably La, Pr, Nd and Gd, more preferably La and Nd, and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga), preferably from Fe or Ni, (more preferably from Ni); optionally with one or more
K.A. Rasmussen 2024-07-19 LIG-001PCT2 elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement; especially if said oxide is selected from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, Nd2NiO4, Nd4Ni3O10, LaFeO3, and LaCoO3, preferably from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, LaFeO3 and LaCoO3; more preferably from LaNiO3, La2NiO4, La4Ni3O10 and NdNiO3. In a preferred OPTION A (in embodiment “OA-01”) of the invention it is preferred if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with B being selected from Fe or Ni, preferably Ni. In this preferred OPTION A (in embodiment “OA-02” also optionally combined with embodiment “OA-01”) of the invention it is also preferred if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Pr, Nd and Gd, preferably from La and Nd. In this preferred OPTION A (in embodiment “OA-03” also optionally combined with embodiments “OA-01” and “OA-02”) of the invention it is also preferred if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe or Ni, preferably Ni; preferably wherein said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe or Ni, preferably Ni. In this preferred OPTION A (in embodiment “OA-04” also optionally combined with embodiments “OA-01” – “OA-03”) of the invention it is also preferred if said oxide is selected from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, Nd2NiO4, Nd4Ni3O10 and LaFeO3, preferably from LaNiO3, NdNiO3 and LaFeO3. In a preferred OPTION B (in embodiment “OB-01”) of the invention it is preferred
K.A. Rasmussen 2024-07-19 LIG-001PCT2 - if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from Pr, Nd and Gd, preferably Nd, and with B being selected from Fe or Ni; or - if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe; preferably - if said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from Pr, Nd and Gd, preferably Nd, and with B being selected from Fe or Ni; or - if said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe. In this preferred OPTION B (in embodiment “OB-02” also optionally combined with embodiment “OB-01”) of the invention it is also preferred if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from Pr, Nd and Gd, preferably Nd, and with B being selected from Fe or Ni; preferably wherein said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from Pr, Nd and Gd, preferably Nd, and with B being selected from Fe or Ni. It is very preferred if the said oxide is selected from NdNiO3, Nd2NiO4, and Nd4Ni3O10, especially is NdNiO3. In this preferred OPTION B (in embodiment “OB-03” also optionally combined with embodiment “OB-01”) of the invention it is also preferred if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe; preferably wherein said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe. It is very preferred if the said oxide is LaFeO3.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 In this preferred OPTION B (in embodiment “OB-04” also optionally combined with embodiments “OB-01” - “OB-03”) of the invention it is also preferred if said oxide is selected from NdNiO3, Nd2NiO4, Nd4Ni3O10 and LaFeO3, preferably from NdNiO3 and LaFeO3. The invention is based on the surprising effect that it is possible to also capture rhodium – if mobilized/volatilized by the high temperature gas reaction from a catalyst – could be captured by selected oxides. The inventors have seen this in their experiments showing a clear advantage over CaO - known from the art to capture platinum. The inventors have found that especially the use of the perovskites in this process was able to capture rhodium and furthermore to a much larger extent than seen in the art (CaO). This came as surprise over what is described in the art FIGURES: Fig.1) shows the result of a 26 days experiment for the catchment of rhodium (starting with 10 wt.% Rh) in a 5- zone furnace at 700, 800 and 900°C with CaO, showing the respective relations of the detected metals Ca, Pt, and Rh at the various temperatures (see Example 1). The results seen on Fig.1) are as follows: - at 700°C the respective relations of the detected metals are: o 100% Ca - at 800°C the respective relations of the detected metals are: o 98% Ca o 2% Pt - at 900°C the respective relations of the detected metals are: o 96% Ca o 1% Pt o 3% Rh
K.A. Rasmussen 2024-07-19 LIG-001PCT2 Fig.2) shows the result of a 26 days experiment for the catchment of rhodium (starting with 10 wt.% Rh) in a 5- zone furnace at 700, 800 and 900°C with NdNiO3, showing the respective relations of the detected metals Nd, Ni, Pt, and Rh at the various temperatures (see Example 1). The results seen on Fig.2) are as follows: - at 700°C the respective relations of the detected metals are: o 48% Nd o 50% Ni o 2% Pt - at 800°C the respective relations of the detected metals are: o 43% Nd o 42% Ni o 14% Pt o 1% Rh - at 900°C the respective relations of the detected metals are: o 42% Nd o 39% Ni o 14% Pt o 5% Rh DETAILED DESCRIPTION OF THE INVENTION: The invention relates to a process for the capture of rhodium lost by volatilization from a catalyst comprising rhodium to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains the volatilized rhodium while such volatilized rhodium is still essentially in the vapor phase and at a temperature of at least 700 °C with a first oxide element comprising at least one oxide being selected from
K.A. Rasmussen 2024-07-19 LIG-001PCT2 - an oxide of formula ABO3, especially as a perovskite, with A being selected from alkali earth, alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, Sr, Ca and Ba, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga; optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement; - an oxide of formula An+1BnO3n+1, with n being 1 or 3, with A being selected from alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Pr, Nd, Sr and Ca, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga; optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement. As said above, the invention is based on the surprising effect that also rhodium – if mobilized by the high temperature gas reaction from a catalyst – could be captured by selected oxides. This is especially true if seen on the experiments of EXAMPLE 1. In these experiments showing the use of a selected perovskite NdNiO3 compared to CaO - known from the art to capture platinum - showed that the use of the perovskites in this process was able to capture rhodium and further more to a much larger extent than seen in the art (CaO). This was not predictable at all as the art is mostly silent on rhodium capture. As a general remark all uses of “comprising” for an embodiment within this description and claims would include as a more specific embodiment also “consisting of”. Thus “first oxide element comprising at least one oxide” could in a more specific embodiment be “first oxide element consisting of at least one oxide”. In a preferred embodiment of the process according to the invention the process also serves for the additional capture of platinum thus also lost by volatilization from a catalyst comprising rhodium and platinum to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which
K.A. Rasmussen 2024-07-19 LIG-001PCT2 comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains thus volatilized rhodium and platinum while such volatilized rhodium and platinum is still essentially in the vapor phase and at a temperature of at least 700 °C with said first oxide element. This even more specific element of the invention is additionally based on the effect that it was found that in many cases also a pronounced Pt capture is seen, for example in the experiments of example 3, Table 1 (which is in some aspects close to the industrial situation) where the oxides were able to capture both Rh and Pt. This was unknown from the art. NdNiO3 was shown to capture both Pt and Rh and the same applies for LaNiO3, La2NiO4 and La4Ni3O10. OPTION A: In a preferred OPTION A (in embodiment “OA-01”) of the invention it is preferred if said oxide (defined above) is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with B being selected from Fe or Ni, preferably Ni. In this preferred OPTION A (in embodiment “OA-02” also optionally combined with embodiment “OA-01”) of the invention it is also preferred if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Pr, Nd and Gd, preferably from La and Nd. Accordingly, there is a preferred aspect of the invention covering OPTION A (furthermore ASPECT A). In this preferred aspect of the invention covering OPTION A (thus ASPECT A), the invention relates to a process for the capture of rhodium (and optionally also platinum) lost by volatilization from a catalyst comprising rhodium to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains the volatilized rhodium while such volatilized rhodium is still essentially in the vapor phase and at a temperature of at least 700 °C with a first oxide element comprising at least one oxide being selected from
K.A. Rasmussen 2024-07-19 LIG-001PCT2 - an oxide of formula ABO3, especially as a perovskite, with A being selected from alkali earth, alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, Sr, Ca and Ba, and with B being selected from Fe or Ni, preferably Ni; - an oxide of formula An+1BnO3n+1, with n being 1 or 3, with A being selected from alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Pr, Nd, Sr and Ca, and with B being selected from Fe or Ni, preferably Ni. In this ASPECT A of the invention it is also preferred if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Pr, Nd and Gd, preferably from La and Nd. In this ASPECT A of the invention it is also further preferred if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe or Ni, preferably Ni; preferably wherein said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe or Ni, preferably Ni. In this ASPECT A of the invention it is also further preferred if said oxide is selected from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, Nd2NiO4, Nd4Ni3O10 and LaFeO3, preferably from LaNiO3, NdNiO3 and LaFeO3. OPTION B: In a preferred OPTION B of the invention it is preferred - if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from Pr, Nd and Gd, preferably Nd, and with B being selected from Fe or Ni; or
K.A. Rasmussen 2024-07-19 LIG-001PCT2 - if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe; preferably - if said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from Pr, Nd and Gd, preferably Nd, and with B being selected from Fe or Ni; or - if said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe. Accordingly, there is a preferred aspect of the invention covering OPTION B (furthermore ASPECT B). In this preferred aspect of the invention covering OPTION B (thus ASPECT B), the invention relates to a process for the capture of rhodium (and optionally also platinum) lost by volatilization from a catalyst comprising rhodium to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains the volatilized rhodium while such volatilized rhodium is still essentially in the vapor phase and at a temperature of at least 700 °C with a first oxide element comprising at least one oxide being selected from - an oxide of formula ABO3, especially as a perovskite and/or an oxide of formula An+1BnO3n+1, with n being 1 or 3, o with A being selected from Pr, Nd and Gd, preferably Nd, and with B being selected from Fe or Ni; or - an oxide of formula ABO3, especially as a perovskite and/or an oxide of formula An+1BnO3n+1, with n being 1 or 3,
K.A. Rasmussen 2024-07-19 LIG-001PCT2 o with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe. In this ASPECT B of the invention it is preferred - if said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from Pr, Nd and Gd, preferably Nd, and with B being selected from Fe or Ni; or - if said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe. In this ASPECT B of the invention it is also preferred if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from Pr, Nd and Gd, preferably Nd, and with B being selected from Fe or Ni; preferably wherein said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from Pr, Nd and Gd, preferably Nd, and with B being selected from Fe or Ni; preferably, wherein the said oxide is selected from NdNiO3, Nd2NiO4, and Nd4Ni3O10, especially is NdNiO3. In this ASPECT B of the invention it is alternatively preferred if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe; preferably wherein said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe. preferably, wherein the said oxide is LaFeO3. In this ASPECT A of the invention it is also further preferred if said oxide is selected from NdNiO3, Nd2NiO4, Nd4Ni3O10 and LaFeO3, preferably from NdNiO3 and LaFeO3.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 In a preferred embodiment of the process according to the invention (and of both ASPECT A and ASPECT B) said highly heated gas stream in addition to contacting said first oxide element is further also contacting a metallic element comprising a metallic material selected from the group consisting of palladium, and palladium alloys, more specifically palladium-nickel alloys and palladium-gold alloys. This preferred embodiment of the invention carries the additional advantage that it is based on the selection of combining a metal element such as the Pd/Ni catchment device and the oxide This is a very advantageous combination as the Pd/Ni catchment device captures platinum and the first oxide element helps capturing rhodium. In this, it is preferred in the process according to the invention when the contact with said metallic element precedes and/or is upstream from the contact with said first oxide element; or follows and/or is downstream from the contact with said first oxide element. In a preferred embodiment of the process according to the invention (and of both ASPECT A and ASPECT B) said highly heated gas stream in addition to contacting said first oxide element is further also contacting a second oxide element, (being different from said first oxide element)comprising at least one further oxide also selected from the oxides as defined so far in the “DETAILED DESCRIPTION OF THE INVENTION” above (and especially in (ASPECT A and ASPECT B) but being different from said at least one oxide comprised in said first oxide element. This preferred embodiment of the invention is also completely unknown in the art and has the additional advantage that in this combination e.g. the second oxide element can be chosen to be better suited to capture platinum while the first oxide element helps capture rhodium etc. In this, it is preferred in the process according to the invention when the contact with said second oxide element precedes and/or is upstream from the contact with said first oxide element;
K.A. Rasmussen 2024-07-19 LIG-001PCT2 or follows and/or is downstream from the contact with said first oxide element. In a preferred embodiment of the process according to the invention (and of both ASPECT A and ASPECT B) said highly heated gas stream after its contact with said catalyst is contacted with said first oxide element at a temperature at around or above 800°C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C), preferably at around 900 °C or above (or at 850°C to 950°C), preferably wherein said high temperature gas reaction is carried out at temperatures of at around or above 800°C, preferably at around 900°C or above. This preferred embodiment of the invention is further based on the surprising finding that rhodium capture on the oxide seems to be connected to a higher temperature. This more pronounced capture of rhodium with these higher temperatures at around 900°C can be seen in Example 1. As can be seen there at around 800 °C Platinum capture seems optimized and dominates. The art is completely silent on this influence of temperature on rhodium (or platinum) capture. In this, it is preferred in the process according to the invention (and of both ASPECT A and ASPECT B) when the process also serves for the additional capture of platinum thus also lost by volatilization from a catalyst comprising rhodium and platinum to a high heated gas stream contacted therewith in a high temperature gas reaction which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains thus volatilized rhodium and platinum while such volatilized rhodium and platinum is still essentially in the vapor phase with said first oxide element at a temperature at around or above 800°C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C), preferably at around 900 °C (or at 850°C to 950°C) or above, preferably wherein said high temperature gas reaction is carried out at temperatures of at around or above 800°C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C), preferably at around 900°C or above, preferably wherein said high temperature gas reaction is carried out at temperatures of at around or above 800°C, preferably at around 900°C. In a preferred embodiment of the process according to the invention (and of both ASPECT A and ASPECT B) the highly heated gas stream also contains N2O, which is
K.A. Rasmussen 2024-07-19 LIG-001PCT2 converted/decomposed upon contact with said first oxide element, preferably wherein the N2O is converted/decomposed to NO, NOx, N2 and/or O2. This is a further preferred embodiment of the invention which is based on the further surprising finding that N2O can also be converted by these oxides. The strong greenhouse gas nitrous oxide (N2O) is an unwanted byproduct of the Ostwald process. This is very advantageous as thus the (first) oxide element or the (at least one) oxide serves a double purpose (or even a triple purpose if both platinum and rhodium are captured) in the process according to the invention with the additional conversion/decomposition of N2O. The art is not suggesting this aspect. In a preferred embodiment of the process according to the invention (and of both ASPECT A and ASPECT B) the catalytic reaction of the high temperature gas reaction is a catalytic ammonia oxidation or catalytic ammonia combustion. This refers mostly to the Ostwald process being the process to which the inventive process refers. It is especially useful for converting N2O that is – as said above - an unwanted byproduct of the Ostwald process. In a very preferred embodiment of the process according to the invention (and of ASPECT A) said at least one oxide of the first oxide element is selected from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, and LaFeO3. In a very preferred embodiment of the process according to the invention (and of ASPECT A) said at least one oxide of the first oxide element is selected from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, and LaFeO3. In a very preferred embodiment of the process according to the invention (and of ASPECT A) said at least one oxide of the first oxide element is selected from LaNiO3, La2NiO4, and La4Ni3O10. In a very preferred embodiment of the process according to the invention (and of both ASPECT A and ASPECT B) said at least one oxide of the first oxide element is selected from NdNiO3, Nd2NiO4, Nd4Ni3O10, and LaFeO3.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 In a very preferred embodiment of the process according to the invention (and of both ASPECT A and ASPECT B) said at least one oxide of the first oxide element is selected from NdNiO3, Nd2NiO4, Nd4Ni3O10, and LaFeO3. In a very preferred embodiment of the process according to the invention (and of ASPECT A) said at least one oxide of the first oxide element is selected from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, Nd2NiO4 and Nd4Ni3O10. In a very preferred embodiment of the process according to the invention (and of ASPECT A) said at least one oxide of the first oxide element is selected from LaNiO3, NdNiO3, and LaFeO3. In a very preferred embodiment of the process according to the invention (and of ASPECT A) said at least one oxide of the first oxide element is selected from LaNiO3 and NdNiO3. In a very preferred embodiment of the process according to the invention (and of both ASPECT A and ASPECT B) said at least one oxide of the first oxide element is selected from NdNiO3, and LaFeO3. In a very preferred embodiment of the process according to the invention (and of both ASPECT A and ASPECT B) said at least one oxide of the first oxide element is LaFeO3. In a very preferred embodiment of the process according to the invention (and of both ASPECT A and ASPECT B) said at least one oxide of the first oxide element is NdNiO3. In a very most preferred embodiment of the process according to the invention (and of ASPECT A) said at least one oxide of the first oxide element is LaNiO3. In another preferred aspect, the invention (also regarding both ASPECT A and ASPECT B) relates to a use of an oxide element comprising at least one oxide selected from the oxides as defined so far in the “DETAILED DESCRIPTION OF THE INVENTION” above (and especially in (ASPECT A and ASPECT B) for said at least one oxide comprised in said first oxide element for the capture of rhodium and/or of platinum and rhodium. In a preferred embodiment of this use according to the invention the use is for the capture of platinum and rhodium, especially in the same process.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 In a further preferred embodiment of this use according to the invention the use further encompasses the decomposition/conversion of N2O, especially in the same process, preferably wherein the N2O is decomposed/converted upon contact with said oxide element, most preferably wherein the N2O is decomposed/converted to NO, NOx, N2 and/or O2. In another preferred aspect, the invention (also regarding both ASPECT A and ASPECT B) relates to a device for the capture of rhodium and/or of platinum and rhodium from a combustion furnace of the type having a noble metal gauze arranged across the furnace in a direction transverse to the flow of gas therethrough, said device being an oxide element comprising or consisting of at least one oxide selected from the oxides as defined so far in the “DETAILED DESCRIPTION OF THE INVENTION” above (and especially in (ASPECT A and ASPECT B) for said at least one oxide comprised in said first oxide element. In another preferred aspect, the invention relates to a catchment device for the capture of rhodium or of platinum and rhodium, in an ammonia oxidation reaction, comprising an oxide element comprising or consisting of at least one oxide selected from the oxides as defined so far in the “DETAILED DESCRIPTION OF THE INVENTION” above (and especially in (ASPECT A and ASPECT B) for said at least one oxide comprised in said first oxide element. Definitions: In the context of the invention “lanthanoid” is to be understood as meaning a series of chemical elements of atomic numbers 57-71, from lanthanum through lutetium. Preferably the “lanthanoids” in the context of the invention are selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd. In the context of the invention “transition metal” is to be understood as meaning a chemical element in d-block of the periodic table, including groups 3 to 12. Preferably the “transition metals” in the context of the invention are selected from Fe, Co, Ni and Zn ….
K.A. Rasmussen 2024-07-19 LIG-001PCT2 In the context of the invention “alkaline earth metal” is to be understood as meaning the chemical elements Be, Mg, Ca, Sr, Ba and Rd from Group 2 of the periodic table. In the context of the invention “alkali metal” is to be understood as meaning the chemical elements Li, Na, K, Rb, Cs and Fr from Group 1 of the periodic table. In the context of the invention “capture” is to be understood as meaning the fixation of the noble metal that was volatilized before on e.g. an oxide element, the oxide or the metal element or a metal of the metal element. In the context of this invention “decompose” and/or “convert” is to be understood as meaning the conversion/decomposition, especially of N2O, especially to NO, NOx, N2 and/or O2. This happens upon contact with an element, e.g. the “first oxide element”, (or the oxide comprised therein) and thus for example leads to an abatement of the laughing gas. In the context of the invention “volatilization (from a catalyst)” is to be understood as meaning the removal of the noble metal like rhodium or platinum from e.g. the solid metal structure of e.g. the catalyst and putting this noble metal or any derivative in its “vapor phase”, including taking it up in this vapor phase e.g. in a gas stream. This volatilization usually happens at “high temperatures”. In the context of the invention “high temperature” is to be understood as meaning at a temperature of or above 700°C. In the context of the invention “contact” is to be understood as meaning a physical contact or close contact e.g. coming within 1 cm or less, e.g. between the gas of a “high heated gas stream” or a volatilized noble metal (or a derivative, e.g. in said gas stream with an oxide element or the metal element. In the context of the invention “high heated gas stream” is to be understood as meaning as steam of gas like N2, NH3, air, O2, CO2 or any other gas at temperatures of or above 700°C. In the context of the invention “perovskite” is to be understood as meaning that a perovskite is a compound, ABX3, that belong to the class of compounds that take a perovskite type structure. When X = O, the perovskite is an oxide ABO3. In the ideal
K.A. Rasmussen 2024-07-19 LIG-001PCT2 perovskite structure, the B-site cation is 6-coordinated to oxygen and A-site is 12- coordinated to oxygen. A site cation is generally from alkali earth, alkaline earth and rare earth elements whereas B site cation is generally selected from 3-5d elements, p-block elements. The perovskite oxide can have lower symmetry, being distorted, and may have oxygen vacancies in random or ordered patterns. In the context of the invention “RP-phase” is to be understood as meaning that an RP phase is a phase that is described by the so-called Ruddlesden-Popper type structure. The general formula for oxides being ABO3 is An+1BnO3n+1 (or (ABO3)n(AO)) whereof n is an integer, preferably with n being 1 or 3. The atomic arrangement in ABO3 (part of the structure) is the same as in the perovskite whereas AO is a structure fragment corresponding to half a rock salt layer. A site cation is generally from alkaline earth and rare earth elements whereas B site cation is generally selected from 3-5d elements, p- block elements. An RP-phase is conveniently described by the parameter “n” in the formula An+1BnO3n+1; for example RP1 is meaning an RP structure with n =1 and hence representing A2BO4. Preferable RP-phases for ABO3 are A2BO or A4B3O10. In the context of the invention “in form of a solid solution” is to be understood as meaning that a solid solution is a uniform mixture of two crystalline solids that share a common crystal lattice. Solid solutions often consist of two or more types of atoms that occupy the same crystallographic site in the crystal structure in a random manner. In the context of the invention “in an ordered arrangement” is to be understood as meaning that an ordered arrangement occurs when two or more types of atoms are having the potential to occupy the same crystallographic site in a crystal structure, however, their distribution is not random in nature as for a solid solution, but rather systematically alternating in manner. Accordingly, in the context of this invention “one or more elements on A position in form of a solid solution or in an ordered arrangement” is to be understood as meaning that the compound has two or more types of category A-atoms that occupy the same crystallographic site in the structure in a random manner (solid solution) or in a systematic manner (ordered arrangement).
K.A. Rasmussen 2024-07-19 LIG-001PCT2 In the context of the invention “rare earth” is to be understood as meaning a cation representing Sc, Y, La or the fourteen 4f-elements; i.e. elements with numbers 21, 38, and 57 to 71 in the Periodic Table. In the context of the invention “lanthanoids/rare earth elements” is to be understood as meaning that the respective “A” is selected from both the lanthanoids or rare earth elements as defined herein. Thus, in a preferred embodiment it encompasses or is selected from Ce, Pr, Nd, Pm, Sm, Eu, Gd, or La, Sc, or Y. In the context of the invention “An+1BnO3n+1(n = 1, 3) – Ruddlesden Popper phases is to be understood as described in the explanation given above for “RP-Phase”. In the context of the invention “3-5d elements” is to be understood as meaning that 3-5d elements refer to 3d, 4d and 5d elements in the periodic table, altogether 10, 10 and 10 elements, respectively In the context of the invention “p-block elements” is to be understood as meaning that p- block elements refer to the elements in groups 13, 14 and 15, in the periodic table. Overview of further embodiments. The invention is further expressed in a separate section below with the help of a number of specific EMBODIMENTS. For all these EMBODIMENTS following below, there are 2 Options separated by the oxides, OPTION A (“OA”) and OPTION B (“OB”) which apply to all these EMBODIMENTS. In a preferred OPTION A (in embodiment “OA-01”) of the invention it is preferred if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with B being selected from Fe or Ni, preferably Ni.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 In this preferred OPTION A (in embodiment “OA-02” also optionally combined with embodiment “OA-01”) of the invention it is also preferred if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Pr, Nd and Gd, preferably from La and Nd. In this preferred OPTION A (in embodiment “OA-03” also optionally combined with embodiments “OA-01” and “OA-02”) of the invention it is also preferred if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe or Ni, preferably Ni; preferably wherein said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe or Ni, preferably Ni. In this preferred OPTION A (in embodiment “OA-04” also optionally combined with embodiments “OA-01” – “OA-03”) of the invention it is also preferred if said oxide is selected from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, Nd2NiO4, Nd4Ni3O10 and LaFeO3, preferably from LaNiO3, NdNiO3 and LaFeO3. In a preferred OPTION B (in embodiment “OB-01”) of the invention it is preferred - if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from Pr, Nd and Gd, preferably Nd, and with B being selected from Fe or Ni; or - if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe; preferably - if said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from Pr, Nd and Gd, preferably Nd, and with B being selected from Fe or Ni;
K.A. Rasmussen 2024-07-19 LIG-001PCT2 or - if said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe. In this preferred OPTION B (in embodiment “OB-02” also optionally combined with embodiment “OB-01”) of the invention it is also preferred if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from Pr, Nd and Gd, preferably Nd, and with B being selected from Fe or Ni; preferably wherein said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from Pr, Nd and Gd, preferably Nd, and with B being selected from Fe or Ni. It is very preferred if the said oxide is selected from NdNiO3, Nd2NiO4, and Nd4Ni3O10, especially is NdNiO3. In this preferred OPTION B (in embodiment “OB-03” also optionally combined with embodiment “OB-01”) of the invention it is also preferred if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe; preferably wherein said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe. It is very preferred if the said oxide is LaFeO3. In this preferred OPTION B (in embodiment “OB-04” also optionally combined with embodiments “OB-01” - “OB-03”) of the invention it is also preferred if said oxide is selected from NdNiO3, Nd2NiO4, Nd4Ni3O10 and LaFeO3, preferably from NdNiO3 and LaFeO3. EMBODIMENT B): RHODIUM CAPTURE WITH OXIDES in Combination with a Pd/Ni capture device OR a second oxide element: B01) A process for the capture of rhodium lost by volatilization from a catalyst comprising rhodium to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which
K.A. Rasmussen 2024-07-19 LIG-001PCT2 comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains the volatilized rhodium while such volatilized rhodium is still essentially in the vapor phase and at a temperature of at least 700 °C with a first oxide element comprising at least one oxide, wherein said highly heated gas stream in addition to contacting said first oxide element is further also contacting a metallic element comprising a metallic material selected from the group consisting of palladium, and palladium alloys, more specifically palladium-nickel alloys and palladium-gold alloys; OR wherein said highly heated gas stream in addition to contacting said first oxide element is further also contacting a second oxide element, (being different from said first oxide element) comprising at least one further oxide being different from said at least one oxide comprised in said first oxide element; wherein said at least one oxide and said at least one further oxide are independently selected from - an oxide of formula ABO3, especially as a perovskite, with A being selected from alkali earth, alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, Sr, Ca and Ba, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga; optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement; - an oxide of formula An+1BnO3n+1, with n being 1 or 3, with A being selected from alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Pr, Nd, Sr and Ca, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga; optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 B02) The process of EMBODIMENT B01), wherein the process also serves for the additional capture of platinum thus also lost by volatilization from a catalyst comprising rhodium and platinum to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains thus volatilized rhodium and platinum while such volatilized rhodium and platinum is still essentially in the vapor phase and at a temperature of at least 700 °C with said first oxide element. These Embodiments B01) and B02) are inventive as based on the selection of combining the Pd/Ni catchment device and the oxide. This is a superior combination as the Pd/Ni catchment device captures platinum and the first oxide element helps capturing rhodium; or the 2 oxide elements can complement each other. In addition, Embodiment B02) is based on the effect that it was found that in many cases also a pronounced Pt capture is seen, for example in the experiments of example 3, Table 1 (which is in some aspects close to the industrial situation) where the oxides were able to capture both Rh and Pt. This was unknown from the art. NdNiO3 was shown to capture both Pt and Rh and the same applies for LaNiO3, La2NiO4, La4Ni3O10 and LaFeO3. EMBODIMENT C): RHODIUM CAPTURE WITH OXIDES in Combination with a raised temperature: C01) A process for the capture of rhodium lost by volatilization from a catalyst comprising rhodium to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains the volatilized rhodium while such volatilized rhodium is still essentially in the vapor phase, with a first oxide element comprising at least one oxide, wherein said highly heated gas stream after its contact with said catalyst is contacted with said first oxide element at a temperature at around or above 800°C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C); and
K.A. Rasmussen 2024-07-19 LIG-001PCT2 wherein said at least one oxide and said at least one further oxide are independently selected from - an oxide of formula ABO3, especially as a perovskite, with A being selected from alkali earth, alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, Sr, Ca and Ba, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga); optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement; - an oxide of formula An+1BnO3n+1, with n being 1 or 3, with A being selected from alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Pr, Nd, Sr and Ca, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga); optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement. C02) The process of EMBODIMENT C01), wherein the process also serves for the additional capture of platinum thus also lost by volatilization from a catalyst comprising rhodium and platinum to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains thus volatilized rhodium and platinum while such volatilized rhodium and platinum is still essentially in the vapor phase with said first oxide element. Embodiment C02) is based on the effect that it was found that in many cases also a pronounced Pt capture is seen, for example in the experiments of example 3, Table 1 (which is in some aspects close to the industrial situation) where the oxides were able to capture both Rh and Pt.This was unknown from the art. NdNiO3 was shown to capture
K.A. Rasmussen 2024-07-19 LIG-001PCT2 both Pt and Rh and the same applies for LaNiO3, La2NiO4, La4Ni3O10 and LaFeO3. In addition, Embodiment C01) is also further inventive as it adds the element of a higher capture of rhodium with these higher temperatures by the first oxide element as can be seen in Example 2. Embodiment C02) even adds the element of a higher capture of better captures the platinum at these specific higher temperatures. The art is silent on this influence of temperature on rhodium (or also platinum) capture. EMBODIMENT D): RHODIUM (ONLY) CAPTURE WITH ABO3-OXIDES (LaNiO3 and NdNiO3, especially and NdNiO3) D01) A process for the capture of rhodium lost by volatilization from a catalyst comprising rhodium to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains the volatilized rhodium while such volatilized rhodium is still essentially in the vapor phase and at a temperature of at least 700 °C with a first oxide element comprising at least one oxide of formula ABO3, in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, wherein A is selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga). EMBODIMENT E); PLATINUM CAPTURE WITH ABO3-OXIDES (LaNiO3 and NdNiO3) or (NdNiO3) E01) A process for the capture of platinum lost by volatilization from a catalyst comprising platinum to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains the volatilized platinum while such volatilized platinum is still essentially in the vapor phase and at a temperature of at least 700 °C with a first oxide element comprising at least one oxide of formula ABO3, in form of a
K.A. Rasmussen 2024-07-19 LIG-001PCT2 perovskite and optionally its respective RP phases like A2BO4, A4B3O10, wherein A is selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga). EMBODIMENT X): RHODIUM (ONLY) CAPTURE WITH OXIDE X02) A process for the capture of rhodium lost by volatilization from a catalyst comprising rhodium to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains the volatilized rhodium while such volatilized rhodium is still essentially in the vapor phase and at a temperature of at least 700 °C with a first oxide element comprising at least one oxide, wherein said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, preferably La, Nd and Gd, more preferably La and Nd, and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga), preferably from Fe or Ni, (more preferably from Ni); optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement; or This Embodiment X) is based on the surprising effect that also rhodium – if mobilized by the high temperature gas reaction from a catalyst – could be captured by selected oxides. This is especially true if seen on the experiments of EXAMPLE 1. In these experiments showing the use of a selected perovskite NdNiO3 compared to CaO - known from the art to capture platinum - showed that the use of the perovskites in this process was able to capture rhodium and further more to a much larger extent than seen in the art (CaO). This was not predictable at all, as the art is mostly silent on rhodium capture. EMBODIMENT Y): PLATINUM (ONLY) CAPTURE WITH OXIDE
K.A. Rasmussen 2024-07-19 LIG-001PCT2 Y02) A process for the capture of platinum lost by volatilization from a catalyst comprising platinum to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains the volatilized platinum while such volatilized platinum is still essentially in the vapor phase and at a temperature of at least 700 °C with a first oxide element comprising at least one oxide, wherein said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, preferably La, Nd and Gd, more preferably La and Nd, and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga), preferably from Fe or Ni, (more preferably from Ni); optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement. This Embodiment Y) is based on the effect that the use of the selected perovskites in this process was superior to the use of CaO for platinum capture that is known from the art (see Table 1). This was not predictable at all from the art. EMBODIMENT Z): PLATINUM AND RHODIUM CAPTURE WITH OXIDE Z02) A process for the capture of rhodium and platinum lost by volatilization from a catalyst comprising rhodium and platinum to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains the volatilized rhodium and platinum while such volatilized rhodium and platinum is still essentially in the vapor phase and at a temperature of at least 700 °C with a first oxide element comprising at least one oxide, wherein said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, preferably La, Nd and
K.A. Rasmussen 2024-07-19 LIG-001PCT2 Gd, more preferably La and Nd, and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga), preferably from Fe or Ni, (more preferably from Ni); optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement. This Embodiment Z) is based on the effect that in many cases also a pronounced Pt capture is seen, for example in the experiments of example 3, Table 1 (which is in some aspects close to the industrial situation) where the oxides were able to capture both Rh and Pt. This was not described in the art. NdNiO3 was shown to capture both Pt and Rh and the same applies for LaNiO3, La2NiO4, La4Ni3O10,and LaFeO3. The present invention is illustrated below with the aid of examples. These illustrations are given solely by way of example and do not limit the general spirit of the present invention. EXAMPLES: Example 1: A laboratory scale six-zone furnace (Entech Energiteknik AB, Sweden) was used in the Pt and Pt+Rh catchment experiments. All the experiments were run in dry air (< 300 ppm H2O) with a flow of approximately 450 mL/min in quartz tubes of inner diameter 4 mm, giving a similar linear gas velocity as in the ammonia oxidation process. Rolled up nets of Pt or Pt-Rh were placed upstream of the oxide rectangular pellets in a zone set to 1000 °C to yield PtO2/RhO2 in the gas phase. The duration of the catchment experiments were in the range from 1 to 26 days, and 3 parallel experiments were run at the same time by placing the oxide pellets in 3 parallel tubes in 3 different zones of different temperatures: 700, 800 and 900 °C. For results see Fig.1) for CaO and 2) for NdNiO3. The results seen on Fig.1) for CaO are as follows: - at 700°C the respective relations of the detected metals are:
K.A. Rasmussen 2024-07-19 LIG-001PCT2 o 100% Ca - at 800°C the respective relations of the detected metals are: o 98% Ca o 2% Pt - at 900°C the respective relations of the detected metals are: o 96% Ca o 1% Pt o 3% Rh The results seen on Fig.2) for NdNiO3 are as follows: - at 700°C the respective relations of the detected metals are: o 48% Nd o 50% Ni o 2% Pt - at 800°C the respective relations of the detected metals are: o 43% Nd o 42% Ni o 14% Pt o 1% Rh - at 900°C the respective relations of the detected metals are: o 42% Nd o 39% Ni o 14% Pt o 5% Rh As can be seen there, the capture of both Pt and Rh was clearly improved in the NdNiO3 over the CaO. The results further seem to indicate that rhodium catchment improves with the rise of the temperature being most effective at temperatures around 900°C or at least favored over Pt. To put these results to scale: if the wire contains 10wt% Rh, the atom % Rh in the wire is 20%; i.e., a 1:1 correlation in Pt-Rh catchment relative to the Pt-Rh catalyst should then give an atomic ratio of Pt/Rh = 80/20.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 On the other hand, these results seem to point at that at 800 °C overall Pt catchment is dominant. Example 2: A laboratory scale six-zone furnace (Entech Energiteknik AB, Sweden) was used in the Pt and Pt+Rh catchment experiments. All the experiments were run in dry air (< 300 ppm H2O) with a flow of approximately 450 mL/min in quartz tubes of inner diameter 4 mm, giving a similar linear gas velocity as in the ammonia oxidation process. Rolled up nets of Pt or Pt-Rh were placed upstream of the oxide rectangular pellets in a zone set to 1000 °C to yield PtO2/RhO2 in the gas phase. The durations of the catchment experiments were in the range from 1 to 26 days, and 3 parallel experiments were run at the same time by placing the oxide pellets in 3 parallel tubes in 3 different zones of different temperatures: 700, 800 and 900 °C. Results on Pt catchment from lab scale experiments at 700, 800 and 900 °C are shown in the Table 1 below. Table 1 shows a summary of EDX results and crystal structure from XRD of surfaces of pellets of catchment oxides after reaction with PtO2(g) at 700, 800 and 900°C for 26 days. The primary cation of each oxide is called A and EDX quantifications are given as Pt/(Pt+A) molar fraction. Table 1: Starting material EDX Pt/(Pt+A) EDX Pt/(Pt+A) EDX Pt/(Pt+A) Pt containing molar fraction molar fraction molar fraction product from XRD @700°C @800°C @900°C La NiO3 0.02 0.40 0.30 La2NiPtO6 La2NiO4 0.05 0.14 0.22 La2NiPtO6 La4Ni3O10 0.01 0.08 0.14 La2NiPtO6 NdNiO3 0.05 0.26 0.30 Nd2NiPtO6 LaFeO3 0* 0* 0* - La0.85Sr0.15FeO3 0.01 0.02 0.02 - CaO 0.50 0.24 0.07 Not measurable
K.A. Rasmussen 2024-07-19 LIG-001PCT2 Example 3: In a pilot plant the following oxides were tested at approx.900 °C for their ability to capture Pt and Rh. A) First round in pilot plant: NdNiO3, LaNiO3, La2NiO4, La4Ni3O10, LaFeO3, CaO, were exposed to the real process conditions based on the Ostwald process (T = 900 °C, P = 5 bar and gas mix of 10 % NOx, 15 % H2O, 5 % O2 and 1300 ppm N2O in N2) for 21 days. Cylindrical pellets of the oxides were sewn into megapyr nets for easier handling. The samples were placed at the top of raching rings in the gas stream after the Pt-Rh catalyst (95:5 wt.%)+Pd-Ni catchment gauze+Co-containing laughing gas. So far only the results for LaNiO3 are available and given below in Table 2. Some of the results for the other oxides were are not available as the influx of Si was maybe too high due to a suspected weakness of the megapyr nets (which contain Si). Others are not finally analyzed, yet, while in some cases the oxide material got damaged. TABLE 2: Oxide Element Mass C. nom. C. Atom C. norm. Error [1 [wt.%] [wt.%] [wt.%] stoich C. Sigma] [wt.%] [wt.%] LaNiO3 Pt 16.24 16.86 9.31 16.86 0.44 Rh 0.33 0.34 0.36 0.34 0.04 La 57.17 59.34 46.03 59.34 1.55 Ni 19.08 19.80 36,35 19.80 0.50 Others* 2.53 3.66 7.95 3.66 - TOTAL: 96,34 100.00 100.00 100.00 * Sum of Si, Co and Pd
K.A. Rasmussen 2024-07-19 LIG-001PCT2 B) Second round in pilot plant LaNiO3, La4Ni3O10, La2NiO4, NdNiO3, CaO and LaFeO3 were exposed to real process conditions (T = 900 °C, P = 5 bar and gas mix of 10 % NOx, 15 % H2O, 5 % O2 and 1300 ppm N2O in N2) for 21 days. Cylindrical pellets of the oxides were sewn into megapyr nets for easier handling. The samples were placed in the gas stream just after the Pt-Rh catalyst (95:5 wt.%) and before a laughing gas catalyst. The results of said second round are given in Table below: TABLE 3: Oxide Element Mass C. nom. C. Atom C. norm. Error [1 [wt.%] [wt.%] [wt.%] stoich C. Sigma] [wt.%] [wt.%] LaNiO3 Pt 13.64 15.78 9.11 15.78 0.37 Rh 3.58 4.14 4.53 4.14 0.15 La 52.08 61.12 49.52 61.12 1.43 Ni 16.16 18.17 35.87 18.71 0.43 Si 0.21 0.25 0.97 0.24 0.04 TOTAL: 86.39 100.00 100.00 100.00 La2NiO4 Pt 23.62 25.23 16.03 25.23 0.60 Rh 1.59 1.70 2.05 1.70 0.08 La 56.50 60.35 53.86 60.35 1.53 Ni 11.41 12.19 25.74 12.19 0.31 Si 0.49 0.52 2.31 0.52 0.05 TOTAL: 93.61 100.00 100.00 100.00 La4Ni3O10 Pt 18.71 21.12 12.67 21.12 0.49 Rh 1.25 1.41 1.61 1.41 0.37 La 54.15 61.12 51.48 61.12 1.47 Ni 13.81 15.59 31.08 15.59 0.37 Si 0.67 0.76 3.16 0.76 0.06 TOTAL: 93.61 100.00 100.00 100.00
K.A. Rasmussen 2024-07-19 LIG-001PCT2 NdNiO3 Pt 11.57 13.32 7.61 13.32 0.33 Rh 0.95 1.10 1.19 1.10 0.07 Nd 55.22 63.54 49.11 63.54 1.46 Ni 19.07 21.94 41.68 21.94 0.51 Si 0.09 0.10 0.41 0.10 0.03 TOTAL: 86.90 100.00 100.00 100.00 LaFeO3 Pt 3.04 3.38 1.71 3.38 0.13 Rh 1.97 2.19 2.10 2.19 0.10 La 60.99 67.83 48.25 67.83 1.66 Fe 23.48 26.11 46.20 26.11 0.63 Si 0.44 0.49 1.73 0.49 0.05 TOTAL: 89.92 100.00 100.00 100.00 CaO Pt 2.92 4.12 0.88 4.12 0.11 Rh 0.43 0.60 0.24 0.60 0.04 Ca 66.94 94.41 97.61 94.41 1.99 Si 0.61 0.86 1.28 0.86 0.06 TOTAL: 70.90 100.00 100.00 100.00 It can be seen in Table 2 and especially in Table 3 that in some cases (see e.g. LaFeO3), where there was no Pt capture in lab scale in Example 2 (see Table 1), a more pronounced Pt capture is seen in the experiments of example 3 (which is in some aspects close to the industrial situation). In addition, there is both platinum and rhodium capture. EMBODIMENTS EMBODIMENT A) GENERAL; THE PCT CLAIMS
K.A. Rasmussen 2024-07-19 LIG-001PCT2 A 01) A process for the capture of rhodium lost by volatilization from a catalyst comprising rhodium to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains the volatilized rhodium while such volatilized rhodium is still essentially in the vapor phase and at a temperature of at least 700 °C with a first oxide element comprising at least one oxide being selected from - an oxide of formula ABO3, especially as a perovskite, with A being selected from alkali earth, alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, Sr, Ca and Ba, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga; optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement; or - an oxide of formula An+1BnO3n+1, with n being 1 or 3, with A being selected from alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Pr, Nd, Sr and Ca, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga. In a preferred OPTION A (in embodiment “OA-01”) of this EMBODIMENT A01) it is preferred if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with B being selected from Fe or Ni, preferably Ni.. In this preferred OPTION A (in embodiment “OA-02” also optionally combined with embodiment “OA-01”) of this EMBODIMENT A01) it is also preferred if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Pr, Nd and Gd, preferably from La and Nd.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 In this preferred OPTION A (in embodiment “OA-03” also optionally combined with embodiments “OA-01” and “OA-02”) of this EMBODIMENT A01) it is also preferred if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe or Ni, preferably Ni; preferably wherein said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe or Ni, preferably Ni. In this preferred OPTION A (in embodiment “OA-04” also optionally combined with embodiments “OA-01” – “OA-03”) of this EMBODIMENT A01) it is also preferred if said oxide is selected from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, Nd2NiO4, Nd4Ni3O10 and LaFeO3, preferably from LaNiO3, NdNiO3 and LaFeO3. In a preferred OPTION B (in embodiment “OB-01”) of this EMBODIMENT A01) it is preferred - if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from Pr, Nd and Gd, preferably Nd, and with B being selected from Fe or Ni; or - if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe; preferably - if said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from Pr, Nd and Gd, preferably Nd, and with B being selected from Fe or Ni; or
K.A. Rasmussen 2024-07-19 LIG-001PCT2 - if said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe. In this preferred OPTION B (in embodiment “OB-02” also optionally combined with embodiment “OB-01”) of this EMBODIMENT A01) it is also preferred if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from Pr, Nd and Gd, preferably Nd, and with B being selected from Fe or Ni; preferably wherein said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from Pr, Nd and Gd, preferably Nd, and with B being selected from Fe or Ni. It is very preferred if the said oxide is selected from NdNiO3, Nd2NiO4, and Nd4Ni3O10, especially is NdNiO3. In this preferred OPTION B (in embodiment “OB-03” also optionally combined with embodiment “OB-01”) of this EMBODIMENT A01) it is also preferred if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe; preferably wherein said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe. It is very preferred if the said oxide is LaFeO3. In this preferred OPTION B (in embodiment “OB-04” also optionally combined with embodiments “OB-01” - “OB-03”) of this EMBODIMENT A01) it is also preferred if said oxide is selected from NdNiO3, Nd2NiO4, Nd4Ni3O10 and LaFeO3, preferably from NdNiO3 and LaFeO3. A02) The process according to EMBODIMENT A01), wherein the process also serves for the additional capture of platinum thus also lost by volatilization from a catalyst comprising rhodium and platinum to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with
K.A. Rasmussen 2024-07-19 LIG-001PCT2 such catalyst, which contains thus volatilized rhodium and platinum while such volatilized rhodium and platinum is still essentially in the vapor phase and at a temperature of at least 700 °C with said first oxide element. A03) The process according to EMBODIMENTS A01) or A02), wherein said highly heated gas stream in addition to contacting said first oxide element is further also contacting a metallic element comprising a metallic material selected from the group consisting of palladium, and palladium alloys, more specifically palladium- nickel alloys and palladium-gold alloys. A04) The process according to EMBODIMENT A03), wherein the contact with said metallic element precedes and/or is upstream from the contact with said first oxide element. A05) The process according to EMBODIMENT A03), wherein the contact with said metallic element follows and/or is downstream from the contact with said first oxide element. A06) The process according to EMBODIMENTS A01) or A02), wherein said highly heated gas stream in addition to contacting said first oxide element is further also contacting a second oxide element, (being different from said first oxide element) comprising at least one further oxide being different from said at least one oxide comprised in said first oxide element being selected from - an oxide of formula ABO3, especially as a perovskite, with A being selected from alkali earth, alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, Sr, Ca and Ba, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga; or - an oxide of formula An+1BnO3n+1, with n being 1 or 3, with A being selected from alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Pr, Nd, Sr and Ca, and with B being selected from 3-5d
K.A. Rasmussen 2024-07-19 LIG-001PCT2 elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga. A08) The process according to EMBODIMENT A07), wherein the contact with said second oxide element precedes and/or is upstream from the contact with said first oxide element. A09) The process according to EMBODIMENT A07), wherein the contact with said second oxide element follows and/or is downstream from the contact with said first oxide element. A10) The process according to any one of EMBODIMENTS A04) to A09), wherein the process also serves for the additional capture of platinum thus also lost by volatilization from a catalyst comprising rhodium and platinum to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains thus volatilized rhodium and platinum while such volatilized rhodium and platinum is still essentially in the vapor phase and at a temperature of at least 700 °C with said oxide element. A11) The process according to any one of EMBODIMENTS A01) to A10), wherein said highly heated gas stream after its contact with said catalyst is contacted with said first oxide element at a temperature at around or above 800°C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C), preferably at around 900 °C or above (or at 850°C to 950°C), preferably wherein said high temperature gas reaction is carried out at temperatures of at around or above 800°C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C), preferably at around 900°C or above. A12) The process according to EMBODIMENT A11), wherein the process also serves for the additional capture of platinum thus also lost by volatilization from a catalyst comprising rhodium and platinum to a high heated gas stream contacted therewith
K.A. Rasmussen 2024-07-19 LIG-001PCT2 in a high temperature gas reaction which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains thus volatilized rhodium and platinum while such volatilized rhodium and platinum is still essentially in the vapor phase with said first oxide element at a temperature at around or above 800°C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C), preferably at around 900 °C or above (or at 850°C to 950°C), preferably wherein said high temperature gas reaction is carried out at temperatures of at around or above 800°C, preferably at around 900°C or above, preferably wherein said high temperature gas reaction is carried out at temperatures of at around or above 800°C, preferably at around 900°C. A13) The process according to any one of EMBODIMENTS A01) to A12), wherein the highly heated gas stream also contains N2O, which is converted/decomposed upon contact with said first oxide element, preferably wherein the N2O is converted/decomposed to NO, NOx, N2 and/or O2. A14) The process according to any one of EMBODIMENTS A01) to A13), wherein the catalytic reaction of the high temperature gas reaction is a catalytic ammonia oxidation or catalytic ammonia combustion. A15) The process according to any one of EMBODIMENTS A01) to A14), wherein the at least one oxide and/or – where applicable - the at least one further oxide is/are of formula ABO3 with A being a metal selected from alkaline earth metals, alkali metals and lanthanoids/rare earth elements/lanthanoids, preferably being selected from lanthanoids/rare earth elements/lanthanoids, especially La, Pr, Nd, Sm, Eu and Gd, especially La or Nd, and B being a metal selected from transition metals, alkaline earth metals and alkali metals, preferably from being selected from transition metals, preferably being selected from Fe, Co, Ni and Zn, especially Ni, preferably wherein the oxide comprised in the first oxide element or second oxide element if present is most preferably is LaNiO3; or is an oxide of formula ANiO3 and optionally its respective RP phases like A2NiO4, A4Ni3O10, A4NiO3, wherein A is selected from La and Nd.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 A16) The process according to any one of EMBODIMENTS A01) to A14), wherein the at least one oxide and/or – where applicable - the at least one further oxide is/are selected from NdNiO3, LaNiO3, La2NiO4, La4Ni3O10, LaFeO3, LaCoO3, La0.85Sr0.15FeO3, Nd2NiO4, Nd4Ni3O10, Nd4NiO3, especially from NdNiO3, Nd2NiO4, Nd4Ni3O10, Nd4NiO3, LaNiO3, La2NiO4, La4Ni3O10, LaFeO3. A19) Use of an oxide element comprising at least one oxide selected from - an oxide of formula ABO3, especially as a perovskite, with A being selected from alkali earth, alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, Sr, Ca and Ba, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga; or - an oxide of formula An+1BnO3n+1, with n being 1 or 3, with A being selected from alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Pr, Nd, Sr and Ca, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga. for the capture of rhodium and/or of platinum and rhodium. A20) The use of EMBODIMENT A19), wherein the use is for the capture of platinum and rhodium, especially in the same process. A21) The use of EMBODIMENTS A19) or A20), wherein the use further encompasses the decomposition/conversion of N2O, especially in the same process, preferably wherein the N2O is decomposed/converted upon contact with said oxide element, most preferably wherein the N2O is decomposed/converted to NO, NOx, N2 and/or O2. A22) A device for the capture of rhodium and/or of platinum and rhodium from a combustion furnace of the type having a noble metal gauze arranged across the furnace in a direction transverse to the flow of gas therethrough, said device being an oxide element comprising or consisting of at least one oxide of formula ABO3, especially as a perovskite, with A being selected from alkali earth, alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La,
K.A. Rasmussen 2024-07-19 LIG-001PCT2 Ce, Pr, Nd, Pm, Sm, Eu and Gd, Sr, Ca and Ba, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga. A23) A catchment device for the capture of rhodium or of platinum and rhodium, in an ammonia oxidation reaction, comprising an oxide element comprising or consisting of at least one oxide of formula of formula ABO3, especially as a perovskite, with A being selected from alkali earth, alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, Sr, Ca and Ba, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga. A24) The use of any one of EMBODIMENTS A19) to A21), the device of EMBODIMENT A22), the catchment device of EMBODIMENT A23), wherein the at least one oxide and/or – where applicable - the at least one further oxide is/are of formula ABO3 with A being a metal selected from alkaline earth metals, alkali metals and lanthanoids/rare earth elements/lanthanoids, preferably being selected from lanthanoids/rare earth elements/lanthanoids, especially La, Pr, Nd, Sm, Eu and Gd, especially La or Nd, and B being a metal selected from transition metals, alkaline earth metals and alkali metals, preferably from being selected from transition metals, preferably being selected from Fe, Co, Ni and Zn, especially Ni, preferably wherein the oxide comprised in the first oxide element or second oxide element if present is most preferably is LaNiO3; or is an oxide of formula ANiO3 and optionally its respective RP phases like A2NiO4, A4Ni3O10, A4NiO3, wherein A is selected from La and Nd; or wherein the at least one oxide and/or – where applicable - the at least one further oxide is/are selected from NdNiO3, LaNiO3, La2NiO4, La4Ni3O10, LaFeO3, LaCoO3, La0.85Sr0.15FeO3, Nd2NiO4, Nd4Ni3O10, Nd4NiO3, especially from NdNiO3, Nd2NiO4, Nd4Ni3O10, Nd4NiO3, LaNiO3, La2NiO4, La4Ni3O10, LaFeO3; preferably is LaNiO3; or
K.A. Rasmussen 2024-07-19 LIG-001PCT2 wherein at least one oxide and/or – where applicable - the at least one further oxide is/are of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, preferably La, Nd and Gd, more preferably La and Nd, and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga), preferably from Fe or Ni, (more preferably from Ni); optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement; or wherein at least one oxide and/or – where applicable - the at least one further oxide is/are selected from LaNiO3, La2NiO4, La4Ni3O10, La4NiO3, NdNiO3, Nd2NiO4, Nd4Ni3O10, Nd4NiO3, LaFeO3 and LaCoO3, preferably from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, LaFeO3, and LaCoO3; more preferably from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3 and LaFeO3. As said above, the invention is further expressed in the following pages below up to the claims with the help of a number of specific EMBODIMENTS like EMBODIMENT B) etc. For all these EMBODIMENTS following below (and thus applicable to these), there are 2 Options for the oxides used, OPTION A (“OA”) and OPTION B (“OB”), which thus apply to all these EMBODIMENTS. In a preferred OPTION A (in embodiment “OA-01”) of the invention it is preferred if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with B being selected from Fe or Ni, preferably Ni. In this preferred OPTION A (in embodiment “OA-02” also optionally combined with embodiment “OA-01”) of the invention it is also preferred if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Pr, Nd and Gd, preferably from La and Nd.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 In this preferred OPTION A (in embodiment “OA-03” also optionally combined with embodiments “OA-01” and “OA-02”) of the invention it is also preferred if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe or Ni, preferably Ni; preferably wherein said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe or Ni, preferably Ni. In this preferred OPTION A (in embodiment “OA-04” also optionally combined with embodiments “OA-01” – “OA-03”) of the invention it is also preferred if said oxide is selected from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, Nd2NiO4, Nd4Ni3O10 and LaFeO3, preferably from LaNiO3, NdNiO3 and LaFeO3. In a preferred OPTION B (in embodiment “OB-01”) of the invention it is preferred - if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from Pr, Nd and Gd, preferably Nd, and with B being selected from Fe or Ni; or - if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe; preferably - if said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from Pr, Nd and Gd, preferably Nd, and with B being selected from Fe or Ni; or - if said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 In this preferred OPTION B (in embodiment “OB-02” also optionally combined with embodiment “OB-01”) of the invention it is also preferred if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from Pr, Nd and Gd, preferably Nd, and with B being selected from Fe or Ni; preferably wherein said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from Pr, Nd and Gd, preferably Nd, and with B being selected from Fe or Ni. It is very preferred if the said oxide is selected from NdNiO3, Nd2NiO4, and Nd4Ni3O10, especially is NdNiO3. In this preferred OPTION B (in embodiment “OB-03” also optionally combined with embodiment “OB-01”) of the invention it is also preferred if said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe; preferably wherein said oxide is an oxide of formula ABO3 in form of a perovskite with A being selected from La, Pr, Nd and Gd, preferably from La and Nd, and with B being selected from Fe. It is very preferred if the said oxide is LaFeO3. In this preferred OPTION B (in embodiment “OB-04” also optionally combined with embodiments “OB-01” - “OB-03”) of the invention it is also preferred if said oxide is selected from NdNiO3, Nd2NiO4, Nd4Ni3O10 and LaFeO3, preferably from NdNiO3 and LaFeO3. EMBODIMENT B) RHODIUM CAPTURE WITH OXIDES in Combination with a Pd/Ni capture device OR a second oxide element: B01) A process for the capture of rhodium lost by volatilization from a catalyst comprising rhodium to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains the volatilized rhodium while such volatilized rhodium is
K.A. Rasmussen 2024-07-19 LIG-001PCT2 still essentially in the vapor phase and at a temperature of at least 700 °C with a first oxide element comprising at least one oxide, wherein said highly heated gas stream in addition to contacting said first oxide element is further also contacting a metallic element comprising a metallic material selected from the group consisting of palladium, and palladium alloys, more specifically palladium-nickel alloys and palladium-gold alloys; OR wherein said highly heated gas stream in addition to contacting said first oxide element is further also contacting a second oxide element, (being different from said first oxide element) comprising at least one further oxide being different from said at least one oxide comprised in said first oxide element; wherein said at least one oxide and said at least one further oxide are independently selected from - an oxide of formula ABO3, especially as a perovskite, with A being selected from alkali earth, alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, Sr, Ca and Ba, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga; optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement; - an oxide of formula An+1BnO3n+1, with n being 1 or 3, with A being selected from alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Pr, Nd, Sr and Ca, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga; optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 B02) The process of EMBODIMENT B01), wherein the process also serves for the additional capture of platinum thus also lost by volatilization from a catalyst comprising rhodium and platinum to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains thus volatilized rhodium and platinum while such volatilized rhodium and platinum is still essentially in the vapor phase and at a temperature of at least 700 °C with said first oxide element. These Embodiments B01) and B02) are inventive as based on the selection of combining the Pd/Ni catchment device and the oxide. This is a superior combination as the Pd/Ni catchment device captures platinum and the first oxide element helps capturing rhodium; or the 2 oxide elements can complement each other. In addition, Embodiment B02) is based on the effect that it was found that in many cases also a pronounced Pt capture is seen, for example in the experiments of example 3, Table 1 (which is in some aspects close to the industrial situation) where the oxides were able to capture both Rh and Pt.. This was unknown from the art. In addition, NdNiO3 was shown to capture both Pt and Rh and the same applies for LaNiO3, La2NiO4, La4Ni3O10, and LaFeO3. B03) The process of EMBODIMENTS B01) and B02), wherein said highly heated gas stream after its contact with said catalyst is contacted with said first oxide element at a temperature at around or above 800°C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C), preferably at around 900 °C or above (or at 850°C to 950°C). B04) The process of EMBODIMENT B02), wherein said high temperature gas reaction is carried out at temperatures of at around or above 800°C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C), preferably at around 900°C or above. B05) The process of any one of EMBODIMENTS B01) to B04), wherein said highly heated gas stream after its contact with said catalyst is contacted with said first oxide element at a temperature at around 800°C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C) or at a temperature at 775°C to 825°C OR at a temperature at around or above 900°C or at a temperature at 875°C to 925°C.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 Embodiments B03) or B04) add the element of a higher capture of rhodium with these higher temperatures by the first oxide element as can be seen in Example 2 The art is silent on this influence of temperature on rhodium capture. B06) The process of any one of EMBODIMENTS B01) to B05), wherein the contact with said metallic element OR said second oxide element precedes and/or is upstream from the contact with said oxide element; or wherein the contact with said metallic element OR said second oxide element follows and/or is downstream from the contact with said oxide element. B07) The process of any one of EMBODIMENTS B01) to B06), wherein the highly heated gas stream also contains N2O, which is converted/decomposed upon contact with said first oxide element, preferably wherein the N2O is converted/decomposed to NO, NOx, N2 and/or O2. B08) The process of any one of EMBODIMENTS B01) to B07), wherein the catalytic reaction of the high temperature gas reaction is a catalytic ammonia oxidation or catalytic ammonia combustion. B09) The process of any one of EMBODIMENTS B01) to B08), wherein the at least one oxide and/or – where applicable - the at least one further oxide is/are of formula ABO3, especially as a perovskite, with A being selected from alkali earth, alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, Sr, Ca and Ba, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga; or wherein the at least one oxide and/or – where applicable - the at least one further oxide is/are of formula ABO3 with A being a metal selected from alkaline earth metals, alkali metals and lanthanoids/rare earth elements/lanthanoids, preferably being selected from lanthanoids/rare earth elements/lanthanoids, especially La, Pr, Nd, Sm, Eu and Gd, especially La or Nd, and B being a metal selected from transition metals, alkaline earth metals and alkali metals, preferably from being
K.A. Rasmussen 2024-07-19 LIG-001PCT2 selected from transition metals, preferably being selected from Fe, Co, Ni and Zn, especially Ni, preferably wherein the oxide comprised in the first oxide element or second oxide element if present is most preferably is LaNiO3; or is an oxide of formula ANiO3 and optionally its respective RP phases like A2NiO4, A4Ni3O10, A4NiO3, wherein A is selected from La and Nd; or wherein the at least one oxide and/or – where applicable - the at least one further oxide is/are selected from NdNiO3, LaNiO3, La2NiO4, La4Ni3O10, LaFeO3, LaCoO3, La0.85Sr0.15FeO3. Nd2NiO4, Nd4Ni3O10, Nd4NiO3; especially is NdNiO3, Nd2NiO4, Nd4Ni3O10, Nd4NiO3, LaNiO3, La2NiO4, La4Ni3O10; preferably is LaNiO3 or NdNiO3; or wherein at least one oxide and/or – where applicable - the at least one further oxide is/are of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, preferably La, Nd and Gd, more preferably La and Nd, and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga), preferably from Fe or Ni, (more preferably from Ni); optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement; or wherein at least one oxide and/or – where applicable - the at least one further oxide is/are selected from LaNiO3, La2NiO4, La4Ni3O10, La4NiO3, NdNiO3, Nd2NiO4, Nd4Ni3O10, Nd4NiO3, LaFeO3, and LaCoO3, preferably from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, LaFeO3, and LaCoO3; more preferably from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3 and LaFeO3. EMBODIMENT C) RHODIUM CAPTURE WITH OXIDES in Combination with a raised temperature:
K.A. Rasmussen 2024-07-19 LIG-001PCT2 C01) A process for the capture of rhodium lost by volatilization from a catalyst comprising rhodium to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains the volatilized rhodium while such volatilized rhodium is still essentially in the vapor phase, with a first oxide element comprising at least one oxide, wherein said highly heated gas stream after its contact with said catalyst is contacted with said first oxide element at a temperature at around or above 800°C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C); and wherein said at least one oxide and said at least one further oxide are independently selected from - an oxide of formula ABO3, especially as a perovskite, with A being selected from alkali earth, alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, Sr, Ca and Ba, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga); optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement; - an oxide of formula An+1BnO3n+1, with n being 1 or 3, with A being selected from alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Pr, Nd, Sr and Ca, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga); optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 C02) The process of EMBODIMENT C01), wherein the process also serves for the additional capture of platinum thus also lost by volatilization from a catalyst comprising rhodium and platinum to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains thus volatilized rhodium and platinum while such volatilized rhodium and platinum is still essentially in the vapor phase with said first oxide element. Embodiment C02) is based on the surprising effect that it was found that in many cases also a pronounced Pt capture is seen, for example in the experiments of example 3, Table 1 (which is in some aspects close to the industrial situation) where the oxides were able to capture both Rh and Pt. This was unknown from the art. NdNiO3 was shown to capture both Pt and Rh and the same applies for LaNiO3, La2NiO4, La4Ni3O10 and LaFeO3. In addition, Embodiment C01) is also further inventive as it adds the element of a higher capture of rhodium with these higher temperatures by the first oxide element as can be seen in Example 2. Embodiment C02) even adds the element of a higher capture of better captures the platinum at these specific higher temperatures. The art is silent on this influence of temperature on rhodium (or also platinum) capture. C03) The process of EMBODIMENTS C01) and C02), wherein said highly heated gas stream after its contact with said catalyst is contacted with said first oxide element at a temperature at around 900 °C or above (or at 850°C to 950°C). C04) The process of any one of EMBODIMENTS C01) to C03), wherein said high temperature gas reaction is carried out at temperatures of at around or above 800°C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C), preferably at around 900°C or above. C05) The process of any one of EMBODIMENTS C01) to C04), wherein said highly heated gas stream after its contact with said catalyst is contacted with said first oxide element at a temperature at around 800°C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C) or at a temperature at 775°C to 825°C OR at a temperature at around or above 900°C or at a temperature at 875°C to 925°C.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 C06) The process of any one of EMBODIMENTS C01) to C05), wherein said highly, wherein said highly heated gas stream in addition to contacting said first oxide element is further also contacting a metallic element comprising a metallic material selected from the group consisting of palladium, and palladium alloys, more specifically palladium-nickel alloys and palladium-gold alloys; OR wherein said highly heated gas stream in addition to contacting said first oxide element is further also contacting a second oxide element, (being different from said first oxide element) comprising at least one further oxide said at least one further oxide being different from said at least one oxide comprised in said first oxide element being selected from - an oxide of formula ABO3, especially as a perovskite, with A being selected from alkali earth, alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, Sr, Ca and Ba, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga; - an oxide of formula An+1BnO3n+1, with n being 1 or 3, with A being selected from alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Pr, Nd, Sr and Ca, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga. The Embodiment C06) adds as a further point based on the selection of combining the Pd/Ni catchment device and the oxide. This is a superior combination as the Pd/Ni catchment device captures platinum and the first oxide element helps capturing rhodium; or the 2 oxide elements can complement each other. C07) The process of EMBODIMENT C06), wherein the contact with said metallic element OR said second oxide element precedes and/or is upstream from the contact with said first oxide element; or
K.A. Rasmussen 2024-07-19 LIG-001PCT2 wherein the contact with said metallic element OR said second oxide element follows and/or is downstream from the contact with said first oxide element. C08) The process of any one of EMBODIMENTS C01) to C07), wherein the highly heated gas stream also contains N2O, which is converted/decomposed upon contact with said first oxide element, preferably wherein the N2O is converted/decomposed to NO, NOx, N2 and/or O2. C09) The process of any one of EMBODIMENTS C01) to C08), wherein the catalytic reaction of the high temperature gas reaction is a catalytic ammonia oxidation or catalytic ammonia combustion. C10) The process of any one of EMBODIMENTS C01) to C09), wherein the at least one oxide and/or – where applicable - the at least one further oxide is/are of formula ABO3, especially as a perovskite, with A being selected from alkali earth, alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, Sr, Ca and Ba, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga; or wherein the at least one oxide and/or – where applicable - the at least one further oxide is/are of formula ABO3 with A being a metal selected from alkaline earth metals, alkali metals and lanthanoids/rare earth elements/lanthanoids, preferably being selected from lanthanoids/rare earth elements/lanthanoids, especially La, Pr, Nd, Sm, Eu and Gd, especially La or Nd, and B being a metal selected from transition metals, alkaline earth metals and alkali metals, preferably from being selected from transition metals, preferably being selected from Fe, Co, Ni and Zn, especially Ni, preferably wherein the oxide comprised in the first oxide element or second oxide element if present is most preferably is LaNiO3; or is an oxide of formula ANiO3 and optionally its respective RP phases like A2NiO4, A4Ni3O10, A4NiO3, wherein A is selected from La and Nd; or
K.A. Rasmussen 2024-07-19 LIG-001PCT2 wherein the at least one oxide and/or – where applicable - the at least one further oxide is/are selected from NdNiO3, LaNiO3, La2NiO4, La4Ni3O10, LaFeO3, LaCoO3, La0.85Sr0.15FeO3, Nd2NiO4, Nd4Ni3O10, Nd4NiO3, especially from NdNiO3, Nd2NiO4, Nd4Ni3O10, Nd4NiO3, LaNiO3, La2NiO4, La4Ni3O10 ; preferably is LaNiO3 or NdNiO3; or wherein at least one oxide and/or – where applicable - the at least one further oxide is/are of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, preferably La, Nd and Gd, more preferably La and Nd, and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga), preferably from Fe or Ni, (more preferably from Ni); optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement; or wherein at least one oxide and/or – where applicable - the at least one further oxide is/are selected from LaNiO3, La2NiO4, La4Ni3O10, La4NiO3, NdNiO3, Nd2NiO4, Nd4Ni3O10, Nd4NiO3, LaFeO3 and LaCoO3, preferably from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, LaFeO3 and LaCoO3; more preferably from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3 and LaFeO3.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 EMBODIMENT D) RHODIUM (ONLY) CAPTURE WITH ABO3-OXIDES (LaNiO3 and NdNiO3, especially and NdNiO3) D01) A process for the capture of rhodium lost by volatilization from a catalyst comprising rhodium to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains the volatilized rhodium while such volatilized rhodium is still essentially in the vapor phase and at a temperature of at least 700 °C with a first oxide element comprising at least one oxide of formula ABO3, in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, wherein A is selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga). D02) The process of EMBODIMENT D01), wherein in the at least one oxide of formula ABO3 A is selected from La, Nd and Gd, preferably from La and Nd, and B being selected from Fe or Ni, preferably from Ni. D03) The process of EMBODIMENT D01), wherein the at least one oxide is selected from La2NiO4, La4Ni3O10, LaFeO3, LaNiO3 or NdNiO3. D04) The process of EMBODIMENT D01), wherein the at least one oxide is NdNiO3; or wherein the at least one oxide is LaNiO3 D05) The process of any one of EMBODIMENTS D01) to D04), wherein said highly heated gas stream in addition to contacting said first oxide element is further also contacting a metallic element comprising a metallic material selected from the group consisting of palladium, and palladium alloys, more specifically palladium- nickel alloys and palladium-gold alloys. D06) The process of EMBODIMENT D05), wherein the contact with said metallic element precedes and/or is upstream from the contact with said first oxide element or
K.A. Rasmussen 2024-07-19 LIG-001PCT2 wherein the contact with said metallic element follows and/or is downstream from the contact with said first oxide element. D07) The process of any one of EMBODIMENTS D01) to D04), wherein said highly heated gas stream in addition to contacting said first oxide element is further also contacting a second oxide element comprising at least one further oxide being different from the ABO3 of the first oxide element and being of formula ABO3, especially as a perovskite, with A being selected from alkali earth, alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, Sr, Ca and Ba, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga. D08) The process of EMBODIMENT D07), wherein the second oxide element comprises at least one further oxide selected from NdNiO3, LaNiO3, La2NiO4, La4Ni3O10, LaFeO3, LaCoO3, La0.85Sr0.15FeO3, Nd2NiO4, Nd4Ni3O10, Nd4NiO3; or of formula ANiO3 and their respective RP phases A2NiO4, A4Ni3O10, and A4NiO3, wherein A is selected from La and Nd. D09) The process of any one of EMBODIMENTS D01) to D08), wherein the process also serves for the capture of platinum lost by volatilization from a catalyst comprising rhodium and platinum to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains thus volatilized rhodium and platinum while such volatilized rhodium and platinum is still essentially in the vapor phase and at a temperature of at least 700 °C with said first oxide element. D10) The process of any one of EMBODIMENTS D01) to D09), wherein the highly heated gas stream after its contact with said catalyst is contacted with said first oxide element at a temperature at around or above 800°C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C) or at around 900 °C or above (or at 850°C to 950°C), preferably at around 900°C (or at 850°C to 950°C).
K.A. Rasmussen 2024-07-19 LIG-001PCT2 D11) The process of any one of EMBODIMENTS D01) to D09), wherein the highly heated gas stream after its contact with said catalyst is contacted with said first oxide element at a temperature from 775°C to 825°C, or at a temperature from 875°C to 925°C preferably at a temperature from 875°C to 925°C. D12) The process of any one of EMBODIMENTS D01) to D11), wherein the highly heated gas stream also contains N2O, which is converted/decomposed upon contact with said first oxide element, preferably wherein the N2O is converted/decomposed to NO, NOx, N2 and/or O2. D13) The process of any one of EMBODIMENTS D01) to D11), wherein the catalytic reaction of the high temperature gas reaction is a catalytic ammonia oxidation or catalytic ammonia combustion. D14) Use of an oxide element comprising at least one oxide of formula ABO3, in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, wherein A is selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga) for the capture of rhodium from a highly heated gas stream, which contains a volatilized rhodium while such volatilized rhodium is still essentially in the vapor phase. D15) The use of EMBODIMENT D14), wherein the highly heated gas stream is at a temperature of at least 800 °C and/or wherein the use is for the capture of rhodium. D16) A device for the capture of rhodium from a combustion furnace of the type having a noble metal gauze arranged across the furnace in a direction transverse to the flow of gas therethrough, said device being an oxide element comprising or consisting of at least one oxide of formula ABO3, in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, wherein A is selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga). D17) A catchment device for the capture of rhodium, in an ammonia oxidation reaction, comprising an oxide element comprising or consisting of at least one oxide of
K.A. Rasmussen 2024-07-19 LIG-001PCT2 formula ABO3, in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, wherein A is selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga). D18) The device of EMBODIMENT D16) or catchment device of EMBODIMENT D17), wherein the device or catchment device is for the capture of rhodium and platinum. D19) The use of EMBODIMENTS D14) or D15), the device of EMBODIMENTS D16) or D18) or catchment device of EMBODIMENT D17) or D18), wherein in the at least one oxide of formula ABO3, A is selected from La, Nd and Gd, preferably from La and Nd, and B being selected from Fe or Ni, preferably from Ni. D20) The use of EMBODIMENTS D14) or D15), the device of EMBODIMENTS D16) or D18) or catchment device of EMBODIMENT D17) or D18), wherein the at least one oxide is selected from La2NiO4, La4Ni3O10, LaFeO3, LaNiO3 or NdNiO3. D21) The use of EMBODIMENTS D14) or D15), the device of EMBODIMENTS D16) or D18) or catchment device of EMBODIMENT D17) or D18), wherein the at least one oxide is NdNiO3; or wherein the at least one oxide is LaNiO3. EMBODIMENT E) PLATINUM CAPTURE WITH ABO3-OXIDES (LaNiO3 and NdNiO3) or (NdNiO3) E01) A process for the capture of platinum lost by volatilization from a catalyst comprising platinum to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains the volatilized platinum while such volatilized platinum is still essentially in the vapor phase and at a temperature of at least 700 °C with a first oxide element comprising at least one oxide of formula ABO3, in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, wherein
K.A. Rasmussen 2024-07-19 LIG-001PCT2 A is selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga). E02) The process of EMBODIMENT E01), wherein in the at least one oxide of formula ABO3 A is selected from La, Nd and Gd, preferably from La and Nd, and B being selected from Fe or Ni, preferably from Ni. E03) The process of EMBODIMENT E01), wherein the at least one oxide is selected from La2NiO4, La4Ni3O10, LaFeO3, LaNiO3 or NdNiO3. E04) The process of EMBODIMENT E01), wherein the at least one oxide is NdNiO3; or wherein the at least one oxide is LaNiO3 E05) The process of any one of EMBODIMENTS E01) to E04), wherein said highly heated gas stream in addition to contacting said first oxide element is further also contacting a metallic element comprising a metallic material selected from the group consisting of palladium, and palladium alloys, more specifically palladium- nickel alloys and palladium-gold alloys. E06) The process of EMBODIMENT E05), wherein the contact with said metallic element precedes and/or is upstream from the contact with said first oxide element or wherein the contact with said metallic element follows and/or is downstream from the contact with said first oxide element. E07) The process of any one of EMBODIMENTS E01) to E04), wherein said highly heated gas stream in addition to contacting said first oxide element is further also contacting a second oxide element comprising at least one further oxide being different from the ABO3 of the first oxide element and being of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, preferably La, Nd and Gd, more preferably La and Nd, and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga), preferably from Fe or Ni, (more preferably from Ni); optionally with one or more elements on A position in form of
K.A. Rasmussen 2024-07-19 LIG-001PCT2 a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement . E08) The process of EMBODIMENT E07), wherein the second oxide element comprises at least one further oxide selected from NdNiO3, LaNiO3, La2NiO4, La4Ni3O10, LaFeO3, LaCoO3, La0.85Sr0.15FeO3, Nd2NiO4, Nd4Ni3O10, Nd4NiO3; or of formula ANiO3 and their respective RP phases A2NiO4, A4Ni3O10, and A4NiO3, wherein A is selected from La and Nd. E09) The process of any one of EMBODIMENTS E01) to E08), wherein the process also serves for the capture of rhodium lost by volatilization from a catalyst comprising rhodium and platinum to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains thus volatilized rhodium and platinum while such volatilized rhodium and platinum is still essentially in the vapor phase and at a temperature of at least 700 °C with said first oxide element. E10) The process of any one of EMBODIMENTS E01) to E09), wherein the highly heated gas stream after its contact with said catalyst is contacted with said first oxide element at a temperature at around or above 800°C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C) or at around 900 °C or above (or at 850°C to 950°C), preferably at around 800°C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C). E11) The process of any one of EMBODIMENTS E01) to E09), wherein the highly heated gas stream after its contact with said catalyst is contacted with said first oxide element at a temperature from 775°C to 825°C, or at a temperature from 875°C to 925°C preferably at a temperature from 775°C to 825°C. E12) The process of any one of EMBODIMENTS E01) to E11), wherein the highly heated gas stream also contains N2O, which is converted/decomposed upon contact with said first oxide element, preferably wherein the N2O is converted/decomposed to NO, NOx, N2 and/or O2.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 E13) The process of any one of EMBODIMENTS E01) to E11), wherein the catalytic reaction of the high temperature gas reaction is a catalytic ammonia oxidation or catalytic ammonia combustion. E14) Use of an oxide element comprising at least one oxide of formula ABO3, in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, wherein A is selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga) for the capture of platinum from a highly heated gas stream, which contains a volatilized platinum while such volatilized platinum is still essentially in the vapor phase. E15) The use of EMBODIMENT E14), wherein the highly heated gas stream is at a temperature of at least 800 °C and/or wherein the use is for the capture of platinum. E16) A device for the capture of platinum from a combustion furnace of the type having a noble metal gauze arranged across the furnace in a direction transverse to the flow of gas therethrough, said device being an oxide element comprising or consisting of at least one oxide of formula ABO3, in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, wherein A is selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga). E17) A catchment device for the capture of platinum, in an ammonia oxidation reaction, comprising an oxide element comprising or consisting of at least one oxide of formula ABO3, in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, wherein A is selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga). E18) The device of EMBODIMENT E16) or catchment device of EMBODIMENT E17), wherein the device or catchment device is for the capture of rhodium and platinum.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 E19) The use of EMBODIMENTS E14) or E15), the device of EMBODIMENTS E16) or E18) or catchment device of EMBODIMENT E17) or E18), wherein in the at least one oxide of formula ABO3, A is selected from La, Nd and Gd, preferably from La and Nd, and B being selected from Fe or Ni, preferably from Ni. E20) The use of EMBODIMENTS E14) or E15), the device of EMBODIMENTS E16) or E18) or catchment device of EMBODIMENT E17) or E18), wherein the at least one oxide is selected from La2NiO4, La4Ni3O10, LaFeO3, LaNiO3 or NdNiO3. E21) The use of EMBODIMENTS E14) or E15), the device of EMBODIMENTS E16) or E18) or catchment device of EMBODIMENT E17) or E18), wherein the at least one oxide is NdNiO3; or wherein the at least one oxide is LaNiO3. EMBODIMENT V) Process for N2O conversion Background of the invention The Ostwald Process is the most common method in manufacturing artificial fertilizer today. This process involves converting ammonia NH3 into Nitric Acid HNO3 in a two-stage process. In the first step, ammonia is oxidized over a Pt-Rh (90:10 wt.%) catalytic gauze at high temperature and moderate pressure (T = 800 - 950 °C and P = 1 - 14 bar) to produce nitric oxide (NO) according to reaction [1]. 4NH3(g) + 5O2(g) ^ 4NO(g) + 6H2O(g); ΔHo = -908 kJ/mol [1] The Nitric Oxide (NO) is in stage 2 absorbed into water forming nitric acid, which again is a precursor for artificial fertilizer. A side reaction to this process is the formation of Nitrous Oxide (N2O) which is also called Laughing Gas, selectivity is less than 2% of the overall reactions. Historically, glass wool filters, marble chips, Rashig rings and various ceramic materials have been used, but the most common abatement catalyst today is made of porous ceramic rashig rings which has been wetted with catalytic active materials and dried and calcinated before located in a tray typically 50 mm thickness directly under the capturing
K.A. Rasmussen 2024-07-19 LIG-001PCT2 screens. The catalytic active material can be typically cobalt oxides or the combination of any oxide from standard transition metals, in combination with oxides from Rare Earth Metals (Lanthanoids). The aim for this project was to develop a way for abatement of Laughing Gas N2O, which would normally dissipate into the air. It has been measured that Laughing Gas has approx. 50 times stronger green-house effect then CO2. This invention describes a new way of mitigating (or capturing and/or converting) Laughing Gas being formed in Ostwald Process using an oxide as described below. As said above, the described oxides might be used in a process for capturing Platinum and Rhodium that is normally lost in the Ostwald Process, e.g. during the same process. N2O abatement catalyst are located preferably downstream directly under the capturing screens. Such N2O abatement catalyst can vary in size and materials. It was found that an N2O abatement catalyst/the oxide element comprising LaNiO3 active material was active in this process. One advantage with this invention is that it abates approximately 50% of the emitted Laughing Gas N2O at operating conditions which is 4 bars and 850oC The advantage with this solution is that the pressure drop through this net package is minor. Another advantage with this invention is the low cost of materials and processing to manufacture the screens with LaNiO3. Kanthal screens are available from many vendors at different shapes and different wire diameters, the deposition of LaNiO3 is a straightforward technique where the screens are dipped into a slurry of Nickel citrate and Lanthanum oxide in citric acid and nitric acid, after that the screens are dried at 180oC and calcinated in a furnace at 400oC. Another advantage with this invention is that it has no decomposition effect on the yield of NO from the first stage of the Ostwald process.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 Experimental design: The perovskite oxide LaNiO3 was tested for its effect on N2O. A stack of 12 woven nets made of Kanthal wires, wire diameter 0,2 mm was cut and shaped to fit the size of the reactor. Each net was coated with LaNiO3. The stack of LaNiO3 coated nets was located directly under a catalyst package, the reactor was ignited and run for (21) days during which time continuous measurements of the content of NO and N2O as well as other gases was analyzed. After the test period, the net package containing LaNiO3 nets were taken out and examined. The N2O abatement catalyst/the oxide element comprising LaNiO3 active material was active in this process. EMBODIMENTS: V01) A process for the conversion/decomposition of N2O developing during a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with a catalyst at a temperature of at least 700 °C with a first oxide element comprising at least one oxide of formula ABO3, in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, wherein A is selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga). V02) The process of EMBODIMENT V01), wherein in the at least one oxide of formula ABO3 A is selected from La, Nd and Gd, preferably from La and Nd, and B being selected from Fe or Ni, preferably from Ni. V03) The process of EMBODIMENT V01), wherein the at least one oxide is selected from La2NiO4, La4Ni3O10, LaFeO3, LaNiO3 or NdNiO3., especially is LaNiO3. V04) The process of any one of EMBODIMENTS V01) to V03), wherein the catalytic reaction of the high temperature gas reaction is a catalytic ammonia oxidation or catalytic ammonia combustion, especially the Ostwald Process.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 V05) The process of any one of EMBODIMENTS V01) to V04), wherein the N2O is decomposed/converted upon contact with said first oxide element, preferably wherein the N2O is decomposed/converted to NO, NOx, N2 and/or O2. V06) The process of any one of EMBODIMENTS V01) to V05), wherein said catalyst comprises at least one noble metal being selected from rhodium and platinum or both. V07) Use of an oxide element comprising at least one oxide of formula ABO3, in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, wherein A is selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga) for the capture and/or conversion of N2O. V08) The use of EMBODIMENTS V07) wherein in the at least one oxide of formula ABO3, A is selected from La, Nd and Gd, preferably from La and Nd, and B being selected from Fe or Ni, preferably from Ni. V09) The use of EMBODIMENTS V07), wherein the at least one oxide is selected from La2NiO4, La4Ni3O10, LaFeO3, LaNiO3 or NdNiO3, especially is LaNiO3. EMBODIMENT W) USE and Devices according to any one of EMBODIMENTS B) – G) and X) – Z) W01) Use of an oxide element comprising at least one oxide being selected from - an oxide of formula ABO3, especially as a perovskite, with A being selected from alkali earth, alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, Sr, Ca and Ba, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga; optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement;
K.A. Rasmussen 2024-07-19 LIG-001PCT2 - an oxide of formula An+1BnO3n+1, with n being 1 or 3, with A being selected from alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Pr, Nd, Sr and Ca, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga; optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement; for the capture of rhodium and/or of platinum and rhodium. W02) The use of EMBODIMENT W01), wherein the use is for the capture of platinum and rhodium, especially in the same process. W03) The use of EMBODIMENTS W01) or W02), wherein the use further encompasses the decomposition/conversion of N2O, especially in the same process, preferably wherein the N2O is decomposed/converted upon contact with said oxide element, most preferably wherein the N2O is decomposed/converted to NO, NOx, N2 and/or O2. W04) A device for the capture of rhodium and/or of platinum and rhodium from a combustion furnace of the type having a noble metal gauze arranged across the furnace in a direction transverse to the flow of gas therethrough, said device being an oxide element comprising or consisting of at least one oxide of being selected from - an oxide of formula ABO3, especially as a perovskite, with A being selected from alkali earth, alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, Sr, Ca and Ba, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga; optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement;
K.A. Rasmussen 2024-07-19 LIG-001PCT2 - an oxide of formula An+1BnO3n+1, with n being 1 or 3, with A being selected from alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Pr, Nd, Sr and Ca, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga; optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement; W05) A catchment device for the capture of rhodium or of platinum and rhodium, in an ammonia oxidation reaction, comprising an oxide element comprising or consisting of at least one oxide of formula being selected from - an oxide of formula ABO3, especially as a perovskite, with A being selected from alkali earth, alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, Sr, Ca and Ba, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga; optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement; - an oxide of formula An+1BnO3n+1, with n being 1 or 3, with A being selected from alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Pr, Nd, Sr and Ca, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga; optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement; W6) The use of any one of EMBODIMENTS W1) to W03), the device of EMBODIMENT W4), the catchment device of EMBODIMENT W5),
K.A. Rasmussen 2024-07-19 LIG-001PCT2 wherein the at least one oxide is of formula ABO3 with A being a metal selected from alkaline earth metals, alkali metals and lanthanoids/rare earth elements/lanthanoids, preferably being selected from lanthanoids/rare earth elements/lanthanoids, especially La, Pr, Nd, Sm, Eu and Gd, especially La or Nd, and B being a metal selected from transition metals, alkaline earth metals and alkali metals, preferably from being selected from transition metals, preferably being selected from Fe, Co, Ni and Zn, especially Ni, preferably wherein the oxide comprised in the first oxide element or second oxide element if present is most preferably is LaNiO3; or is an oxide of formula ANiO3 and optionally its respective RP phases like A2NiO4, A4Ni3O10, A4NiO3, wherein A is selected from La and Nd; or or wherein the at least one oxide is selected from NdNiO3, LaNiO3, La2NiO4, La4Ni3O10, LaFeO3, LaCoO3, La0.85Sr0.15FeO3, Nd2NiO4, Nd4Ni3O10, Nd4NiO3, especially from NdNiO3, Nd2NiO4, Nd4Ni3O10, Nd4NiO3, LaNiO3, La2NiO4, La4Ni3O10; preferably is LaNiO3; or wherein at least one oxide is of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, preferably La, Nd and Gd, more preferably La and Nd, and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga), preferably from Fe or Ni, (more preferably from Ni); optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement; or or wherein at least one oxide is selected from LaNiO3, La2NiO4, La4Ni3O10, La4NiO3, NdNiO3, Nd2NiO4, Nd4Ni3O10, Nd4NiO3, LaFeO3 and LaCoO3, preferably from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, LaFeO3 and LaCoO3; more preferably from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3 and LaFeO3.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 EMBODIMENT X) RHODIUM (ONLY) CAPTURE WITH OXIDE X01) A process for the capture of rhodium lost by volatilization from a catalyst comprising rhodium to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains the volatilized rhodium while such volatilized rhodium is still essentially in the vapor phase and at a temperature of at least 700 °C with a first oxide element comprising at least one oxide being selected from - an oxide of formula ABO3, especially as a perovskite, with A being selected from alkali earth, alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, Sr, Ca and Ba, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga; optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement; - an oxide of formula An+1BnO3n+1, with n being 1 or 3, with A being selected from alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Pr, Nd, Sr and Ca, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga; optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement; This Embodiment X) is based on the surprising effect that also rhodium – if mobilized by the high temperature gas reaction from a catalyst – could be captured by selected oxides. This is especially true if seen on the experiments of EXAMPLE 1. In these experiments showing the use of a selected perovskite NdNiO3 compared to CaO - known from the art
K.A. Rasmussen 2024-07-19 LIG-001PCT2 to capture platinum - showed that the use of the perovskites in this process was able to capture rhodium and further more to a much larger extent than seen in the art (CaO). This was not predictable at al, as the art is mostly silent on rhodium capture. X02) A process for the capture of rhodium lost by volatilization from a catalyst comprising rhodium to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains the volatilized rhodium while such volatilized rhodium is still essentially in the vapor phase and at a temperature of at least 700 °C with a first oxide element comprising at least one oxide, wherein said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, preferably La, Nd and Gd, more preferably La and Nd, and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga), preferably from Fe or Ni, (more preferably from Ni); optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement; or X03) The process according to Embodiments X01 or X02), wherein said oxide is selected from LaNiO3, La2NiO4, La4Ni3O10, La4NiO3, NdNiO3, Nd2NiO4, Nd4Ni3O10, Nd4NiO3, LaFeO3 and LaCoO3, preferably from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, LaFeO3 and LaCoO3; more preferably is NdNiO3. X04) The process according to Embodiment X01), wherein said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, preferably La, Nd and Gd, more preferably La and Nd, and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga), preferably from Fe or Ni, (more preferably from Ni). X05) The process according to Embodiment X04), wherein said oxide is selected from LaNiO3, La2NiO4, La4Ni3O10, La4NiO3, NdNiO3, Nd2NiO4, Nd4Ni3O10, Nd4NiO3,
K.A. Rasmussen 2024-07-19 LIG-001PCT2 LaFeO3 and LaCoO3, preferably from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, LaFeO3 and LaCoO3, more preferably from LaNiO3 and NdNiO3., most preferably NdNiO3. X06) The process according to any one of Embodiments X01) to X05), wherein the highly heated gas stream also contains N2O, which is converted/decomposed upon contact with said first oxide element, preferably wherein the N2O is converted/decomposed to NO, NOx, N2 and/or O2. X07) The process according to any one of Embodiments X01) to X06), wherein the catalytic reaction of the high temperature gas reaction is a catalytic ammonia oxidation or catalytic ammonia combustion. X + B): X) RHODIUM (ONLY) CAPTURE WITH OXIDE in Combination B) with a Pd/Ni capture device OR a second oxide element: XB08) The process according to any one of Embodiment X01) to X07), wherein said highly heated gas stream in addition to contacting said first oxide element is further also contacting a metallic element comprising a metallic material selected from the group consisting of palladium, and palladium alloys, more specifically palladium-nickel alloys and palladium-gold alloys; OR wherein said highly heated gas stream in addition to contacting said first oxide element is further also contacting a second oxide element, (being different from said first oxide element) comprising at least one further oxide being different from said at least one oxide comprised in said first oxide element, wherein said further oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, preferably La, Nd and Gd, more preferably La and Nd, and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga), preferably from Fe or Ni, (more preferably from Ni); optionally with one or more elements on A position in form of a solid solution or in an ordered
K.A. Rasmussen 2024-07-19 LIG-001PCT2 arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement; or XB09) The process according to any one of Embodiment X01) to X07), wherein said highly heated gas stream in addition to contacting said first oxide element is further also contacting a metallic element comprising a metallic material selected from the group consisting of palladium, and palladium alloys, more specifically palladium-nickel alloys and palladium-gold alloys. This Embodiment XB09) is also further (above and besides the inventive advantages of Embodiment X) inventive as based on the selection of combining the Pd/Ni catchment device and the oxide. This is a good combination as the Pd/Ni catchment device captures platinum and the first oxide element helps capturing rhodium. XB10) The process according to EMBODIMENT XB09), wherein the contact with said metallic element precedes and/or is upstream from the contact with said first oxide element. XB11) The process according to EMBODIMENT XB09), wherein the contact with said metallic element follows and/or is downstream from the contact with said first oxide element. XB12) The process according to any one of EMBODIMENTS X01) to X07), wherein said highly heated gas stream in addition to contacting said first oxide element is further also contacting a second oxide element, (being different from said first oxide element) comprising at least one further oxide being different from said at least one oxide comprised in said first oxide element, wherein said further oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, preferably La, Nd and Gd, more preferably La and Nd, and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga), preferably from Fe or Ni, (more preferably from Ni); optionally with one or more
K.A. Rasmussen 2024-07-19 LIG-001PCT2 elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement. This Embodiment XB12) is also further (above and besides the inventive advantages of Embodiment X) inventive as it is a good combination in which e.g. the second oxide element can be chosen to be better suited to capture platinum while the first oxide element helps capture rhodium etc., or vice versa (maybe also relying on different temperatures of around 800° or 900° C depending on which noble metal to capture). XB13) The process according to EMBODIMENT XB12), wherein the contact with said second oxide element precedes and/or is upstream from the contact with said first oxide element. XB14) The process according to EMBODIMENT XB12), wherein the contact with said second oxide element follows and/or is downstream from the contact with said first oxide element. X + B + C): X) RHODIUM (ONLY) CAPTURE WITH OXIDE in Combination B) with a Pd/Ni capture device OR a second oxide element, and C) at a higher temperature: XBC15) The process according to any one of EMBODIMENTS XB08) to XB14), wherein said highly heated gas stream after its contact with said catalyst is contacted with said first oxide element at a temperature at around or above 800°C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C), preferably at around 900 °C or above (or at 850°C to 950°C).
K.A. Rasmussen 2024-07-19 LIG-001PCT2 XBC16) The process according to EMBODIMENT XB15), wherein said high temperature gas reaction is carried out at temperatures of at around or above 800°C, preferably at around 900°C or above. This Embodiment XBC15) is also further (above and besides the inventive advantages of Embodiments XB08 to XB14) inventive as it adds the element of a higher capture of rhodium with these higher temperatures as can be seen in Example 1. The art is completely silent on this influence of temperature on rhodium capture. XBC17) The process according to any one of EMBODIMENTS XB09) to XB11), wherein said highly heated gas stream after its contact with said catalyst is contacted with said first oxide element at temperatures of around 900 °C or above (or at 850°C to 950°C) or at temperatures of 875°C to 925 °C. XBC18) The process according to EMBODIMENT XB17), wherein said high temperature gas reaction is carried out at temperatures of at around 900°C or above. This Embodiment XBC17) is also further (above and besides the inventive advantages of Embodiments XB09) inventive as it adds the element of a higher capture of rhodium with these higher temperatures by the first oxide element as can be seen in Example 1, while the Pd/Ni element captures the platinum. The art is completely silent on this influence of temperature on rhodium capture. XBC19) The process according to any one of EMBODIMENTS XB12) to XB14), wherein said highly heated gas stream after its contact with said catalyst is contacted with said first oxide element at temperatures of around 900 °C or above (or at 850°C to 950°C) or at temperatures of 875°C to 925 °C and with said second oxide element at temperatures of around 800 °C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C) or at temperatures of 775°C to 825 °C.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 XBC20) The process according to EMBODIMENT XBC19), wherein said high temperature gas reaction is carried out at temperatures of at around or above 800°C or at around 900°C or above. This Embodiment XBC19) is also further (above and besides the inventive advantages of Embodiment XB12) inventive as it adds the element of a higher capture of rhodium with these higher temperatures by the first oxide element as can be seen in Example 1, while the second oxide element better captures the platinum. The art is completely silent on this influence of temperature on rhodium (or also platinum) capture. X + C): X) RHODIUM (ONLY) CAPTURE WITH OXIDE in Combination with C) a higher capture temperature XC21) The process according to any one of Embodiment X01) to X07), wherein said highly heated gas stream after its contact with said catalyst is contacted with said first oxide element at a temperature at around or above 800°C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C), preferably at around 900 °C or above (or at 850°C to 950°C). XC22) The process according to EMBODIMENT XC21), wherein said high temperature gas reaction is carried out at temperatures of at around or above 800°C, preferably at around 900°C or above. XC23) The process according to any one of Embodiment X01) to X07), wherein said highly heated gas stream after its contact with said catalyst is contacted with said first oxide element at a temperature at around 900 °C or above (or at 850°C to 950°C) or at temperatures of 875°C to 925 °C. XC24) The process according to EMBODIMENT XC23), wherein said high temperature gas reaction is carried out at temperatures of at around or above 900°C.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 These Embodiments XC21) and XC23) is also further (above and besides the inventive advantages of Embodiment X) inventive as it adds the element of a higher capture of rhodium with these higher temperatures as can be seen in Example 1. The art is completely silent on this influence of temperature on rhodium capture. EMBODIMENT Y) PLATINUM (ONLY) CAPTURE WITH OXIDE Y01) A process for the capture of platinum lost by volatilization from a catalyst comprising platinum to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains the volatilized platinum while such volatilized platinum is still essentially in the vapor phase and at a temperature of at least 700 °C with a first oxide element comprising at least one oxide being selected from - an oxide of formula ABO3, especially as a perovskite, with A being selected from alkali earth, alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, Sr, Ca and Ba, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga; optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement; - an oxide of formula An+1BnO3n+1, with n being 1 or 3, with A being selected from alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Pr, Nd, Sr and Ca, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga; optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 This Embodiment Y) is based on the effect that the use of the selected perovskites in this process was superior to the use of CaO for platinum capture that is known from the art (see Table 1). This was not predictable at all from the art. Y02) A process for the capture of platinum lost by volatilization from a catalyst comprising platinum to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains the volatilized platinum while such volatilized platinum is still essentially in the vapor phase and at a temperature of at least 700 °C with a first oxide element comprising at least one oxide, wherein said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, preferably La, Nd and Gd, more preferably La and Nd, and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga), preferably from Fe or Ni, (more preferably from Ni); optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement. Y03) The process according to Embodiments Y01 or Y02), wherein said oxide is selected from LaNiO3, La2NiO4, La4Ni3O10, La4NiO3, NdNiO3, Nd2NiO4, Nd4Ni3O10, Nd4NiO3, LaFeO3 and LaCoO3, preferably from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, LaFeO3 and LaCoO3; more preferably from LaNiO3, La2NiO4, La4Ni3O10 and NdNiO3. Y04) The process according to Embodiment Y01), wherein said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, preferably La, Nd and Gd, more preferably La and Nd, and with B being selected
K.A. Rasmussen 2024-07-19 LIG-001PCT2 from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga), preferably from Fe or Ni, (more preferably from Ni). Y05) The process according to Embodiment Y04), wherein said oxide is selected from LaNiO3, La2NiO4, La4Ni3O10, La4NiO3, NdNiO3, Nd2NiO4, Nd4Ni3O10, Nd4NiO3, LaFeO3 and LaCoO3, preferably from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, LaFeO3 and LaCoO3, more preferably from LaNiO3 and NdNiO3., most preferably LaNiO3, La2NiO4, La4Ni3O10 and NdNiO3. Y06) The process according to any one of Embodiments Y01) to Y05), wherein the highly heated gas stream also contains N2O, which is converted/decomposed upon contact with said first oxide element, preferably wherein the N2O is converted/decomposed to NO, NOx, N2 and/or O2. Y07) The process according to any one of Embodiments Y01) to Y0), wherein the catalytic reaction of the high temperature gas reaction is a catalytic ammonia oxidation or catalytic ammonia combustion. Y + B): Y) PLATINUM (ONLY) CAPTURE WITH OXIDE in Combination B) with a Pd/Ni capture device OR a second oxide element: YB08) The process according to any one of Embodiment Y01) to Y07), wherein said highly heated gas stream in addition to contacting said first oxide element is further also contacting a metallic element comprising a metallic material selected from the group consisting of palladium, and palladium alloys, more specifically palladium-nickel alloys and palladium-gold alloys; OR wherein said highly heated gas stream in addition to contacting said first oxide element is further also contacting a second oxide element, (being different from said first oxide element) comprising at least one further oxide being different from said at least one oxide comprised in said first oxide element, wherein said further oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Ce, Pr,
K.A. Rasmussen 2024-07-19 LIG-001PCT2 Nd, Pm, Sm, Eu and Gd, preferably La, Nd and Gd, more preferably La and Nd, and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga), preferably from Fe or Ni, (more preferably from Ni); optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement. YB09) The process according to any one of Embodiment Y01) to Y07), wherein said highly heated gas stream in addition to contacting said first oxide element is further also contacting a metallic element comprising a metallic material selected from the group consisting of palladium, and palladium alloys, more specifically palladium-nickel alloys and palladium-gold alloys. This Embodiment YB09) is also further (above and besides the inventive advantages of Embodiment Y) inventive as based on the selection of combining the Pd/Ni catchment device and the oxide. This is a good combination as the Pd/Ni catchment device captures platinum and the first oxide element helps capturing even more platinum. YB10) The process according to EMBODIMENT YB09), wherein the contact with said metallic element precedes and/or is upstream from the contact with said first oxide element. YB11) The process according to EMBODIMENT YB09), wherein the contact with said metallic element follows and/or is downstream from the contact with said first oxide element. YB12) The process according to any one of EMBODIMENTS Y01) to Y07), wherein said highly heated gas stream in addition to contacting said first oxide element is further also contacting a second oxide element, (being different from said first oxide element) comprising at least one further oxide being different from said at least one oxide comprised in said first oxide element, wherein said further oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, preferably La, Nd and Gd, more preferably La and Nd, and with
K.A. Rasmussen 2024-07-19 LIG-001PCT2 B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga), preferably from Fe or Ni, (more preferably from Ni); optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement. This Embodiment YB12) is also further (above and besides the inventive advantages of Embodiment Y) inventive as it is a good combination in which e.g. the second oxide element can be chosen to be better suited to capture rhodium or even more platinum while the first oxide element captures platinum etc., or vice versa (maybe also relying on different temperatures of around 800° or 900° C depending on which noble metal to capture). YB13) The process according to EMBODIMENT YB12), wherein the contact with said second oxide element precedes and/or is upstream from the contact with said first oxide element. YB14) The process according to EMBODIMENT YB12), wherein the contact with said second oxide element follows and/or is downstream from the contact with said first oxide element. Y + B + C): Y) PLATINUM (ONLY) CAPTURE WITH OXIDE in Combination B) with a Pd/Ni capture device OR a second oxide element, and C) at a higher temperature: YBC15) The process according to any one of EMBODIMENTS YB08) to YB14), wherein said highly heated gas stream after its contact with said catalyst is contacted with said first oxide element at a temperature at around or above 800°C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C), preferably at around 900 °C or above (or at 850°C to 950°C).
K.A. Rasmussen 2024-07-19 LIG-001PCT2 YBC16) The process according to EMBODIMENT YBC15), wherein said high temperature gas reaction is carried out at temperatures of at around or above 800°C, preferably at around 900°C or above. This Embodiment YBC15) is also further (above and besides the inventive advantages of Embodiments YB08 to YB14) inventive as it adds the element of a higher capture of platinum with these higher temperatures as can be seen in Example 1. YBC17) The process according to any one of EMBODIMENTS YB09) to YB11), wherein said highly heated gas stream after its contact with said catalyst is contacted with said first oxide element at temperatures of around 800 °C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C) or above or at temperatures of 775°C to 825 °C. YBC18) The process according to EMBODIMENT YBC17), wherein said high temperature gas reaction is carried out at temperatures of at around or above 800°C. This Embodiment YBC17) is also further (above and besides the inventive advantages of Embodiment YB09) inventive as it adds the element of the more effective capture of platinum with these optimized temperatures as can be seen in Example 1. The art is mute on this specific influence of temperature on platinum capture. YBC19) The process according to any one of EMBODIMENTS YB12) to YB14), wherein said highly heated gas stream after its contact with said catalyst is contacted with said second oxide element at temperatures of around 800 °C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C) or at temperatures of 775°C to 825 °C and with said first oxide element at temperatures of around 800 °C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C) or at temperatures of 775°C to 825 °C.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 YBC20) The process according to EMBODIMENT YBC19), wherein said high temperature gas reaction is carried out at temperatures of at around or above 800°C. This Embodiment YBC19) is also further (above and besides the inventive advantages of Embodiment YB12) inventive as it adds the element of the more effective capture of platinum with these optimized temperatures as can be seen in Example 1. The art is mute on this specific influence of temperature on platinum capture. Y + C): Y) PLATINUM (ONLY) CAPTURE WITH OXIDE in Combination with C) a higher capture temperature YC21) The process according to any one of Embodiment Y01) to Y07), wherein said highly heated gas stream after its contact with said catalyst is contacted with said first oxide element at a temperature at around or above 800°C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C), preferably at around 900 °C or above (or at 850°C to 950°C). YC22) The process according to EMBODIMENT YC21), wherein said high temperature gas reaction is carried out at temperatures of at around or above 800°C, preferably at around 900°C or above. YC23) The process according to any one of Embodiment Y01) to Y07), wherein said highly heated gas stream after its contact with said catalyst is contacted with said first oxide element at a temperature at around 800 °C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C) or above or at temperatures of 775°C to 825 °C. YC24) The process according to EMBODIMENT YB23), wherein said high temperature gas reaction is carried out at temperatures of at around or above 800°C. These Embodiments YC21) and YC23) is also further (above and besides the inventive advantages of Embodiment Y) inventive as it adds the element of the more effective
K.A. Rasmussen 2024-07-19 LIG-001PCT2 capture of platinum with these optimized temperatures as can be seen in Example1. The art is mute on this specific influence of temperature on platinum capture. EMBODIMENT Z) PLATINUM AND RHODIUM CAPTURE WITH OXIDE Z01) A process for the capture of rhodium and platinum lost by volatilization from a catalyst comprising rhodium and platinum to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains the volatilized rhodium and platinum while such volatilized rhodium and platinum is still essentially in the vapor phase and at a temperature of at least 700 °C with a first oxide element comprising at least one oxide being selected from - an oxide of formula ABO3, especially as a perovskite, with A being selected from alkali earth, alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, Sr, Ca and Ba, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga; optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement; - an oxide of formula An+1BnO3n+1, with n being 1 or 3, with A being selected from alkaline earth and rare earth elements/lanthanoids, preferably with A being selected from La, Pr, Nd, Sr and Ca, and with B being selected from 3-5d elements, and p-block elements, preferably with B being selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga; optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement;
K.A. Rasmussen 2024-07-19 LIG-001PCT2 This Embodiment Z) is based on the surprising effect that it was found that in many cases also a pronounced Pt capture is seen, for example in the experiments of example 3, Table 1 (which is in some aspects close to the industrial situation) where the oxides were able to capture both Rh and Pt. This was unknown from the art. NdNiO3 was shown to capture both Pt and Rh and the same applies for LaNiO3, La2NiO4, La4Ni3O10 and LaFeO3. Z02) A process for the capture of rhodium and platinum lost by volatilization from a catalyst comprising rhodium and platinum to a high heated gas stream contacted therewith in a high temperature gas reaction carried out at temperatures of at least 700°C which comprises contacting such highly heated gas stream, after its contact with such catalyst, which contains the volatilized rhodium and platinum while such volatilized rhodium and platinum is still essentially in the vapor phase and at a temperature of at least 700 °C with a first oxide element comprising at least one oxide, wherein said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, preferably La, Nd and Gd, more preferably La and Nd, and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga), preferably from Fe or Ni, (more preferably from Ni); optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement. Z03) The process according to Embodiments Z01) or Z02), wherein said capture of rhodium and platinum is simultaneous capture of rhodium and platinum. Z04) The process according to any one of Embodiments Z01 to Z03), wherein said oxide is selected from LaNiO3, La2NiO4, La4Ni3O10, La4NiO3, NdNiO3, Nd2NiO4, Nd4Ni3O10, Nd4NiO3, LaFeO3 and LaCoO3, preferably from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, LaFeO3 and LaCoO3; more preferably is NdNiO3. Z05) The process according to Embodiments Z01) or Z02), wherein said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Ce, Pr, Nd, Pm, Sm,
K.A. Rasmussen 2024-07-19 LIG-001PCT2 Eu and Gd, preferably La, Nd and Gd, more preferably La and Nd, and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga), preferably from Fe or Ni, (more preferably from Ni); optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement. Z06) The process according to Embodiment Z05), wherein said oxide is selected from LaNiO3, La2NiO4, La4Ni3O10, La4NiO3, NdNiO3, Nd2NiO4, Nd4Ni3O10, Nd4NiO3, LaFeO3 and LaCoO3, preferably from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, LaFeO3 and LaCoO3, more preferably from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, and LaFeO3. Z07) The process according to any one of Embodiments Z01) to Z08), wherein the highly heated gas stream also contains N2O, which is converted/decomposed upon contact with said first oxide element, preferably wherein the N2O is converted/decomposed to NO, NOx, N2 and/or O2. Z08) The process according to any one of Embodiments Z01) to Z09), wherein the catalytic reaction of the high temperature gas reaction is a catalytic ammonia oxidation or catalytic ammonia combustion. Z + B): Z) RHODIUM AND PLATINUM CAPTURE WITH OXIDE in Combination B) with a Pd/Ni capture device OR a second oxide element: ZB09) The process according to any one of Embodiment Z01) to Z08), wherein said highly heated gas stream in addition to contacting said first oxide element is further also contacting a metallic element comprising a metallic material selected from the group consisting of palladium, and palladium alloys, more specifically palladium-nickel alloys and palladium-gold alloys; OR
K.A. Rasmussen 2024-07-19 LIG-001PCT2 wherein said highly heated gas stream in addition to contacting said first oxide element is further also contacting a second oxide element, (being different from said first oxide element), comprising at least one further oxide being different from said at least one oxide comprised in said first oxide element, wherein said further oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, preferably La, Nd and Gd, more preferably La and Nd, and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga), preferably from Fe or Ni, (more preferably from Ni); optionally with one or more elements on A position in form of a solid solution or in an ordered arrangement and/or optionally with one or more elements in B-position in form of a solid solution or in an ordered arrangement; or ZB10) The process according to any one of Embodiment Z01) to Z08), wherein said highly heated gas stream in addition to contacting said first oxide element is further also contacting a metallic element comprising a metallic material selected from the group consisting of palladium, and palladium alloys, more specifically palladium-nickel alloys and palladium-gold alloys. This Embodiment ZB10) is also further (above and besides the inventive advantages of Embodiment Z)) inventive as based on the selection of combining the Pd/Ni catchment device and the oxide. This is a good combination as the Pd/Ni catchment device captures platinum and the first oxide element helps capturing rhodium. ZB11) The process according to EMBODIMENT ZB10), wherein the contact with said metallic element precedes and/or is upstream from the contact with said first oxide element. ZB12) The process according to EMBODIMENT ZB10), wherein the contact with said metallic element follows and/or is downstream from the contact with said first oxide element.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 ZB13) The process according to any one of EMBODIMENTS Z01) to Z08), wherein said highly heated gas stream in addition to contacting said first oxide element is further also contacting a second oxide element, (being different from said first oxide element) comprising at least one further oxide being different from said at least one oxide comprised in said first oxide element, wherein said further oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A2BO4, A4B3O10, with A being selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd, preferably La, Nd and Gd, more preferably La and Nd, and with B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga), preferably from Fe or Ni, (more preferably from Ni). This Embodiment ZB13) is also further (above and besides the inventive advantages of Embodiment Z)) inventive as it is a good combination in which e.g. the second oxide element can be chosen to be better suited to capture platinum while the first oxide element helps capture rhodium or the other way around etc., or vice versa (maybe also relying on different temperatures of around 800° or 900° C depending on which noble metal to capture). ZB14) The process according to EMBODIMENT ZB13), wherein the contact with said second oxide element precedes and/or is upstream from the contact with said first oxide element. ZB15) The process according to EMBODIMENT ZB13), wherein the contact with said second oxide element follows and/or is downstream from the contact with said first oxide element. Z + B + C): Z) RHODIUM AND PLATINUM CAPTURE WITH OXIDE in Combination B) with a Pd/Ni capture device OR a second oxide element, and C) at a higher temperature:
K.A. Rasmussen 2024-07-19 LIG-001PCT2 ZBC16) The process according to any one of EMBODIMENTS ZB09) to ZB15), wherein said highly heated gas stream after its contact with said catalyst is contacted with said first oxide element at a temperature at around or above 800°C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C), preferably at around 900 °C or above (or at 850°C to 950°C). ZBC17) The process according to EMBODIMENT ZBC16), wherein said high temperature gas reaction is carried out at temperatures of at around or above 800°C, preferably at around 900°C or above. This Embodiment ZBC16) is also further (above and besides the inventive advantages of Embodiments ZB09 to ZB15) inventive as it adds the element of a higher capture of rhodium with these higher temperatures as can be seen in Example 1. The art is completely silent on this influence of temperature on rhodium capture. ZBC18) The process according to any one of EMBODIMENTS ZB10) to ZB12), wherein said highly heated gas stream after its contact with said catalyst is contacted with said first oxide element at temperatures of around 900 °C or above or at temperatures of 875°C to 925 °C. ZBC19) The process according to EMBODIMENT ZBC18), wherein said high temperature gas reaction is carried out at temperatures of at around or above 900°C. This Embodiment ZBC18) is also further (above and besides the inventive advantages of Embodiment ZB10) inventive as it adds the element of a higher capture of rhodium with these higher temperatures by the first oxide element as can be seen in Example 1, while the Pd/Ni element captures the platinum. The art is completely silent on this influence of temperature on rhodium capture. ZBC20) The process according to any one of EMBODIMENTS ZB13) to ZB15), wherein said highly heated gas stream after its contact with said catalyst is contacted with said first oxide element at temperatures of around 900 °C or above (or at 850°C to 950°C) or at temperatures of 875°C to 925 °C and with said second oxide element at temperatures of around 800 °C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C) or at temperatures of 775°C to 825 °C.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 ZBC21) The process according to EMBODIMENT ZBC20), wherein said high temperature gas reaction is carried out at temperatures of at around or above 800°C or at temperatures of at around 900°C or above. This Embodiment ZBC20) is also further (above and besides the inventive advantages of Embodiment ZB13) inventive as it adds the element of a higher capture of rhodium with these higher temperatures by the first oxide element as can be seen in Example 1, while the second oxide element better captures the platinum. The art is completely silent on this influence of temperature on rhodium (or also platinum) capture. Z + C): Z) RHODIUM AND PLATINUM) CAPTURE WITH OXIDE in Combination with C) a higher capture temperature ZC22) The process according to any one of Embodiment Z01) to Z08), wherein said highly heated gas stream after its contact with said catalyst is contacted with said first oxide element at a temperature at around or above 800°C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C), preferably at around 900 °C or above (or at 850°C to 950°C). ZC23) The process according to EMBODIMENT ZC22), wherein said high temperature gas reaction is carried out at temperatures of at around or above 800°C, preferably at around 900°C or above. ZC24) The process according to any one of Embodiment Z01) to Z08), wherein said highly heated gas stream after its contact with said catalyst is contacted with said first oxide element at a temperature at around 900 °C or above (or at 850°C to 950°C) or at temperatures of 875°C to 925 °C or at a temperature at around 800 °C (or at 750°C to 900°C or at 750°C to 850°C or at 800°C to 900°C) or at temperatures of 775°C to 825 °C. ZC25) The process according to EMBODIMENT ZC24), wherein said high temperature gas reaction is carried out at temperatures of at around or above 800°C, or at around 900°C or above.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 These Embodiments ZC22) and ZC24) is also further (above and besides the inventive advantages of Embodiment Z) inventive as it adds the element of a higher capture of platinum and/or rhodium with these higher temperatures as can be seen in Example 1. The art is mute on this influence of a specific temperature on rhodium/platinum capture.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 COMMON ELEMENT OF ALL EMBODIMENTS ABOVE, NAMELY EMBODIMENTS A), B), C), D), E), V), W), X), Y) and Z): In a very preferred embodiment of EMBODIMENTS A), B), C), D), E), V), W), X), Y) and Z) according to the invention said at least one oxide of the first oxide element is selected from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, Nd2NiO4, Nd4Ni3O10, LaFeO3, and LaCoO3. In a very preferred embodiment of EMBODIMENTS A), B), C), D), E), V), W), X), Y) and Z) according to the invention the oxide is selected from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, Nd2NiO4, Nd4Ni3O10, and LaFeO3. In a very preferred embodiment of EMBODIMENTS A), B), C), D), E), V), W), X), Y) and Z) according to the invention said at least one oxide of the first oxide element is selected from LaNiO3, La2NiO4, La4Ni3O10, LaFeO3, LaCoO3. In a very preferred embodiment of EMBODIMENTS A), B), C), D), E), V), W), X), Y) and Z) according to the invention said at least one oxide of the first oxide element is selected from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3 and LaFeO3. In a very preferred embodiment of EMBODIMENTS A), B), C), D), E), V), W), X), Y) and Z) according to the invention said at least one oxide of the first oxide element is selected from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3 and LaFeO3. In a very preferred embodiment of EMBODIMENTS A), B), C), D), E), V), W), X), Y) and Z) according to the invention said at least one oxide of the first oxide element is selected from LaNiO3, La2NiO4, and La4Ni3O10. In a very preferred embodiment of EMBODIMENTS A), B), C), D), E), V), W), X), Y) and Z) according to the invention said at least one oxide of the first oxide element is selected from NdNiO3, Nd2NiO4, Nd4Ni3O10, and LaFeO3. In a very preferred embodiment of EMBODIMENTS A), B), C), D), E), V), W), X), Y) and Z) according to the invention said at least one oxide of the first oxide element is selected from NdNiO3, Nd2NiO4, Nd4Ni3O10, and LaFeO3.
K.A. Rasmussen 2024-07-19 LIG-001PCT2 In a very preferred embodiment of EMBODIMENTS A), B), C), D), E), V), W), X), Y) and Z) according to the invention said at least one oxide of the first oxide element is selected from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, Nd2NiO4 and Nd4Ni3O10. In a very preferred embodiment of EMBODIMENTS A), B), C), D), E), V), W), X), Y) and Z) according to the invention said at least one oxide of the first oxide element is selected from LaNiO3, NdNiO3, and LaFeO3. In a very preferred embodiment of EMBODIMENTS A), B), C), D), E), V), W), X), Y) and Z) according to the invention said at least one oxide of the first oxide element is selected from LaNiO3 and NdNiO3. In a very preferred embodiment of EMBODIMENTS A), B), C), D), E), V), W), X), Y) and Z) according to the invention said at least one oxide of the first oxide element is selected from NdNiO3, and LaFeO3. In a very preferred embodiment of EMBODIMENTS A), B), C), D), E), V), W), X), Y) and Z) according to the invention said at least one oxide of the first oxide element is LaFeO3. In a very preferred embodiment of EMBODIMENTS A), B), C), D), E), V), W), X), Y) and Z) according to the invention said at least one oxide of the first oxide element is NdNiO3. In a very most preferred embodiment of EMBODIMENTS A), B), C), D), E), V), W), X), Y) and Z) according to the invention said at least one oxide of the first oxide element is LaNiO3.