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WO2025021699A1 - Procédé de capture d'un métal noble, en particulier du rhodium, perdu par volatilisation d'un catalyseur à un flux gazeux hautement chauffé à l'aide d'un oxyde - Google Patents

Procédé de capture d'un métal noble, en particulier du rhodium, perdu par volatilisation d'un catalyseur à un flux gazeux hautement chauffé à l'aide d'un oxyde Download PDF

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Publication number
WO2025021699A1
WO2025021699A1 PCT/EP2024/070598 EP2024070598W WO2025021699A1 WO 2025021699 A1 WO2025021699 A1 WO 2025021699A1 EP 2024070598 W EP2024070598 W EP 2024070598W WO 2025021699 A1 WO2025021699 A1 WO 2025021699A1
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Prior art keywords
oxide
rhodium
optionally
elements
perovskite
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PCT/EP2024/070598
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English (en)
Inventor
Johan Skjelstad
Anja Olafsen SJÅSTAD
Helmer FJELLVÅG
Asbjørn Slagtern FJELLVÅG
Julie HESSEVIK
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KARasmussen
Oslo Uio, University of
Yara International ASA
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KARasmussen
Oslo Uio, University of
Yara International ASA
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Publication of WO2025021699A1 publication Critical patent/WO2025021699A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
    • C22B11/02—Obtaining noble metals by dry processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
    • C01B21/24—Nitric oxide (NO)
    • C01B21/26—Preparation by catalytic or non-catalytic oxidation of ammonia
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
    • C22B11/02—Obtaining noble metals by dry processes
    • C22B11/021—Recovery of noble metals from waste materials
    • C22B11/026—Recovery of noble metals from waste materials from spent catalysts
    • C22B11/028—Recovery of noble metals from waste materials from spent catalysts using solid sorbents, e.g. getters or catchment gauzes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/464—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/485—Impregnating or reimpregnating with, or deposition of metal compounds or catalytically active elements
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • 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.
  • Nitrogen-based inorganic fertilizers are produced from nitric acid obtained in the Ostwald process.
  • ammonia is oxidized over a Pt-Rh (typically 95:5 wt%) catalytic gauze at high temperature and moderate pressure to produce nitric oxide (NO).
  • Pt-Rh typically 95:5 wt%
  • NO nitric oxide
  • the yields achieved with the catalytic gauzes are 95–97 % depending on pressure and temperature.
  • the strong greenhouse gas nitrous oxide (N 2 O) 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.
  • Pt 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.
  • 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
  • said oxide is an oxide of formula ABO3 in form of a perovskite and optionally its respective RP phases like A 2 BO 4 , A 4 B 3 O 10 , 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.
  • a preferred OPTION A in embodiment “OA-01”) of the invention it is preferred if said oxide is an oxide of formula ABO 3 in form of a perovskite and optionally its respective RP phases like A 2 BO 4 , A 4 B 3 O 10 , with B being selected from Fe or Ni, preferably Ni.
  • 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.
  • oxide 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 A 2 BO 4 , A 4 B 3 O 10 , 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 ABO 3 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.
  • 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.
  • OPTION B in embodiment “OB-01” of the invention it is preferred K.A.
  • oxide 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 ABO 3 in form of a perovskite and optionally its respective RP phases like A 2 BO 4 , 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.
  • the said oxide is selected from NdNiO3, Nd 2 NiO 4 , and Nd 4 Ni 3 O 10 , especially is NdNiO 3 .
  • 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 ABO 3 in form of a perovskite and optionally its respective RP phases like A 2 BO 4 , A 4 B 3 O 10 , 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.
  • the said oxide is LaFeO3.
  • OPTION B in embodiment “OB-04” also optionally combined with embodiments “OB-01” - “OB-03”
  • 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.
  • 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).
  • 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
  • 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
  • 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 NdNiO 3 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.
  • first oxide element comprising at least one oxide could in a more specific embodiment be “first oxide element consisting of at least one oxide”.
  • 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.
  • 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 ABO 3 in form of a perovskite and optionally its respective RP phases like A 2 BO 4 , A 4 B 3 O 10 , 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).
  • the invention in this preferred aspect of the invention covering OPTION A (thus ASPECT A), 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 A n+1 B n O 3n+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.
  • 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.
  • said oxide is an oxide of formula ABO 3 in form of a perovskite and optionally its respective RP phases like A 2 BO 4 , A 4 B 3 O 10 , 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 ABO 3 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.
  • 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.
  • 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
  • said oxide is an oxide of formula ABO 3 in form of a perovskite and optionally its respective RP phases like A 2 BO 4 , A 4 B 3 O 10 , 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 ABO 3 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.
  • 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 ABO 3 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 LaFeO 3 .
  • 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.
  • 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.
  • 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.
  • 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.
  • N2O 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.
  • N2O 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.
  • the strong greenhouse gas nitrous oxide (N2O) is an unwanted byproduct of the Ostwald process.
  • 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 N 2 O.
  • 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.
  • said at least one oxide of the first oxide element is selected from LaNiO 3 , La 2 NiO 4 , La 4 Ni 3 O 10 , NdNiO 3 , and LaFeO 3 .
  • said at least one oxide of the first oxide element is selected from LaNiO 3 , La 2 NiO 4 , La 4 Ni 3 O 10 , NdNiO 3 , and LaFeO 3 .
  • said at least one oxide of the first oxide element is selected from LaNiO3, La2NiO4, and La4Ni3O10.
  • said at least one oxide of the first oxide element is selected from NdNiO 3 , Nd 2 NiO 4 , Nd 4 Ni 3 O 10 , and LaFeO 3 . K.A.
  • said at least one oxide of the first oxide element is selected from LaNiO 3 , NdNiO 3 , and LaFeO 3 .
  • said at least one oxide of the first oxide element is selected from LaNiO 3 and NdNiO 3 .
  • said at least one oxide of the first oxide element is selected from NdNiO3, and LaFeO3.
  • 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.
  • the use is for the capture of platinum and rhodium, especially in the same process.
  • 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 N 2 O is decomposed/converted to NO, NO x , N 2 and/or O 2 .
  • 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.
  • the invention in another preferred aspect, 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.
  • lanthanoid is to be understood as meaning a series of chemical elements of atomic numbers 57-71, from lanthanum through lutetium.
  • the “lanthanoids” in the context of the invention are selected from La, Ce, Pr, Nd, Pm, Sm, Eu and Gd.
  • transition metal is to be understood as meaning a chemical element in d-block of the periodic table, including groups 3 to 12.
  • 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
  • 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.
  • 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.
  • 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.
  • decompose and/or “convert” is to be understood as meaning the conversion/decomposition, especially of N 2 O, especially to NO, NOx, N 2 and/or O 2 . This happens upon contact with an element, e.g.
  • volatilization from a catalyst
  • volatilization 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”.
  • high temperature is to be understood as meaning at a temperature of or above 700°C.
  • contact is to be understood as meaning a physical contact or close contact e.g.
  • 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.
  • 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.
  • ABO 3 The general formula for oxides being ABO 3 is A n+1 B n O 3n+1 (or (ABO 3 ) n (AO)) whereof n is an integer, preferably with n being 1 or 3.
  • n an integer, preferably with n being 1 or 3.
  • a site cation is generally from alkaline earth and rare earth elements
  • B site cation is generally selected from 3-5d elements, p- block elements.
  • Preferable RP-phases for ABO3 are A2BO or A4B3O10.
  • 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 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.
  • 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).
  • 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.
  • 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
  • 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.
  • OA OPTION A
  • OB OPTION B
  • oxide in embodiment “OA-01”) of the invention it is preferred if said oxide is an oxide of formula ABO 3 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, A 4 B 3 O 10 , with A being selected from La, Pr, Nd and Gd, preferably from La and Nd.
  • oxide 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 ABO 3 in form of a perovskite and optionally its respective RP phases like A 2 BO 4 , A 4 B 3 O 10 , 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.
  • oxide is selected from LaNiO 3 , La 2 NiO 4 , La 4 Ni 3 O 10 , NdNiO 3 , Nd 2 NiO 4 , Nd 4 Ni 3 O 10 and LaFeO 3 , preferably from LaNiO 3 , NdNiO 3 and LaFeO 3 .
  • a preferred OPTION B (in embodiment “OB-01”) of the invention it is preferred - if said oxide is an oxide of formula ABO 3 in form of a perovskite and optionally its respective RP phases like A 2 BO 4 , A 4 B 3 O 10 , 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.
  • oxide 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 ABO 3 in form of a perovskite and optionally its respective RP phases like A 2 BO 4 , A 4 B 3 O 10 , 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.
  • the said oxide is selected from NdNiO3, Nd2NiO4, and Nd4Ni3O10, especially is NdNiO3.
  • 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 ABO 3 in form of a perovskite and optionally its respective RP phases like A 2 BO 4 , A 4 B 3 O 10 , 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.
  • the said oxide is LaFeO3.
  • said oxide is selected from NdNiO 3 , Nd 2 NiO 4 , Nd 4 Ni 3 O 10 and LaFeO 3 , preferably from NdNiO 3 and LaFeO 3 .
  • 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 ABO 3 , especially as a perovskit
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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 optional
  • EMBODIMENT E PLATINUM CAPTURE WITH ABO3-OXIDES (LaNiO3 and NdNiO3) or (NdNiO3) E01)
  • EMBODIMENT X RHODIUM (ONLY) CAPTURE WITH OXIDE X02)
  • 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 ABO 3 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),
  • 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)
  • 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.
  • 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 PtO 2 /RhO 2 in the gas phase.
  • 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 NiO 3 0.02 0.40 0.30 La 2 NiPtO 6 La2NiO4 0.05 0.14 0.22 La2NiPtO6 La4Ni3O10 0.01 0.08 0.14 La2NiPtO6 NdNiO 3 0.05 0.26 0.30 Nd 2 NiPtO 6 LaFeO 3 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 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,
  • 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 A 2 BO 4 , A 4 B 3 O 10 , with B being selected from Fe or Ni, preferably Ni..
  • 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 ABO 3 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.
  • 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.
  • 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 A 2 BO 4 , A 4 B 3 O 10 , 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.
  • the said oxide is selected from NdNiO3, Nd2NiO4, and Nd4Ni3O10, especially is NdNiO3.
  • said oxide is an oxide of formula ABO 3 in form of a perovskite and optionally its respective RP phases like A 2 BO 4 , A 4 B 3 O 10 , 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.
  • the said oxide is LaFeO3.
  • said oxide is selected from NdNiO 3 , Nd 2 NiO 4 , Nd 4 Ni 3 O 10 and LaFeO 3 , preferably from NdNiO 3 and LaFeO 3 .
  • 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 ABO 3 , 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
  • 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 N 2 O is converted/decomposed to NO, NO x , N 2 and/or O 2 .
  • 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, A 4 NiO 3 , wherein A is
  • an oxide element comprising at least one oxide selected from - an oxide of formula ABO 3 , 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.
  • 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 ABO 3 , 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.
  • 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,
  • 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 A 2 BO 4 , A 4 B 3 O 10 , 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 ABO 3 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.
  • oxide is selected from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, Nd2NiO4, Nd4Ni3O10 and LaFeO3, preferably from LaNiO3, NdNiO3 and LaFeO3.
  • 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 ABO 3 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 ABO 3 in form of a perovskite with A being selected from La,
  • the said oxide is selected from NdNiO 3 , Nd2NiO4, and Nd4Ni3O10, especially is NdNiO3.
  • NdNiO 3 , Nd2NiO4, and Nd4Ni3O10 especially is NdNiO3.
  • 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 ABO 3 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.
  • the said oxide is LaFeO3.
  • 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
  • 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
  • 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.
  • 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.
  • 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).
  • 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 N 2 O, which is converted/decomposed upon contact with said first oxide element, preferably wherein the N 2 O 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.
  • 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 A 2 NiO 4 , A 4 Ni 3 O 10 , A 4 NiO 3 , 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.
  • EMBODIMENT C RHODIUM CAPTURE WITH OXIDES in Combination with a raised temperature: K.A. Rasmussen 2024-07-19 LIG-001PCT2 C01)
  • 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 LaNiO 3 , La 2 NiO 4 , La 4 Ni 3 O 10 and LaFeO 3 .
  • 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).
  • 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,
  • 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, NO x , N 2 and/or O 2 .
  • 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.
  • 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, Nd 4 Ni 3 O 10 , Nd 4 NiO 3 , LaNiO 3 , La 2 NiO 4 , La 4 Ni 3 O 10 ; preferably is LaNiO 3 or NdNiO 3 ; 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, N
  • 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 ABO 3 of the first oxide element and being of formula ABO 3 , 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.
  • the second oxide element comprises at least one further oxide selected from NdNiO 3 , LaNiO 3 , La 2 NiO 4 , La 4 Ni 3 O 10 , LaFeO 3 , LaCoO 3 , La 0.85 Sr 0.15 FeO 3 , Nd 2 NiO 4 , Nd 4 Ni 3 O 10 , Nd 4 NiO 3 ; or of formula ANiO 3 and their respective RP phases A 2 NiO 4 , A 4 Ni 3 O 10 , and A 4 NiO 3 , wherein A is selected from La and Nd.
  • 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 N 2 O, which is converted/decomposed upon contact with said first oxide element, preferably wherein the N 2 O is converted/decomposed to NO, NO x , N 2 and/or O 2 .
  • 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).
  • 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.
  • EMBODIMENTS D14) or D15 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 NdNiO 3 ; or wherein the at least one oxide is LaNiO 3 .
  • 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).
  • B being selected from Fe, Co and Ni (or Ti, V, Cr, Mn, Fe, Co, Ni, Mg, Al, Ga).
  • 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 La 2 NiO 4 , La 4 Ni 3 O 10 , LaFeO 3 , LaNiO3 or NdNiO 3 .
  • E04 The process of EMBODIMENT E01), wherein the at least one oxide is NdNiO 3 ; or wherein the at least one oxide is LaNiO 3 E05)
  • 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 ABO 3 of the first oxide element and being of formula ABO 3 in form of a perovskite and optionally its respective RP phases like A 2 BO 4 , A 4 B 3 O 10 , 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,
  • 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 .
  • 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 ANiO 3 and their respective RP phases A 2 NiO 4 , A 4 Ni 3 O 10 , and A 4 NiO 3 , wherein A is selected from La and Nd.
  • 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).
  • 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.
  • 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 ABO 3 , in form of a perovskite and optionally its respective RP phases like A 2 BO 4 , A 4 B 3 O 10 , 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).
  • 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).
  • 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 La 2 NiO 4 , La 4 Ni 3 O 10 , LaFeO 3 , LaNiO3 or NdNiO 3 .
  • 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
  • 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 (N 2 O) which is also called Laughing Gas, selectivity is less than 2% of the overall reactions.
  • 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.
  • 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 850 o C
  • 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 LaNiO 3 .
  • Kanthal screens are available from many vendors at different shapes and different wire diameters, the deposition of LaNiO 3 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 180 o C and calcinated in a furnace at 400 o C.
  • 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.
  • 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 ABO 3 , in form of a perovskite and optionally its respective RP phases like A 2 BO 4 , A 4 B 3 O 10 , 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.
  • 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.
  • 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
  • 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)
  • 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
  • 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 N 2 O, especially in the same process, preferably wherein the N 2 O is decomposed/converted upon contact with said oxide element, most preferably wherein the N 2 O is decomposed/converted to NO, NO x , N 2 and/or O 2 .
  • 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 NdNiO
  • 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 N 2 O is converted/decomposed to NO, NO x , N 2 and/or O 2 .
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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
  • 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 A 2 BO 4 , A 4 B 3 O 10 , with A being selected from La, Ce, Pr,
  • Embodiment 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.
  • 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.
  • 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.
  • 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.
  • said 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.
  • Embodiments YC21) and YC23) are 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 ABO 3 , 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,
  • Rasmussen 2024-07-19 LIG-001PCT2 Eu and Gd preferably La, Nd and Gd, more preferably La and Nd
  • 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.
  • 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 ABO 3 in form of a perovskite and optionally its respective RP phases like A 2 BO 4 , A 4 B 3 O 10 , 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
  • 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.
  • 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 ABO 3 in form of a perovskite and optionally its respective RP phases like A 2 BO 4 , A 4 B 3 O 10 , 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Embodiments ZC22) and ZC24 are 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.
  • said at least one oxide of the first oxide element is selected from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, Nd2NiO4, Nd4Ni3O10, LaFeO3, and LaCoO3.
  • the oxide is selected from LaNiO 3 , La 2 NiO 4 , La 4 Ni 3 O 10 , NdNiO 3 , Nd 2 NiO 4 , Nd 4 Ni 3 O 10 , and LaFeO 3 .
  • said at least one oxide of the first oxide element is selected from LaNiO 3 , La 2 NiO 4 , La 4 Ni 3 O 10 , LaFeO 3 , LaCoO 3 .
  • said at least one oxide of the first oxide element is selected from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3 and LaFeO3.
  • said at least one oxide of the first oxide element is selected from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3 and LaFeO3.
  • said at least one oxide of the first oxide element is selected from LaNiO 3 , La 2 NiO 4 , and La 4 Ni 3 O 10 .
  • said at least one oxide of the first oxide element is selected from NdNiO 3 , Nd 2 NiO 4 , Nd 4 Ni 3 O 10 , and LaFeO 3 .
  • said at least one oxide of the first oxide element is selected from NdNiO3, Nd2NiO4, Nd4Ni3O10, and LaFeO3.
  • said at least one oxide of the first oxide element is selected from LaNiO3, La2NiO4, La4Ni3O10, NdNiO3, Nd2NiO4 and Nd4Ni3O10.
  • said at least one oxide of the first oxide element is selected from LaNiO 3 , NdNiO 3 , and LaFeO 3 .
  • said at least one oxide of the first oxide element is selected from LaNiO 3 and NdNiO 3 .
  • said at least one oxide of the first oxide element is selected from NdNiO3, and LaFeO3.
  • said at least one oxide of the first oxide element is LaFeO3.
  • said at least one oxide of the first oxide element is NdNiO3.
  • said at least one oxide of the first oxide element is LaNiO3.

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Abstract

La présente invention concerne un procédé de capture d'un métal noble, notamment de rhodium, perdu par volatilisation d'un catalyseur à un flux gazeux hautement chauffé (y compris un chauffage local dû à une réaction hautement exothermique) par mise en contact du flux gazeux hautement chauffé contenant le métal noble volatilisé avec un premier élément oxyde comprenant au moins un oxyde, de préférence choisi parmi la formule ABO3 (notamment sous forme de pérovskite ou ses phases RP/An+1BnO3n+1 (n = nombre entier, de préférence n = 1, 3)). Ce procédé est particulièrement utile par rapport aux procédés industriels tels que le procédé Ostwald (montrant une réaction hautement exothermique) où un catalyseur contenant du rhodium (et du platine) est utilisé. Dans des circonstances choisies, ces oxydes peuvent également agir sur la décomposition/conversion de N2O indésirable survenant dans ledit procédé Ostwald. D'autres aspects de la présente invention concernent l'utilisation dudit oxyde pour la capture de rhodium ou des dispositifs comprenant cet oxyde qui sont utilisés dans la capture de rhodium.
PCT/EP2024/070598 2023-07-21 2024-07-19 Procédé de capture d'un métal noble, en particulier du rhodium, perdu par volatilisation d'un catalyseur à un flux gazeux hautement chauffé à l'aide d'un oxyde Pending WO2025021699A1 (fr)

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EPPCT/EP2023/070348 2023-07-21
PCT/EP2023/070348 WO2025021282A1 (fr) 2023-07-21 2023-07-21 Procédé de capture d'un métal noble, en particulier du rhodium, perdu par volatilisation d'un catalyseur à un flux gazeux hautement chauffé à l'aide d'un oxyde

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PCT/EP2024/070598 Pending WO2025021699A1 (fr) 2023-07-21 2024-07-19 Procédé de capture d'un métal noble, en particulier du rhodium, perdu par volatilisation d'un catalyseur à un flux gazeux hautement chauffé à l'aide d'un oxyde

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WO2004096703A2 (fr) * 2003-04-29 2004-11-11 Johnson Matthey Plc Procede d'oxydation de l'ammoniac
WO2007104403A1 (fr) * 2006-03-10 2007-09-20 Umicore Ag & Co. Kg Catalyseur et procede de decomposition d'oxyde nitreux et procede et dispositif pour la preparation d'acide nitrique
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WO2012110780A1 (fr) * 2011-02-14 2012-08-23 Johnson Matthey Public Limited Company Catalyseurs utilisés dans des procédés d'oxydation de l'ammoniac
US8394353B2 (en) * 2008-10-20 2013-03-12 Johnson Matthey Plc Catalyst containment unit
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* Cited by examiner, † Cited by third party
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US4774069A (en) * 1985-06-28 1988-09-27 Johnson Matthey Public Limited Company Process for the manufacture of nitric oxide
WO2004096703A2 (fr) * 2003-04-29 2004-11-11 Johnson Matthey Plc Procede d'oxydation de l'ammoniac
WO2007104403A1 (fr) * 2006-03-10 2007-09-20 Umicore Ag & Co. Kg Catalyseur et procede de decomposition d'oxyde nitreux et procede et dispositif pour la preparation d'acide nitrique
US20120076710A1 (en) * 2006-09-08 2012-03-29 David Waller Method and device for catchment of platinum group metals in a gas stream
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WO2012110780A1 (fr) * 2011-02-14 2012-08-23 Johnson Matthey Public Limited Company Catalyseurs utilisés dans des procédés d'oxydation de l'ammoniac
US20200032690A1 (en) * 2015-12-17 2020-01-30 Umicore Ag & Co. Kg Method for preventing a selective catalytic reduction (scr) catalyst from being contaminated with platinum
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N.I. ZAKHARCHENKO: "Recovery of platinum with calcium oxide sorbent in ammonia oxidation", RUSS. J. APPL. CHEM., vol. 75, 2002, pages 402 - 407

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