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WO2025008502A1 - Système de récupération de pt et/ou de rh volatils et procédé associé - Google Patents

Système de récupération de pt et/ou de rh volatils et procédé associé Download PDF

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Publication number
WO2025008502A1
WO2025008502A1 PCT/EP2024/068982 EP2024068982W WO2025008502A1 WO 2025008502 A1 WO2025008502 A1 WO 2025008502A1 EP 2024068982 W EP2024068982 W EP 2024068982W WO 2025008502 A1 WO2025008502 A1 WO 2025008502A1
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volatile
oxide
rare earth
recovery
catalytic
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David Waller
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Yara International ASA
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Yara International ASA
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    • 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
    • C22B7/009—General processes for recovering metals or metallic compounds from spent catalysts
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J23/42—Platinum
    • 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
    • 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
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • 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
    • C01B21/267—Means for preventing deterioration or loss of catalyst or for recovering lost catalyst
    • 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

Definitions

  • the present application is in the field of the recovery of volatile precious metals, particularly volatile Pt and/or Rh from a gas phase.
  • platinum group metals are ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt).
  • platinum (Pt) and/or rhodium (Rh) are commonly used as catalysts among others in the Ostwald process for nitric acid production, for oxidising ammonia into nitric oxide, and in the Andrussow process for hydrogen cyanide production, for reacting ammonia with oxygen and methane.
  • a problem associated with catalysis using platinum group metals, particularly Pt and/or Rh is that, due the high temperature at which catalysis is performed, for example from 700 to 950 °C or over 1000 °C or over 1100 °C, some of these metals, such as Rh and/or Pt metal evaporate, in particular when the catalysis is performed in the presence of oxygen.
  • GB1343637 relates to a process and a related device for recovering platinum metals entrained in a hot gas stream (as in the manufacture of nitric acid) wherein the gas is passed through a gettering device in the form of an inert ceramic honeycomb structure which is coated with a getter containing Pd to absorb the volatile platinum.
  • EP63450 generally discloses a getter device and a related process for recovery of a precious metal lost from a precious metal-containing catalyst operating at elevated temperature, wherein the getter comprises an agglomeration or assemblage of unwoven fibres made from a metal selected from the group ruthenium, palladium, iridium, platinum, gold, silver, rhodium and alloys containing one or more or the said metals.
  • the document primarily focuses on Pd/Au alloys.
  • GB668935 relates to a process and related device for platinum recovery of volatilized platinum, originating from a catalyst.
  • GB668935 claims a process for recovery of platinum, wherein the platinum is trapped on the surface of baffles, disposed at a place where the temperature is at least 700 °C and wherein some of the baffles have a coating of silver or of a silver alloy with gold, palladium or platinum.
  • LIS20130149207 relates to an exhaust system arrangement comprising a Pt+Pd catalyst and a downstream SCR catalyst and a component capable of trapping and/or alloying with a gas phase platinum group metal, wherein this component is typically a metal selected from the group consisting of gold, palladium and silver, preferably a Pd/Au alloy.
  • US4774069A discloses a process for the manufacture of nitric oxide by oxidising ammonia in the presence of a catalyst comprising platinum and from 0 to 20 wt % of rhodium and from 0 to 40 wt % of palladium (based on the weight of alloy), the catalyst being located upstream from a catchment trap for scavenging platinum or rhodium lost from the catalyst.
  • the catchment trap comprises an alloy of Pd with at least one compound selected from the group consisting of the oxides, borides, carbides, silicides, nitrides and silicates of aluminum, zirconium, boron, silicon, magnesium, titanium, yttrium, beryllium, thorium, manganese, lanthanum, scandium, calcium, uranium, chromium, niobium and hafnium.
  • Rh The rhodium capture is significantly less documented than platinum capture, which indicates that it is more challenging to achieve. Nonetheless, at the moment the most expensive precious metal is Rh. Thus, it is of great interest to recover as much volatile Rh as possible.
  • the present application addresses one or more of the above indicated needs.
  • the inventors have surprisingly found that certain oxides of rare earth metals as further defined herein are stable and effective recovery agents for recovering or trapping at least volatile Rh or at least volatile Pt and/or Rh.
  • Yara has established that not all rare earth metal oxides are suitable for recovering volatile Pt and/or Rh.
  • a catalytic system comprises: a Pt-containing and/or Rh-containing catalyst; and a recovery system downstream of the catalyst.
  • the system is characterised in that the recovery system comprises one or more oxide of a rare earth metal selected from the group consisting of Er 2 C>3, So a and Yb 2 Oa.
  • the system is characterised in that the recovery system comprises an oxide of a rare earth metal selected from Er 2 0s and Sm 2 O3
  • the catalytic system is a catalytic system for the catalytic conversion of ammonia into nitric oxide, for the generation of nitric acid, such as present in an ammonia oxidation burner, or the catalytic system is a catalytic system for the catalytic conversion of ammonia, oxygen and methane into hydrogen cyanide, such as present in a reactor for reacting ammonia, oxygen and methane, thereby generating hydrogen cyanide.
  • the recovery system comprises Sm 2 C>3. In one embodiment according to the system of the disclosure, the recovery system comprises Sm 2 C>3 and the catalyst system comprises a Rh-containing catalyst.
  • the Pt-containing and/or Rh- containing catalyst is in the form of a catalytic gauze
  • the recovery system has the shape of a honeycomb, a tablet, a pellet, a sponge, a net or a gauze.
  • the use of one or more oxides of a rare earth metal selected from the group consisting of Er 2 Os, Sm 2 Os and Yb 2 C>3, for recovering volatile Pt and/or Rh, or for recovering volatile Rh or volatile Rh and/or Pt, is disclosed.
  • volatile Pt and/or Rh is generated during the catalytic oxidation of ammonia into nitric oxide, or volatile Pt and/or Rh is generated during the catalytic reaction of ammonia with oxygen and methane, thereby generating hydrogen cyanide.
  • the oxide of the rare earth metal is Sm 2 C>3 and/or Er 2 Os, in particular is Sm 2 C>3.
  • volatile Rh is recovered.
  • the oxide of the rare earth metal is Sm 2 C>3 and volatile Rh is recovered.
  • the oxide of a rare earth metal is comprised in a recovery system that has the shape of a honeycomb, a tablet, a pellet, a sponge, a net or a gauze.
  • a method for oxidising ammonia into nitric oxide or for reacting ammonia with oxygen and methane, thereby generating hydrogen cyanide comprises the steps of: a) catalytically oxidising ammonia into nitric oxide or catalytically reacting ammonia with oxygen and methane thereby generating hydrogen cyanide, whereby volatile Pt and/or Rh is generated; b) contacting the volatile Pt and/or Rh generated in step a) with a recovery system comprising one or more oxide of a rare earth metal selected from the group consisting of Er2C>3, So a and Yb 2 C>3 to form a compound or a solid solution with Pt and/or Rh; and c) recovering Pt and/or Rh from the compound or the solid solution generated in step b)
  • step a) is performed with a catalytic gauze
  • step b) is performed with a recovery system that has the shape of a honeycomb, a tablet, a pellet, a sponge, a net or a gauze.
  • step b) is performed with a recovery system comprising Sm 2 O3 and/or Er 2 0s, in particular comprising Sm 2 C>3.
  • step a) is performed with a Rh-containing catalytic system and step b) is performed with a recovery system comprising Sm 2 O 3 .
  • step a) comprises catalytically oxidising ammonia into nitric oxide at a temperature ranging from 700 to 950 °C.
  • a method for revamping a palladium-containing recovery gauze for recovering volatile platinum and/or rhodium comprises the step of replacing at least part of the palladium comprised in the recovery gauze for one or more oxide of a rare earth metal selected from the group consisting of Er 2 Os, Sm 2 C>3 and Yb 2 O 3 .
  • Figure 1 shows the XRD analysis of the pellet before exposure to the reactor (“fresh”) and the upper surface of the reactor exposed (“pilot tested” or “pilot”) Sm 2 O3 pellet.
  • the fresh surface is indicated by the solid line
  • the pilot tested surface is indicated by the dashed line.
  • Figure 2 shows the XRD patterns of the pellet before exposure and the upper surface of the reactor exposed Er 2 Os pellet. The pattern for the pellet before exposure is indicated by the solid line, the pattern for the exposed surface is indicated by the dashed line.
  • Figure 3 shows the XRD patterns of the pellet before exposure and the upper side of a reactor exposed Yb 2 Os pellet.
  • the pattern for the pellet before exposure is indicated by the solid line, the pattern for the exposed surface is indicated by the dashed line.
  • numeric values by means of ranges of figures comprises all values and fractions in these ranges, as well as the cited end points.
  • the terms “ranging from ... to ...” or “range from ... to ...” or “up to” as used when referring to a range for a measurable value, such as a parameter, an amount, a time period, and the like, is intended to include the limits associated to the range that is disclosed.
  • the present application generally provides methods and systems for the recovery of one or more volatile platinum group metals, present in a gas phase.
  • a solid solution as used herein generally refers to a homogeneous mixture of two different kinds of atoms or components in solid state and having a single crystal structure. Stated differently, and in line with the IUPAC definition, a solid solution is a solid in which its components are compatible and form a unique phase, such as a single crystal structure.
  • one component i.e. the element that is recovered, in particular Rh, or Rh and/or Pt, fits into and is distributed in the crystal lattice of a second component, in particular one or more oxides of a rare earth metal selected from the group consisting of Er 2 C>3, Sm 2 O3, and Yb 2 C>3.
  • the recovery or capture of a particular element by a recovery system according to the present application can be determined by scanning electron microscope (SEM) with energy dispersive X-ray fluorescence analysis (EDS) and/or by X-Ray diffraction (XRD) analysis, particularly by comparing the data obtained by these techniques before and after contacting the recovery system according to the present application with a gas comprising one or more volatile platinum group metals, in particular Pt and/or Rh.
  • EDS analysis will demonstrate the presence or absence of the metal of interest to be recovered in the recovery system.
  • XRD shows the effect of the incorporation of the metal of interest to be recovered in the recovery system, particularly in the crystal structure of the recovery agent, as further described herein, or as a formed compound or solid solution with the recovery agent.
  • a catalytic system comprising a catalyst comprising one or more platinum-group metals, and a recovery system, positioned downstream of the catalyst, for recovering volatile platinum-group metals that are released from the catalyst during operation.
  • the system according to the present disclosure comprises a catalyst comprising at least Pt and/or Rh and a recovery system downstream of the catalyst.
  • the system is characterised in that the recovery system comprises one or more oxides of a rare earth metal selected from the group consisting of Er 2 Os, Sm 2 C>3, and Yb 2 C>3, particularly in crystalline form.
  • the system is characterised in that the recovery system comprises oxide of a rare earth metal selected from Er 2 Os and Sm 2 C>3.
  • the system is characterized in that the recovery system comprises Sm 2 C>3.
  • a catalytic system it is meant herein, a system comprising a catalyst, with which the chemical activation barrier for reacting two chemicals is lowered, such that the reaction can be performed using less energy.
  • the catalyst as considered herein typically comprises at least Pt and/or Rh, but may contain other metals or metal containing compounds as well, including but not limited to other platinum group metals, such as Pd, Ir, Ru, Os; and/or other metals, such as Au, Ar, Cu, Fe, Ni, Co and the like; and/or compounds or alloys containing one or more of said metals.
  • platinum group metals such as Pd, Ir, Ru, Os
  • other metals such as Au, Ar, Cu, Fe, Ni, Co and the like
  • compounds or alloys containing one or more of said metals such as Au, Ar, Cu, Fe, Ni, Co and the like.
  • the catalyst system comprises Rh and volatile Rh is generated.
  • recovery system it is meant a system in which the volatile catalyst metal, in particular the volatile platinum group metal, more in particular volatile Pt and/or Rh, present in the gas phase and generated during a catalytic reaction in the catalytic system is recovered, as defined above.
  • the recovery system according to the present disclosure particularly recovers at least Rh, or at least Pt and/or Rh through retaining or capturing at least Rh, or at least Pt and/or Rh with the rare earth metal oxide as further defined herein, in particular by incorporating Rh, or Pt and/or Rh into the crystal lattice of the rare earth metal oxide.
  • E ⁇ Ch, Sm 2 O3 and Yb2C>3 retain volatile Pt and Rh, thereby allowing to recover the volatile Pt and Rh that would otherwise be lost in the gas phase. Thereby, both emissions in the air and loss of precious and expensive metals are mitigated. It was further observed that in contrast to the above-mentioned oxides, CeC>2 did not retain volatile Pt and Rh. Hence, Er 2 C>3, Sm 2 O3 and Yb 2 O3 have the ability to form a compound or a solid solution with Rh and Pt.
  • the formed compound or solid solution is stable: upon shut-down of the reactor and exposure to ambient temperature and ambient air, the compound or solid solution does not hydrate and do not become brittle and dusty.
  • the catalytic system is an ammonia oxidation reactor or burner, whereby nitric oxide therefore is generated.
  • the catalytic system is a reactor for reacting ammonia, oxygen and methane, thereby generating hydrogen cyanide.
  • the catalytic system is a system for the catalytic conversion of ammonia into nitric oxide, for the generation of nitric acid, or the catalytic system is a system for the catalytic conversion of ammonia, oxygen and methane, for the generation of hydrogen cyanide.
  • the present invention thus considers an ammonia oxidation reactor or burner comprising a catalytic system according to the present disclosure, or a reactor for the manufacture of hydrogen cyanide by the catalytic reaction of ammonia, methane and oxygen, comprising a catalytic system according to the present disclosure.
  • the present disclosure addresses the recovery of at least volatile Pt and/or Rh from a gas phase.
  • Two very well know industrial production processes are the production of nitric acid according to the Ostwald process and the production of hydrogen cyanide according to the Andrussow process. Both these processes involve the presence of a Pt and/or Rh containing catalyst.
  • the first step involves the reaction of gaseous ammonia with gaseous oxygen provided for example through air onto a Pt/Rh catalyst, thereby producing gaseous nitric oxide.
  • the catalyst comprising Pt and Rh usually is part of a so-called ammonia oxidation burner in which the Pt/Rh catalyst is located at the top surface of a so-called burner basket and supported by Raschig rings or catalyst particles for example for N2O gas conversion and abatement located inside the burner basket.
  • the ammonia and oxygen react at suitable temperatures and pressures as known to the skilled person to form gaseous nitric oxide, which passes through the burner basket and is further subject to the subsequent steps of the nitric acid production process.
  • EP3727667A1 and W02004/005187A1 describe potential designs for the ammonia oxidation burner basket.
  • catalytic system of the disclosure is particularly helpful for performing the Ostwald and Andrussow processes generating nitric acid and hydrogen cyanide respectively, particularly for recovering at least volatile Pt and/or Rh generated during the Ostwald and Andrussow processes.
  • the recovery system comprises Sm 2 O3.
  • the inventor has found that the catchment of volatile Pt and Rh is even more increased when the rare earth oxide in the recovery system is Sm 2 O3. Said otherwise, there are benefits in terms of volatile Pt and Rh recovery associated with a recovery system comprising Sm 2 O3.
  • the recovery system comprises Sm 2 C>3 and the catalyst system comprises a Rh-containing catalyst.
  • Rh recovery is also then improved, that is more selective, with respect to Pt catchment. Said otherwise, the combination of a Rh containing catalyst and Sm 2 C>3 in the recovery system of the system of the disclosure results in improved Rh recovery.
  • the system of the present disclosure may further comprise a second recovery system, particularly for the capture of volatile catalyst metals, such as volatile platinum group metals.
  • the second recovery system comprises metals or compounds suitable for the capture of volatile catalyst metals, such as volatile platinum group metals, in the gas phase.
  • metals or compounds include but are not limited to Pd, Au, Ag, and mixtures of alloys thereof.
  • the second recovery system comprises Pd or Ag for the capture of volatile Pt.
  • the second recovery system may be positioned between the catalyst and the recovery system according to the present disclosure and comprising Er 2 C>3, Sri a, and/or Yb2C>3, such as comprising Er 2 C>3 and/or Sm 2 O3, and/or may be positioned downstream of the recovery system according to the present disclosure comprising Er 2 O3, Sm 2 C>3, and/or Yb 2 C>3, such as comprising Er 2 Os and/or Sm 2 C>3.
  • the recovery system comprising Er 2 Os, Sm 2 C>3 and/or Yb 2 Os, such as comprising Er 2 Os and/or Sm 2 C>3, according to the present disclosure may further comprise other metals, compounds or alloys suitable for the capture of volatile catalyst metals, such as volatile platinum group metals.
  • volatile catalyst metals such as volatile platinum group metals.
  • Such metals or compounds include but are not limited to Pd, Au, Ag, and mixtures of alloys thereof.
  • the presence of a second recovery system or the presence of further metals or compounds suitable for the capture of volatile platinum group metals allows to maximize the recovery of volatile catalyst metals from the gas phase or to obtain the recovery of volatile catalyst metals from the gas phase in the most cost-effective way, particularly to maximize the recovery of volatile platinum group metals from the gas phase.
  • the Pt-containing and/or Rh- containing catalyst is in the form of a catalytic gauze
  • the recovery system has the shape of a honeycomb, a tablet, a pellet, a sponge, a net or a gauze.
  • Honeycomb monoliths and nets offer a large geometric surface area and also very low pressure drop, which is of benefit for the gas to contact either the Pt and/or Rh catalytic metal or the rare earth oxide recovery metal.
  • Gauzes also offer the advantage of low pressure drop, in addition to high mass transfer which favours both the catalytic conversion onto the Pt and/or Rh metal and the interaction of the volatile Pt and/or Rh with the rare earth oxide, resulting in the retaining of the volatile Pt and/or Rh by the rare earth oxide.
  • pellets or tablets can be adjusted and optimised such as to offer a maximised geometric surface area. Further, pellets and tablets are easy to produce, and large volumes can be easily installed and subsequently used in large sized reactors such as circular ammonia oxidation burners. Sponges, foams and ceramics also offer a large geometric surface area and also exhibit a very low pressure drop, which is of benefit for the gas to contact either the Pt and/or Rh catalytic metal or the rare earth oxide recovery metal. Moreover, sponges, foams and ceramics present the advantage of increased mass transfer with respect to other shapes. When the recovery system has the shape of a honeycomb, a tablet, a pellet or a net, the recovery system can be made by coating the rare earth oxide onto a support having the preferred shape. Coating of the rare earth oxide onto a support with a defined shape is particularly straightforward to perform and to achieve.
  • the shape can be produced from a composite of the rare earth oxide or from the solid pure rare earth oxide.
  • Examples of production from a composite of the rare earth oxide or the pure rare earth oxide are extrusion, moulding, pressing or granulating the composite of the rare earth oxide or from the solid pure rare earth oxide.
  • the use of one or more oxides of a rare earth metal oxide selected from the group consisting of Er 2 C>3, Sm 2 C>3 and/or Yb 2 C>3, such as Er 2 Os and/or Sm 2 C>3, particularly in crystalline form, for recovering one or more volatile platinum group metals, in particular for recovering at least volatile Pt and/or Rh from a gas phase, or for recovering at least volatile Rh, and optionally volatile Pt, is disclosed.
  • the inventor has surprisingly found that, contrary to cerium oxide, CeO 2 and as shown in the examples, Er 2 Os, Sm 2 C>3 and Yb 2 Os retain volatile Pt and Rh, thereby recovering the volatile Pt and Rh that would otherwise be lost in the gas phase. Thereby, both emissions in the air and loss of precious and expensive metals are mitigated.
  • the present disclosure thus also provides for the use of one or more oxides of a rare earth metal oxide selected from the group consisting of Er 2 Os, Sm 2 Os and/or Yb 2 Os, such as Er 2 Os and/or Sm 2 C>3, in crystalline form, for incorporating one or more volatile platinum group metals, in particular at least volatile Pt and/or Rh or at least volatile Rh, into the crystal lattice of the one or more oxides of a rare earth metal oxide selected from the group consisting of Er 2 Os, Sm 2 Os and/or Yb 2 Os, such as Er 2 Os and/or Sm 2 C>3, in crystalline form.
  • a rare earth metal oxide selected from the group consisting of Er 2 Os, Sm 2 Os and/or Yb 2 Os, such as Er 2 Os and/or Sm 2 C>3, in crystalline form.
  • Er 2 Os, Sm 2 Os and Yb 2 Os have the ability to form a compound or a solid solution with Rh and Pt. Further, the formed compound or solid solution is stable: upon shut-down of the reactor and exposure to ambient temperature and ambient air, the compound or solid solution does not hydrate and do not become brittle and dusty.
  • volatile Pt and/or Rh is generated during the catalytic oxidation of ammonia into nitric oxide, particularly using a Pt and Rh containing catalyst, or volatile Pt and/or Rh is generated from the catalytic reaction of ammonia with oxygen and methane into hydrogen cyanide.
  • the present disclosure addresses the recovery of volatile Pt and Rh, even more in particular the recovery of volatile Rh.
  • Two very well know industrial production processes are the production of nitric acid according to the Ostwald process and the production of hydrogen cyanide according to the Andrussow process, as described elsewhere herein.
  • E ⁇ Ch, Sm 2 O3 and/or Yb2O3 such as the use of E ⁇ Ch and/or Sm 2 O3 for recovering volatile Pt and/or Rh, is particularly helpful for performing the Ostwald and Andrussow processes generating nitric acid and hydrogen cyanide, respectively.
  • the oxide of the rare earth metal is S1TI2O3.
  • the inventor has found that the catchment of volatile Pt and Rh is even more increased when the rare earth oxide in the recovery system is Sm 2 O3. Said otherwise, there are benefits in terms of volatile Pt and Rh recovery associated with a recovery system comprising Sm 2 O3.
  • volatile Rh is recovered.
  • the oxide of the rare earth metal is Sm 2 O3 and volatile Rh is recovered.
  • the oxide of a rare earth metal is comprised in a recovery system that has the shape of a honeycomb, a tablet, a pellet, a sponge, a net or a gauze, as described elsewhere herein.
  • a method for oxidising ammonia into nitric oxide or for reacting ammonia with oxygen and methane, thereby generating hydrogen cyanide comprises the steps of a) catalytically oxidising ammonia into nitric oxide or catalytically reacting ammonia with oxygen and methane thereby generating hydrogen cyanide, whereby volatile Pt and/or Rh is generated, or stated differently whereby a gas phase is obtained comprising at least volatile Pt and/or Rh; and b) recovering the volatile Pt and/or Rh generated in step a) on a recovery system comprising one or more oxide of a rare earth metal selected from the group consisting of E ⁇ Ch, Sm 2 O3 and Yb2C>3, particular in crystalline form, in particular by contacting the gas phase comprising at least volatile Pt and/or Rh, at suitable temperatures and pressures as known to the skilled person, with a recovery system comprising one or more oxide of a rare earth metal selected from the group consist
  • the present disclosure provides a method for oxidising ammonia into nitric oxide or for reacting ammonia with oxygen and methane, thereby generating hydrogen cyanide, is disclosed.
  • the method comprises the steps of a) catalytically oxidising ammonia into nitric oxide or catalytically reacting ammonia with oxygen and methane thereby generating hydrogen cyanide, whereby volatile Pt and/or Rh is generated, or stated differently whereby a gas phase is obtained comprising at least volatile Pt and/or Rh, particularly a gas phase comprising at least volatile Rh; b) contacting the volatile Pt and/or Rh generated in step a) with a recovery system comprising one or more oxide of a rare earth metal selected from the group consisting of Er2C>3, So a and Yb 2 C>3, such as Er 2 O 2 and/or Sm 2 C>3, particular in crystalline form, in particular by contacting the gas phase comprising at least volatile Pt and/or Rh, at suitable temperatures and pressures as known
  • Pt may be captured with a recovery system comprising one or more oxide of a rare earth metal selected from the group consisting of Er 2 0a, Sm 2 C>3 and Yb 2 Oa, wherein it stays in an oxidised state, or it may easily lose oxygen and react with Pd in a metallic state to form a solid solution.
  • a recovery system comprising one or more oxide of a rare earth metal selected from the group consisting of Er 2 0a, Sm 2 C>3 and Yb 2 Oa, wherein it stays in an oxidised state, or it may easily lose oxygen and react with Pd in a metallic state to form a solid solution.
  • RhO 2 vapour is much more stable than PtO 2 and can be captured with a recovery system comprising one or more oxide of a rare earth metal selected from the group consisting of Er 2 0a, Sm 2 C>3 and Yb 2 O 2 to form a respective compound.
  • the inventor has surprisingly found that, contrary to cerium oxide, CeO2 and as shown in the examples, Er 2 0a, Sm 2 C>3 and Yb 2 O 2 retain volatile Pt and Rh, thereby recovering the volatile Pt and Rh that would otherwise be lost in the gas phase. Thereby, both the emissions in the air and the loss of precious and expensive metals are mitigated.
  • Er 2 0a, Sm 2 C>3 and Yb 2 O 2 have the ability to form a compound or a solid solution with Rh and Pt. Further, the formed compound or solid solution is stable: upon shut-down of the reactor and exposure to ambient temperature and ambient air, the compound or solid solution does not hydrate and do not become brittle and dusty.
  • the recovery of Pt and/or Rh from the compound or solid solution generated in step c) is performed by any method as known to the skilled person.
  • Some known methods include chelation, ion exchange, chemical precipitation, solvent extraction leaching, adsorption, and biosorption methods.
  • step a) is performed with a catalytic gauze
  • step b) is performed with a recovery system that has the shape of a honeycomb, a tablet, a pellet, a sponge, a net or a gauze, wherein these shapes are described elsewhere herein.
  • step b) is performed with a recovery system comprising Sm 2 O3.
  • the inventor has found that the catchment of volatile Pt and Rh is even more increased when the rare earth metal oxide in the recovery step is Sm 2 O3. Said otherwise, there are benefits in terms of volatile Pt and Rh recovery associated with a recovery step comprising Sm 2 C>3.
  • step a) is performed with a Rh-containing catalytic system and step b) is performed with a recovery system comprising Sm 2 C>3.
  • Rh recovery is also then improved, that is more selective, with respect to Pt catchment. Said otherwise, the combination of a Rh catalyst and Sm 2 C>3 in the recovery step of the method of the disclosure results in improved Rh recovery.
  • step b) of the methods of the present disclosure further comprises recovering volatile catalyst metal, such as volatile platinum group metals generated in step a) with a second recovery system.
  • the second recovery system comprises Pd for the capture of at least volatile Pt.
  • step a) comprises catalytically oxidising ammonia into nitric oxide at a temperature ranging from 700 to 950 °C, particularly at a pressure ranging between 2 bar and 20 bar.
  • nitric oxide can then be converted through further oxidation into the NOx gases NO 2 and N 2 C>4 which when absorbed in water provide the very important chemical that is nitric acid.
  • a method for revamping a palladium-containing recovery gauze for recovering volatile platinum and/or rhodium is disclosed.
  • the method comprises the step of replacing at least part of the palladium comprised in the recovery gauze for one or more oxide of a rare earth metal selected from the group consisting of Er 2 C>3, Sm 2 O3 and Yb2C>3, such as Er 2 C>3 and/or Sm 2 O3.
  • a rare earth metal selected from the group consisting of Er 2 C>3, Sm 2 O3 and Yb2C>3, such as Er 2 C>3 and/or Sm 2 O3.
  • Example 1 use of Sm 2 O3 for Pt and Rh catchment
  • Samarium oxide (So a) was pressed into a pellet of 10mm diameter and 5 mm thickness.
  • the tablets were sintered at 1100 °C for 12 hours.
  • a pellet was installed downstream of seven Pt/Rh gauzes in an ammonia combustion reactor.
  • the reactor was operated at 5 bara pressure and the combusted gas contacting the Sm 2 O3 tablet was at 900 °C, containing circa 10% NO, 15% H 2 O, 6% O 2 and nitrogen. In addition to these gases, the gas contained traces of volatile platinum and rhodium.
  • the reactor was operated for 23 days. After this period of exposure, the pellet was recovered from the pilot reactor for analysis. Prior to installation in the reactor, the lower side of the pellet had been marked, so that after exposure the upper side of the pellet that had most direct contact with the incoming flow of combusted gas (upper surface) could be identified.
  • X-Ray diffraction (XRD) analysis of the upper side of the tablet was carried out to identify changes to the Sm 2 C>3 structure.
  • the diffraction patterns of the pellet before exposure to the reactor and of the upper side of the reactor exposed Sm 2 C>3 pellet are shown in Figure 1.
  • the monoclinic structure is consistent with the sample annealed at 1100 °C, but on cooling below 900 °C, the cooling rate was not sufficiently slow to allow the transition to the body centred cubic structure.
  • reactor exposure the “pilot tested” sample
  • An Erbium oxide (Er 2 Os) pellet was produced in the same manner as the corresponding Sm 2 C>3 pellet produced in Example 1. After sintering and marking of the lower surface, the pellet was installed in the reactor in the same manner as the corresponding Sm 2 C>3 pellet produced in Example 1. The exposure of the Er 2 Os pellet in the reactor was carried out in parallel with the Sm 2 C>3 pellet produced in Example 1. Average surface compositions of Er, Rh and Pt after exposition in the reactor was determined in the SEM equipped with an EDS analyser. The results are shown in Table 2. Only Rh was recovered on the Er 2 Os pellet.
  • X-Ray diffraction (XRD) analysis of the pellet before exposure and of the upper side of the reactor exposed pellet was carried out to identify changes to the Er 2 Os structure.
  • the diffraction patterns of the pellet before reactor exposure (solid line) and the upper side (dashed line) of the plant exposed Er 2 Os pellet are shown in Figure 2.
  • Ytterbium oxide (Yb 2 O3) oxide pellet was prepared in the same manner as the corresponding Sm 2 O3 pellet produced in Example 1 . After sintering and marking of the lower surface, the pellet was installed in the reactor in the same manner as the corresponding Sm 2 O3 pellet produced in Example 1 . The exposure of the Yb 2 Os pellet in the reactor was carried out in parallel with the Sm 2 C>3 pellet produced in Example 1. Average surface compositions of Yb, Rh and Pt after exposition in the reactor was determined in the SEM equipped with an EDS analyser. The results are shown in Table 3.
  • X-Ray diffraction (XRD) analysis of the upper side of the pellet was carried out to identify changes to the Yb 2 Os structure.
  • the diffraction patterns of the lower and upper sides of the reactor exposed Yb 2 Os pellet are shown in Figure 3.
  • the Yb 2 C>3 pellet before exposure to the reactor had a body centered cubic structure. After reactor exposure, the Yb 2 C>3 pellet retained the body centered cubic structure but the lattice had contracted, as indicated by a shift in lines to a higher two theta angle.
  • CeO 2 cerium oxide is found in the form of cerium dioxide, CeO 2 , with a fluorite structure.
  • the lattice parameter is reported to be 5.4112 A (Powder Diffraction File number 01-089-8436, Maintained by the International Centre for Diffraction Data (ICDD).
  • Yara produces a catalyst for nitrous oxide abatement that is designed to be installed directly below the combustion gauzes in the ammonia burner of a nitric acid plant.
  • the catalyst contains 97 mole% of CeO 2 , with the remainder being an oxide active phase.
  • the lattice parameter of the CeO 2 in a freshly produced catalyst gave a value of 5.4090 A, which is within 0.04% of the reference material. After operation in a plant, no significant change to the CeO 2 lattice parameter was observed and no additional diffraction lines were observed in a corresponding XRD pattern. We concluded that CeO 2 does not retain Rh or Pt.

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Abstract

La présente divulgation divulgue un système catalytique comprenant un catalyseur contenant du Pt et/ou contenant du Rh, ainsi qu'un système de récupération en aval du catalyseur, le système de récupération comprenant un ou plusieurs oxydes d'un métal des terres rares choisi dans le groupe constitué par Er2O3, Sm2O3 et Yb2O3. La présente divulgation concerne en outre l'utilisation d'un ou de plusieurs oxydes d'un métal des terres rares choisi dans le groupe constitué par Er2O3, Sm2O3 et Yb2O3 pour récupérer le Pt et/ou le Rh volatils, ainsi qu'un procédé de récupération de Pt et/ou Rh volatils.
PCT/EP2024/068982 2023-07-06 2024-07-05 Système de récupération de pt et/ou de rh volatils et procédé associé Pending WO2025008502A1 (fr)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB668935A (en) 1948-10-02 1952-03-26 Degussa Process for the recovery of platinum volatilising during a catalytic process
GB1343637A (en) 1970-03-05 1974-01-16 Engelhard Min & Chem Recovery of platinum group metals
EP0063450A1 (fr) 1981-04-10 1982-10-27 Johnson Matthey Public Limited Company Récupération des métaux précieux
US4774069A (en) 1985-06-28 1988-09-27 Johnson Matthey Public Limited Company Process for the manufacture of nitric oxide
WO2004005187A1 (fr) 2002-07-03 2004-01-15 Yara International Asa Procede et dispositif de maintien de gazes catalytiques dans un dans un bruleur d'oxydation par l'ammoniac
WO2004096703A2 (fr) * 2003-04-29 2004-11-11 Johnson Matthey Plc Procede d'oxydation de l'ammoniac
US20130149207A1 (en) 2011-12-12 2013-06-13 Johnson Matthey Public Limited Company Substrate monolith comprising scr catalyst
EP3727667A1 (fr) 2017-12-19 2020-10-28 Yara International ASA Systèmes de support de catalyseur pour des brûleurs d'oxydation d'ammoniac
WO2023050324A1 (fr) * 2021-09-30 2023-04-06 Basf Corporation Matériaux de capture de métaux du groupe du platine

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB668935A (en) 1948-10-02 1952-03-26 Degussa Process for the recovery of platinum volatilising during a catalytic process
GB1343637A (en) 1970-03-05 1974-01-16 Engelhard Min & Chem Recovery of platinum group metals
EP0063450A1 (fr) 1981-04-10 1982-10-27 Johnson Matthey Public Limited Company Récupération des métaux précieux
US4774069A (en) 1985-06-28 1988-09-27 Johnson Matthey Public Limited Company Process for the manufacture of nitric oxide
WO2004005187A1 (fr) 2002-07-03 2004-01-15 Yara International Asa Procede et dispositif de maintien de gazes catalytiques dans un dans un bruleur d'oxydation par l'ammoniac
WO2004096703A2 (fr) * 2003-04-29 2004-11-11 Johnson Matthey Plc Procede d'oxydation de l'ammoniac
US20130149207A1 (en) 2011-12-12 2013-06-13 Johnson Matthey Public Limited Company Substrate monolith comprising scr catalyst
EP3727667A1 (fr) 2017-12-19 2020-10-28 Yara International ASA Systèmes de support de catalyseur pour des brûleurs d'oxydation d'ammoniac
WO2023050324A1 (fr) * 2021-09-30 2023-04-06 Basf Corporation Matériaux de capture de métaux du groupe du platine

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Title
DUARTE R B ET AL: "Understanding the effect of Sm2O3and CeO2promoters on the structure and activity of Rh/Al2O3catalysts in methane steam reforming", JOURNAL OF CATALYSIS, vol. 296, 24 October 2012 (2012-10-24), pages 86 - 98, XP028956193, ISSN: 0021-9517, DOI: 10.1016/J.JCAT.2012.09.007 *
LEROY EYRING: "Handbook on the Physics and Chemistry of Rare Earths", vol. 3, 1979, LEROY EYRING, article "The binary rare earth oxides", pages: 341
UNDERWOOD RICHARD P ET AL: "CO HYDROGENATION OVER RHODIUM SUPPORTED ON SiO2, La203, Nd203 and Sm203", 14 February 1986 (1986-02-14), XP093207121, Retrieved from the Internet <URL:https://doi.org/10.1016/S0166-9834(00)81336-6> *

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