EP1173277A1 - Procedes et catalyseurs de methanation d'oxydes de carbone - Google Patents

Procedes et catalyseurs de methanation d'oxydes de carbone

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Publication number
EP1173277A1
EP1173277A1 EP99948603A EP99948603A EP1173277A1 EP 1173277 A1 EP1173277 A1 EP 1173277A1 EP 99948603 A EP99948603 A EP 99948603A EP 99948603 A EP99948603 A EP 99948603A EP 1173277 A1 EP1173277 A1 EP 1173277A1
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EP
European Patent Office
Prior art keywords
oxide
catalyst
nickel
rare earth
oxides
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EP99948603A
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German (de)
English (en)
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EP1173277A4 (fr
Inventor
Kim Elizabeth Henville
Graeme John Millar
Jose Antonio Alarco
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University of Queensland UQ
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University of Queensland UQ
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Publication of EP1173277A1 publication Critical patent/EP1173277A1/fr
Publication of EP1173277A4 publication Critical patent/EP1173277A4/fr
Withdrawn legal-status Critical Current

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    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • This invention relates to processes and catalysts for the conversion of oxides of carbon to methane and/or other hydrocarbons, and to processes for making such catalysts, and to precursors of such catalysts.
  • Carbon dioxide is the major greenhouse gas arising from anthropogenic sources. It is released mainly by burning fossil fuels (oil, coal, natural gas) in electric power generation, blast furnaces and automotive vehicles. Only about half of these carbon dioxide emissions are absorbed by oceans, forests or otherwise. The remainder stays in the atmosphere, acting as a greenhouse gas. It is estimated that if the current rate of CO 2 emissions continues, the average global temperature will rise by 1.5 to 4.5°C over the next 40 to 50 years, without taking into account the warming caused by increases in other greenhouse gas concentrations.
  • renewable energy sources also represent a secure and stable source of energy for centuries. Renewable energy sources are those which do not run out or are replaced as quickly as they are used. Energy from the sun, wind, tides, geothermal and hydro electric sources are examples of renewable resources. Energy from waste, landfill gases, bagasse, plantation timber or other biological sources, if managed properly, can also be considered renewable. In contrast, fossil fuels form so slowly in comparison to our energy use that we are essentially mining finite, nonrenewable resources and could exhaust quality supplies within the foreseeable future.
  • biomass fuels are "environmentally friendly". In particular, they produce virtually no sulfur emissions, thus helping to mitigate acid rain; they "recycle” atmospheric carbon, hence minimising global warming impact; and they generate low NOx levels and create few particulates.
  • Gasification of biomass is an important technology in the primary conversion of biomass for electricity production. This latter process typically involves the partial oxidation of biomass to give a mixture of gases and organic vapours. After the gasification products are cleaned, the gas mix (termed “synfuel”) can be introduced to a boiler or the combustion section of a turbine system. Synfuel is usually composed of a mixture of carbon monoxide, carbon dioxide, methane and hydrogen in addition to small concentrations of tars, alkali metals and sulfur compounds. For use of the synfuel in a gas turbine-based generation facility it is desirable to reduce explosion risk by minimising the concentration of hydrogen present in the synfuel. Consequently, an attractive route would be to react the oxides of carbon with the hydrogen present in the synfuel to produce methane. This approach can be represented by the following general reaction equations: CO + 3H 2 ⁇ CH 4 + H 2 O (1)
  • methane is in itself advantageous as it is an excellent fuel for power generation.
  • Reactions of the type represented in equations (1) to (3) are collectively known as "methanation" reactions.
  • Another renewable energy source of particular interest is solar energy.
  • solar energy Application of solar energy hinges on development of means to convert this diffuse and intermittent source of energy to forms amenable for transport and storage.
  • Thermochemical energy conversion offers the potential to store and to transport solar energy at ambient temperature with the release of energy in the form of heat at temperatures up to 1000K and with overall efficiencies of about 90%.
  • Chemical energy can be accumulated by utilizing heat of reaction in a reversible reaction. If a reaction proceeds endothermically then the same heat of reaction can be recovered from the reverse reaction.
  • the reaction of most interest in this respect is the carbon dioxide reforming reaction:
  • Figure 1 represents a closed loop configuration
  • Figure 2 shows an open loop cycle. Briefly, in the closed loop configuration, concentrated solar energy is used to supply the process heat for the CO 2 reforming reaction. Subsequently, the CO and H 2 reaction products can be stored and/or transported to a separate site where the reverse methanation reaction is performed to release the stored solar energy. The methanation products are then recycled to the reformer reactor to complete the closed loop.
  • an open loop cycle can be employed, as illustrated in Figure 2.
  • the product syngas is combusted to produce heat and power (typically in a gas turbine system integrated to an IGCC power plant).
  • catalytic methanation is a central technology for power generation options involving the use of renewable energy sources such as biomass or solar energy. Consequently, there is a need to develop catalysts for the methanation process which exhibit excellent activity, stability, resistance to coking and economic viability. Desirably, such catalysts will be capable of catalysing the methanation reactions at atmospheric pressure or higher and relatively low temperatures while exhibiting sufficiently high activity, stability and resistance to coking to be useful in large scale operations.
  • Catalytic methanation is carried out in ammonia synthesis plants as a means of reducing the concentration of carbon oxides before the reactant gas enters the ammonia synthesis catalyst bed.
  • Another application for methanation catalysts is in the production of substitute natural gas (SNG) from sources such as oil and coal.
  • SNG substitute natural gas
  • the main difference in these applications is the composition of the gas streams involved.
  • a typical gaseous feedstock entering the methanation reactor in an ammonia plant has the approximate composition 0.4% CO, 0.1% CO 2 , 73.7% H 2 , 24.4% N 2 , 0.4% CH 4 and 1% H 2 O.
  • the gas stream derived from gasification of oil or gas may consist of 0- 30% CO 2 , 10-60% CO, 25-75% H 2 and 0-20% CH 4 (on a dry basis).
  • Catalysts for the above processes must exhibit the desirable properties of good activity at low temperatures, structural stability at high temperatures, resistance to deactivation by coking (relevant to the situation where the gas stream is derived from a gasification reaction) and resistance to poisoning by sulfur compounds.
  • the most common catalysts in use are based upon nickel supported on alumina prepared by a co-precipitation method. The use of additives to this catalyst system is also known.
  • European Patent No 0 044 1 17 discloses the benefits of inclusion of magnesium in the nickel/alumina structure and also indicates the incorporation of lanthanum is beneficial in dispersing the nickel component.
  • the amount of lanthanum added is, however, significantly less than the amount of nickel present.
  • catalysts including nickel (or cobalt) and a noble metal, together with a rare earth oxide has been described previously by Inui and co-workers (T. Inui et al.. J. Chem. Soc. Faraday Trans. /, 75, 787 (1979), l.E. C. Res... 28, 427 ( 1989), l.E. C. Res. , 28, 1285 ( 1989), Stud. Surf Sci. Catal , 17, 181 ( 1983)).
  • the catalysts described all include a minor amount, compared to the amount of nickel, of the rare earth oxide, and further include a noble metal such as rhodium or ruthenium.
  • Methanation catalysts which are not based on nickel or cobalt, but instead include a noble metal such as ruthenium, rhodium or platinum, are also known.
  • catalysts which have been described in the prior art all suffer from one or more disadvantages.
  • catalysts containing noble metals suffer from the disadvantage that they are expensive and the noble metal may be in short supply.
  • some catalysts of the prior art do not exhibit particularly high activity in the conversion of carbon oxides and hydrogen to methane and/or other hydrocarbons, and many catalysts of the prior art tend to deactivate after a relatively short time owing to "coking" : the formation of deposits of carbon on the surface of the catalyst.
  • nickel-containing catalyst which has sufficiently high activity to be of practical use in catalysis of the methanation reaction, and which is relatively resistant to coking during the reaction leading to loss of activity. It is an object of the present invention to provide a nickel-containing catalyst for use in the catalytic conversion of carbon dioxide and/or carbon monoxide to methane and/or other hydrocarbons which ameliorates at least one of the disadvantages of the nickel containing methanation catalysts which were known prior to the present invention.
  • a catalyst which includes nickel and at least an equal amount by weight of one or more refractory oxides selected from the group consisting of rare earth oxides and rare earth-containing perovskites is effective in a process for the conversion of carbon dioxide and/or carbon monoxide to methane and/or other hydrocarbons and has an enhanced lifetime compared to nickel containing catalysts which have hitherto been used in such a process.
  • the invention provides a process for producing a hydrocarbon product which includes the step of contacting a gaseous mixture including hydrogen and one or more oxides of carbon with a methanation catalyst at a temperature and pressure, wherein the catalyst includes:
  • a catalyst capable of at least partially reducing, or converting, an oxide of carbon to a hydrocarbon product is, as will be readily apparent to a person of ordinary skill in the relevant art, a reference to a catalyst which is capable of catalysing the reaction of an oxide of carbon with hydrogen to produce a hydrocarbon product under some conditions of temperature and pressure. That is, in the presence of such a catalyst an oxide of carbon is reduced to a hydrocarbon product under appropriate conditions of temperature and pressure at a greater rate than would occur in the absence of the catalyst under the same conditions.
  • the invention also relates to precursors to a catalyst for use in a process of the first embodiment.
  • precursors include one or more refractory oxides selected from the group consisting of rare earth oxides and rare earth-containing perovskites and an amount of nickel oxide such that, after reduction of the nickel oxide in the precursor to nickel metal so as to provide a methanation catalyst, the amount of refractory oxide or oxides in the methanation catalyst is at least equal to the weight of nickel in the methanation catalyst.
  • the catalyst precursor will include about 35% by weight, based on the total weight of the catalyst precursor, of nickel oxide, with the balance made up of the refractory oxide or oxides.
  • a catalyst precursor which includes one or more refractory oxides selected from the group consisting of rare earth oxides and rare earth-containing perovskites and an amount of nickel oxide sufficient for a catalyst obtainable by reducing the nickel oxide in the catalyst precursor to be capable of at least partially reducing an oxide of carbon to a hydrocarbon product, wherein the amount of refractory oxide or oxides in the methanation catalyst is at least equal to the weight of nickel in the methanation catalyst.
  • the nickel oxide at least in part, forms a solid solution with the refractory oxide or oxides.
  • a catalyst precursor which includes one or more refractory oxides selected from the group consisting of rare earth oxides and rare earth-containing perovskites and an amount of nickel oxide sufficient for a catalyst obtainable by reducing the nickel oxide in the catalyst precursor to be capable of at least partially reducing an oxide of carbon to a hydrocarbon product, wherein at least part of the nickel oxide forms a solid solution with the refractory oxide or oxides and wherein the amount of refractory oxide or oxides in the methanation catalyst is at least equal to the weight of nickel in the methanation catalyst.
  • a process for preparing a catalyst precursor including the steps of
  • the catalysts for use in the process of the first embodiment of the invention may also include one or more additives.
  • a methanation catalyst which includes
  • noble metals selected from the group consisting of Pt, Ir, Rh, Ru, Os, Pd and Re;
  • oxides selected from the group consisting of TiO 2 . MoO 3 , WO 3 , ZrO 2 , V 2 O s , Nb 2 O 5 , Sc 2 O 5 and Ta 2 O 5 ;
  • the invention further provides a catalyst precursor containing nickel oxide and capable of being converted to a methanation catalyst of the fourth embodiment by contacting the catalyst precursor with a reducing gas at an elevated temperature and for a time sufficient to reduce at least part of the nickel oxide to nickel metal.
  • the invention provides a catalyst precursor produced by the process of the third embodiment.
  • the invention also provides in a sixth embodiment, a methanation catalyst which is obtainable from a catalyst precursor of the second or fifth embodiments by contacting the catalyst precursor with a reducing gas at an elevated temperature and for a time sufficient to reduce at least part of the nickel oxide to nickel metal.
  • a process for preparing a catalyst precursor including the steps of
  • the invention provides a catalyst precursor produced by the process of the seventh embodiment.
  • the invention also provides in a ninth embodiment a methanation catalyst which is obtainable from a catalyst precursor of the eighth embodiment by contacting the catalyst precursor with a reducing gas at an elevated temperature and for a time sufficient to reduce at least part of the nickel oxide to nickel metal.
  • the invention also relates to precursors to a catalyst for use in a process of the first embodiment.
  • a catalyst precursor which includes one or more refractory oxides selected from the group consisting of rare earth oxides and rare earth-containing perovskites, said precursor including nickel or nickel cations sufficient for a catalyst obtainable by reducing the catalyst precursor to be capable of at least partially reducing an oxide of carbon to a hydrocarbon product.
  • the nickel oxide at least in part, forms a solid solution with the refractory oxide or oxides.
  • a catalyst precursor which includes one or more refractory oxides selected from the group consisting of rare earth oxides and rare earth-containing perovskites, said precursor 5 including nickel or nickel cations sufficient for a catalyst obtainable by reducing the nickel oxide in the catalyst precursor to be capable of at least partially reducing an oxide of carbon to a hydrocarbon product, wherein at least part of the nickel oxide forms a solid solution with the refractory oxide or oxides.
  • the invention provides a catalyst precursor produced by the process of the eleventh embodiment.
  • the invention also provides in a thirteenth embodiment, a methanation catalyst which is obtainable from a catalyst precursor of the twelfth embodiments by contacting the catalyst precursor with a reducing gas at an elevated temperature and for a time sufficient to reduce at least part of the nickel oxide to nickel metal.
  • a process for preparing a catalyst precursor including the steps of (i) impregnating a support material selected from the group consisting of rare earth oxides and rare earth-containing perovskites with a solution of a nickel compound so that the weight of nickel impregnated in the support material is not greater than the support material;
  • the invention provides a catalyst precursor produced by the process of the fourteenth embodiment.
  • the invention also provides in a sixteenth embodiment a methanation catalyst which is obtainable from a catalyst precursor of the fifteenth embodiment by contacting the catalyst precursor with a reducing gas at an elevated temperature and for a time sufficient to at least partically reduce the catalyst precursor and form the methanation catalyst.
  • Fig. 1 is a diagrammatic representation of a Closed Loop thermochemical heat pipe.
  • Fig. 2 is a diagrammatic representation of an Open Loop thermochemical heat pipe.
  • Fig. 3 is a graph showing the relationship between the concentration of methane, carbon monoxide, carbon dioxide and hydrogen in the presence of a 30 wt % Ni on yttrium oxide catalyst as a function of reaction temperature.
  • Figs. 4(a) to 4(c) are XRD traces for nickel oxide/yttrium oxide catalyst precursors including 0, 5 and 30 wt% nickel, respectively.
  • Fig. 5 includes XRD traces for nickel oxide/silica catalyst precursors, not in accordance with the present invention, having three different weight loadings of nickel.
  • Fig. 6 is a graph showing the relationship between the concentration of methane, carbon monoxide, carbon dioxide and hydrogen in the presence of a 30 wt% Ni on terbium oxide catalyst as a function of reaction temperature.
  • Fig. 7 is a graph showing the relationship between the concentration of methane, carbon monoxide, carbon dioxide and hydrogen in the presence of a 30 wt% Ni on terbium oxide catalyst as a function of reaction time.
  • Figs. 8(a) to 8(c) are XRD traces for nickel oxide/terbium oxide catalyst precursors including 0, 5 and 30 wt% nickel, respectively.
  • Fig. 9 is a graph showing the relationship between the concentration of methane, carbon monoxide, carbon dioxide and hydrogen in the presence of a 30 wt% Ni on praseodymium oxide catalyst as a function of reaction temperature.
  • Figs. 10(a) to 10(c) are XRD traces for nickel oxide/praseodymium oxide catalyst precursors including 0, 5 and 30 wt% nickel, respectively.
  • Fig. 1 1 is a graph showing the relationship between the concentration of methane, carbon monoxide, carbon dioxide and hydrogen in the presence of a 30 wt% Ni on samarium oxide catalyst as a function of reaction temperature.
  • Fig. 12 is a graph showing the relationship between the concentration of methane, carbon monoxide, carbon dioxide and hydrogen in the presence of a 30 wt% Ni on samarium oxide catalyst as a function of reaction time.
  • Fig. 13 is a graph showing the relationship between the concentration of methane, carbon monoxide, carbon dioxide and hydrogen in the presence of a 5 wt% Ni on samarium oxide catalyst as a function of reaction temperature.
  • Fig. 14 is a graph showing the relationship between the concentration of methane, carbon monoxide, carbon dioxide and hydrogen in the presence of a 30 wt% Ni on high area yttrium oxide catalyst as a function of reaction temperature.
  • Fig. 15(a) to 15(c) are XRD traces for nickel oxide/high area yttrium oxide catalyst precursors including 0, 5 and 30 wt% nickel, respectively.
  • Fig. 16 is a graph showing the relationship between the concentration of methane, carbon monoxide, carbon dioxide and hydrogen in the presence of a 30 wt% Ni on high surface area yttrium oxide catalyst as a function of reaction time.
  • Fig. 17 is a graph showing the relationship between the concentration of methane, carbon monoxide, carbon dioxide and hydrogen in the presence of a 5 wt% Ni on lanthanum strontium gallium magnesium oxide catalyst as a function of reaction temperature.
  • Fig. 18 is a graph showing the relationship between the concentration of methane, carbon monoxide, carbon dioxide and hydrogen in the presence of a prior art 10 wt% Ni on silica catalyst as a function of reaction temperature.
  • Fig. 19 is a graph showing the relationship between the concentration of methane, carbon monoxide, carbon dioxide and hydrogen in the presence of a prior art 30 wt% Ni on silica catalyst as a function of reaction temperature.
  • Fig. 20 is a graph showing the relationship between the concentration of methane, carbon monoxide, carbon dioxide and hydrogen in the presence of a prior art 4 wt% Ru on silica catalyst as a function of reaction temperature.
  • Fig. 21 is a graph showing the relationship between the concentration of methane, carbon monoxide, carbon dioxide and hydrogen in the presence of a prior art 30 wt% Ni on magnesium oxide catalyst as a function of reaction temperature.
  • Fig. 22 is a graph showing the relationship between the concentration of methane, carbon monoxide, carbon dioxide and hydrogen in the presence of a prior art 20 wt% Ni on magnesium-aluminium oxide catalyst as a function of reaction temperature.
  • Fig. 23 is a graph showing the relationship between the concentration of methane, carbon monoxide, carbon dioxide and hydrogen in the presence of a prior art 20 wt% Ni and 25 wt% MoO 3 on magnesium-aluminium oxide catalyst as a function of reaction temperature.
  • Fig. 24 is a graph showing the relationship between the concentration of methane, carbon monoxide, carbon dioxide and hydrogen in the presence of a prior art coprecipitated nickel-lanthanum-aluminium oxide catalyst as a function of reaction temperature.
  • the hydrocarbon product is methane, or methane and one or more other hydrocarbons, such as ethane, propane and butane.
  • the amount of nickel in the methanation catalyst for use in the process of the first embodiment, and in a methanation catalyst obtainable by reducing the nickel oxide in a catalyst precursor of the second embodiment to nickel metal, and in the catalyst of the fourth embodiment is in the range of from about 1% to 50% by weight, more typically from about 5% to about 40% by weight, or from about 6% to about 40% by weight, or from about 7% to about 40% by weight, or from about 8% to about 40% by weight, or from about 9% to about 40% by weight, still more typically from about 10% to about 40% by weight, even more typically from about 10% to about 30% by weight, based on the total weight of the catalyst.
  • the expression "rare earth” means an element selected from yttrium, uranium and the elements of atomic number 57 to 71 inclusive.
  • an oxide of a rare earth metal included in the catalyst for use in the process of the first embodiment, and in a catalyst precursor of the second embodiment and a catalyst of the fourth embodiment is selected from the group consisting of terbium oxide, erbium oxide, praseodymium oxide, samarium oxide, yttrium oxide, ytterbium oxide, lanthanum oxide, dysprosium oxide, cerium oxide, neodymium oxide, europium oxide, holmium oxide, lutetium oxide, thulium oxide and gadolinium oxide. More typically, the rare earth oxide is selected from the group consisting of terbium oxide, praseodymium oxide, samarium oxide and yttrium oxide.
  • a rare earth-containing perovskite for inclusion in the catalyst for use in the process of the first embodiment, and in a catalyst precursor of the second embodiment and a catalyst of the fourth embodiment is typically a substance of the general formula
  • B is a metal from Group II of the Periodic Table of the Elements
  • C and D are independently selected from metals of Groups IIA, IIIA, IVB, VB, VIB, VIIB and VIII of the Periodic Table of the Elements;
  • B is an alkaline earth metal selected from Mg, Ca, Sr and Ba.
  • C and D are independently selected from Fe, Co, Ni, Ru, R , Pt, Mg, Ca, Ba,
  • rare earth-containing perovskites examples include perovskites of the formula
  • rare earth-containing perovskites include MMn 0 5 Y 0 5 O 3 and MYO 3 where Y is Fe, Co or Ni, MTiO 3 , MCrO 3 , MRuO 3 , MGaO 3 , MRhO 3 , M 1 -x Sr MnO 3 , M,.
  • M is Fe, Co or Ni
  • lanthanum-containing perovskites such as lanthanum-strontium-gallium-magnesium oxides, for example La 0 Sr 0 1 Ga 0 8 Mgo 2 ⁇ 3-7 or La ⁇ S Sro 2 Gao 8 Mgo ⁇ 5 O 3-z , LaMn 0 5 Ni 0 5 O 3 , LaCoO 3 , LaNiO 3 , LaFeO 3 , LaMn 0 ⁇ Ee 0 5 O 3 , LaTi 0 iFe 0 ⁇ O 3 , LaRu 0 ⁇ Fe 0 5 O 3 , LaRu 0 5 Ni 0 5 O 3 , LaFe,.
  • LaMn 0 5 Ni 0 5 O 3 LaCoO 3 , LaNiO 3 , LaFeO 3 , LaMn 0 ⁇ Ee 0 5 O 3 , LaTi 0 iFe 0 ⁇ O 3 , LaRu 0 ⁇ Fe 0 5 O 3
  • the rare earth-containing perovskite is typically an oxygen ion conductor at an elevated temperature.
  • perovskites examples include CeBaO 3 , Tb 0 I ⁇ o ⁇ BaO 3 , Ce radical «,Er 0
  • the amounts included are typically in the range of:
  • the catalyst components may be dispersed on the surface of a support material of high: surface area, such as alumina, silica, zirconia, thoria. clay, or derivatives of clay etc, or mixtures thereof such as silica-alumina, which may provide greater structural stability to the catalyst. Formation of a supported catalyst of this kind may readily be achieved by impregnation of soluble precursors of nickel, rare earth etc on the support of choice, followed by drying and calcination. Alternatively, the catalyst components may be mixed with a material such as alumina, zirconia, clay or derivatives of clay to provide mechanical strength or increase the dispersion of the catalyst components.
  • the process of the first embodiment may be carried out under conditions generally known for catalytic methanation processes.
  • the process may be carried out at atmospheric pressure, or at elevated or reduced pressure.
  • the pressure of the gaseous mixture of hydrogen and one or more oxides of carbon is from atmospheric to about 10 MPa, more typically from atmospheric to about 1 MPa, still more typically from l OOkPa to 500kPa.
  • it is carried out at atmospheric pressure.
  • the heating temperature in step (ii) is typically carried out in an oxygen containing atmosphere. More typically the atmosphere is air or oxygen gas.
  • the process of the first embodiment may be carried out at ambient temperature or at elevated temperature, but is typically carried out at an elevated temperature, such as from about 150°C to about 1000°C, more typically from 250°C to 550°C.
  • the contact time of the catalyst with the gaseous mixture is sufficient for at least a part of the oxide(s) of carbon to be converted to methane or other hydrocarbon(s).
  • the gaseous mixture is passed as a flowing stream over or through a bed of the catalyst so as to provide a gas hourly space velocity (GHSV) of from about lOOh " to about 250000 h " , more typically about lOOOh "1 to about lOOOOOh “1 .
  • GHSV gas hourly space velocity
  • the gaseous mixture may contain gases other than hydrogen and one or more oxides of carbon.
  • gases other than hydrogen may contain substantially inert gases such as nitrogen, helium and/or argon, and/or one or more hydrocarbons such as methane, ethane, etc, and/or small amounts of oxygen.
  • substantially inert gases such as nitrogen, helium and/or argon, and/or one or more hydrocarbons such as methane, ethane, etc, and/or small amounts of oxygen.
  • the proportion of hydrogen relative to the amount of oxide(s) of carbon will be sufficient to provide at least a stoichiometric amount as calculated according to equations (1) to (3) above.
  • gas compositions which include less than a stoichiometric amount of hydrogen may be used.
  • the molar ratio of H 2 /(CO + CO 2 ) ⁇ nay be in the range of from 1 :20 to 20: 1, and is more usually in the range of from 1:2 to 10:1, still more usually in the range of from 1:1 to 5:1, such as from 1:1 to 4.5:1 or 1:1 to 4.3:1 or 1:1 to 4.1:lor 1:1 to 4.0:lor 1:1 to 3.9:lor 1:1 to 3.8:lor 1:1 to 3.7:lor 1:1 to 3.6:lor 1:1 to 3.5:lor 1:1 to 3.4:lor 1:1 to 3.3:lor 1:1 to 3.2:lor 1:1 to 3.1:lor 1:1 to3:lor 1:1 to2.9:lor 1:1 to2.8:lor 1:1 to 2.7:lor 1:1 to 2.6:lor 1:1 to2.5:lor 5 1:1 to2.4:lor 1:1 to2.3:lor 1:1 to 2.2:1 or 1:1 to 2.1:1 or 1:1 to 2.0:1.
  • the catalysts for use in the process of the first embodiment may be prepared using techniques which are generally known in the art.
  • the catalysts for use in the process of the first embodiment may be prepared using techniques which are generally known in the art.
  • the catalysts for use in the process of the first embodiment may be prepared using techniques which are generally known in the art.
  • the catalysts for use in the process of the first embodiment may be prepared using techniques which are generally known in the art.
  • the catalysts for use in the process of the first embodiment may be prepared using techniques which are generally known in the art.
  • the catalysts for use in the process of the first embodiment may be prepared using techniques which are generally known in the art.
  • the catalysts may be prepared using techniques which are generally known in the art.
  • the support material lo may be impregnated with an aqueous solution of a water-soluble nickel salt, such as nickel nitrate, which is capable of being converted in situ to nickel oxide, for example by the application of heat, or oxidising in an oxidising atmosphere.
  • a nickel salt which is soluble in a non-aqueous solvent can be used, in which case it will be appreciated that the impregnating will be carried out using a non-aqueous solvent.
  • the impregnated support material is typically calcined in air at a temperature in the range selected from the group consisting of from 250°C to 1500°C,
  • 250°C to 1400°C 250°C to 1300°C, 250°C to 1200°C, 250°C to 1100°C, 250°C to
  • the preparation method for the catalyst precursor of a methanation catalyst for use in the process of the first embodiment is however not restricted to wet impregnation techniques, and alternative synthesis routes known to those skilled in the art can also be employed, examples of which include co-precipitation, solid state reaction, vapor phase
  • the methanation catalyst includes a rare earth oxide which has been prepared so as to possess an enhanced surface area, compared to commercially available rare earth oxides.
  • a process for preparing such a rare earth oxide typically includes the steps of dissolving a commercially available rare earth oxide 3o in an excess of an acid, usually nitric acid, followed by the addition of sufficient of a precipitating anion to substantially completely precipitate the rare earth as an insoluble salt at an appropriate pH.
  • the resulting insoluble salt is then dried under controlled conditions, such as by spray drying, to minimise compaction of the powder.
  • the insoluble salt ⁇ s next fired to decompose it to the corresponding oxide.
  • the decomposition pathway of a sample of the insoluble salt is first monitored by thermal analysis such as differential thermal analysis (DTA), thermogravimetric analysis (TGA) and/or differential scanning calorimetry (DSC). From the observed decomposition profile, a firing procedure is determined which minimises formation of undesirable intermediates.
  • thermal analysis such as differential thermal analysis (DTA), thermogravimetric analysis (TGA) and/or differential scanning calorimetry (DSC).
  • the precipitant is suitably a dicarboxylic acid or one or more derivatives thereof.
  • the derivatives may include salts, esters, anhydrides, amides and the like.
  • Ammonium oxalate is one suitable derivative. Dimethyl oxalate or diethyl oxalate are also suitable.
  • a suitable dicarboxylic acid is oxalic acid.
  • Another suitable solution of precipitant is an aqueous solution of tartaric acid.
  • a solution of ammonium carbonate as well as ammonia can also be used as a solution of precipitant.
  • aqueous solutions of sodium carbonate or potassium carbonate are also suitable as precipitants.
  • An example of such a solution of coprecipitating ions is an aqueous solution of hydroxide and carbonate ions such as a solution of an alkylammonium hydroxide and carbonate ions together with oxalic acid or derivatives of oxalic acid.
  • an alkaline solution of an oxalate is used as a solution of coprecipitating ions, such as an aqueous solution of sodium hydroxide or potassium hydroxide and oxalic acid or derivatives of oxalic acid.
  • Another suitable precipitant is an aqueous solution of ammonium polyacrylate, which when mixed with the solution of rare earth metal ions results in rare earth metal polyacrylate precipitates.
  • the solution of precipitant may typically include a pH adjusting agent in order that the pH can be adjusted to maximise precipitation.
  • a pH adjusting agent in order that the pH can be adjusted to maximise precipitation.
  • An aqueous solution of triethanolamine and oxalic acid in a molar ratio of about 1 to about 3. or about 1 to about 2.5 or about 1.8 to about 2.2 is one such example.
  • an aqueous solution of oxalic acid and urea is envisaged as a solution of precipitating ions with urea acting as a solvent to control pH.
  • organic solvent miscible with water can be used to make the solution of precipitating ions.
  • organic solvents such as methanol, ethanol, propanol, butanol, pentanol, hexanol or acetone can be used to make a solution of precipitating ions such as an oxalic acid solution.
  • the catalyst precursor includes more than one rare earth oxide
  • a mixture of rare earth oxides may be obtained by a procedure substantially as described above, by co-precipitating insoluble salts of the rare earth elements.
  • the catalyst for the process of the first embodiment of the invention is produced by reduction of a catalyst precursor, including but not limited to a catalyst precursor of the second embodiments, or a catalyst precursor produced according to the process of the third or seventh embodiments or a precursor of the methanation catalyst of the fourth embodiment.
  • This reduction may be achieved either concomitantly with or immediately prior to the methanation reaction as a result of contacting the catalyst precursor with the reactant gaseous mixture of hydrogen and carbon oxide(s), or more typically, the reduction may be carried out by pre-reducing the catalyst at a temperature of 300°C or greater with a gas stream consisting at least predominantly of hydrogen or any other readily available gaseous reductant such as carbon monoxide, methane and/or other hydrocarbons, or mixtures of the foregoing.
  • the catalyst precursor temperature is typically raised to a temperature in excess of 500°C until the precursor is substantially completely reduced.
  • the precursor may be reduced at a temperature as low as 300°C, although a temperature in excess of 500°C is more typical.
  • Other catalyst precursor compositions may require reduction at still higher temperatures, such as up to about 900°C.
  • the reduction procedure employed should preferably be at a temperature which will facilitate reduction of a fraction of the nickel ions to nickel metal.
  • the identification of a solid solution in a catalyst precursor of the latter of the second embodiments may be made by inspection of an X-ray powder diffraction profile for the precursor.
  • the nature of the solid solution depends to a large extent on the pre- treatment that the catalyst precursor receives prior to reduction.
  • Parameters which influence the formation of a solid solution are calcination temperature (T c ), calcination time (t c ) and nickel loading.
  • the calcination temperature that is, the temperature used in step (iii) of the process of the third embodiment is usually in the range 250 to 800°C, and is more typically in the range of 350 to 600°C.
  • Another feature of the catalysts of the present invention is the general observation that the catalyst surface area increases as the nickel loading increases.
  • Table 1 illustrates the surface areas as calculated by the standard BET method for several of the catalysts revealed in this disclosure, and for comparison purposes, surface areas of silica and nickel oxide/silica composites obtained by similar methods are also shown.
  • a 30 weight % nickel/yttrium oxide catalyst was made by impregnating yttrium oxide (Pi-Kem, UK) with an appropriate amount of aqueous solution of nickel nitrate, followed by drying the sample at 1 10°C, and calcination in air at 500°C for 2 hours.
  • the methanation activity was evaluated by contacting the catalyst with a gaseous feedstock comprising of 20% methane, 17% carbon dioxide, 30% carbon monoxide and 32% hydrogen at a flow rate sufficient to give a gas hourly space velocity (GHSV) of 10,000 If
  • the catalyst was allowed to equilibrate at specific temperatures in the range 250 to
  • Figures 4(a) to 4(c) shows X-ray diffraction (XRD) patterns for yttrium oxide, 5 wt% nickel oxide-yttrium oxide and the 30 wt% nickel oxide-yttrium oxide precursor of this Example, respectively.
  • XRD X-ray diffraction
  • the 30 wt% nickel oxide - yttrium oxide catalyst precursor exhibits extremely broad lines due to the yttrium oxide component which is recognized by those skilled in the art to be representative of an amorphous or nanocrystalline oxide material (see Fig. 4(c)).
  • the presence of very wide reflections attributable to nickel oxide which again not only indicates the presence of amorphous or nanocrystalline nickel oxide but also the weak intensity of these latter features can be interpreted as meaning that there may exist a fraction of the nickel species in a solid solution with the yttrium oxide.
  • FIG. 5 illustrates XRD profiles recorded for a series of calcined nickel/silica catalysts.
  • the silica support is characterized by an amorphous "lump" at low values of 2-theta, whereas sharp, intense peaks are apparent for nickel oxide at 37, 43 and
  • Example 2 63 degrees 2-theta. As the loading of nickel becomes higher, the XRD peaks become narrower, thus indicating that the nickel particles were becoming larger and more crystalline in character. Electron microscopy observations are consistent with this interpretation. Importantly, the silica support of the nickel/silica catalyst does not have the ability to form a solid solution with nickel. Consequently, the nickel particles are neither as well dispersed as in those catalysts described in this invention or as small and amorphous or nanocrystalline in structure.
  • Example 2
  • a 30 weight% nickel/terbium oxide catalyst was made by impregnating terbium oxide (Pi-Kem, UK) with an appropriate amount of aqueous solution of nickel nitrate, followed by drying the sample at 110°C, and calcination in air at 500°C for 2 hours.
  • the methanation activity was evaluated in the same manner as outlined in Example 1.
  • a plot of the concentration of each species in the gas phase as a function of reaction temperature is displayed in Figure 6. Significantly, the theoretical maximum for methane formation was obtained using this catalyst at low temperature (400°C or less) conditions and moreover, no coking of the catalyst bed was detected.
  • the activity of the 30wt% nickel/terbium oxide catalyst was evaluated as a function of reaction time to determine not only the stability but also the extent of catalyst coking.
  • a gaseous feed consisting of 19% methane, 17% carbon dioxide, 30% carbon monoxide and 34% hydrogen was passed over a catalyst sample at a flow rate such as to give a space velocity of 10,000 h "1 and at a temperature of 400°C.
  • a plot of the concentration of each species in the gas phase as a function of reaction time is displayed in Figure 7. Not only was the catalytic activity stable but no coke deposition was noted on the catalyst bed following reaction.
  • Figures 8(a) to 8(c) display XRD patterns for terbium oxide, 5 wt% nickel oxide/terbium oxide and the 30 wt% nickel oxide/terbium oxide catalyst precusor of this Example, respectively.
  • the features for the terbium oxide component diminish in intensity as the nickel loading is increased, again indicative of a more amorphous or nanocrystalline material.
  • the reflections characteristic for nickel oxide are extremely weak in intensity in Fig. 8(c).
  • the nickel component may at least in part be forming a solid solution with the rare earth oxide or at least the rare earth oxide has the ability to disperse the nickel component to a greater extent, than that for a silica support.
  • a 30 weight% nickel/praseodymium oxide catalyst was made by impregnating praseodymium oxide (Pi-Kem, UK) with an appropriate amount of aqueous solution of nickel nitrate, followed by drying the sample at 110°C, and calcination in air at 500°C for
  • Example 1 A plot of the concentration of each species in the gas phase as a function of reaction temperature is displayed in Figure 9. The theoretical maximum for methane formation was obtained using this catalyst at low temperature (400°C or less) conditions and no coking of the catalyst bed was detected.
  • Figures 6(a) to 6(c) display XRD patterns for praseodymium oxide, 5 wt% nickel oxide/praseodymium oxide and the 30 wt% nickel oxide/praseodymium oxide catalyst precusor of this Example, respectively.
  • the nickel oxide/praseodymium oxide system behaves similarly to the nickel oxide/yttrium oxide and nickel oxide/terbium oxide systems.
  • the XRD traces in Figures 10(a) to 10(c) clearly illustrate that the reflections assigned to praseodymium oxide become very broad and weak in intensity as the nickel loading increases.
  • Example 4 A 30 weight% nickel/samarium oxide catalyst was made by impregnating samarium oxide (Pi-Kem, UK) with an appropriate amount of aqueous solution of nickel nitrate, followed by drying the sample at 110°C, and calcination in air at 500°C for 2 hours. The methanation activity was evaluated in the same manner as outlined in Example 1. A plot of the concentration of each species in the gas phase as a function of reaction temperature is displayed in Figure 11. The theoretical maximum for methane formation was obtained using this catalyst at low temperature (400°C or less) conditions and no coking of the catalyst bed was detected.
  • the activity of the 30 wt% nickel/samarium oxide catalyst was evaluated as a function of reaction time to determine not only the stability but also the extent of catalyst coking.
  • a gaseous feed consisting of 19% methane, 17% carbon dioxide, 30% carbon monoxide and 34% hydrogen was passed over a catalyst sample at a flow rate such as to give a space velocity of 10,000 h "1 and at a temperature of 400°C.
  • a plot of the concentration of each species in the gas phase as a function of reaction time is displayed in Figure 12. Not only was the catalytic activity stable but no coke deposition was noted on the catalyst bed following reaction.
  • Example 5 A 5 weight% nickel/samarium oxide catalyst was made by impregnating samarium oxide (Pi-Kem, UK) with an appropriate amount of aqueous solution of nickel nitrate, followed by drying the sample at 110°C, and calcination in air at 500°C for 2 hours. The methanation activity was evaluated in the same manner as outlined in Example 1. A plot of the concentration of each species in the gas phase as a function of reaction temperature is displayed in Figure 13. This catalyst containing only 5% nickel was very active for the methanation reaction.
  • Example 6 Commercial yttrium oxide (Pi-Kem, UK) was reprocessed by a novel material synthesis procedure to produce a material of enhanced surface area (20 m 2 g " '). Yttrium oxide was initially dissolved in 10 % excess nitric acid then sufficient oxalate ions were added to completely precipitate yttrium as yttrium oxalate at appropriate pH to optimise precipitation. The product was dried under controlled conditions by spray drying, to minimise compaction of powder. Following thermal analysis of the decomposition pathway, a firing procedure was determined which minimises formation of undesirable intermediates.
  • a 30 weight% nickel/yttrium oxide catalyst was made by impregnating the high area yttrium oxide obtained in this way with an appropriate amount of aqueous solution of nickel nitrate, followed by drying the sample at 110°C, and calcination in air at 500°C for 2 hours.
  • the methanation activity was evaluated in the same manner as outlined in Example 1.
  • a plot of the concentration of each species in the gas phase as a function of reaction temperature is displayed in Figure 14.
  • the low temperature methanation activity temperature of 350°C or less
  • the theoretical maximum for methane formation was obtained using this catalyst at low temperature (400°C or less) conditions and no coking of the catalyst bed was detected.
  • Figures 15(a) to 15(c) shows X-ray diffraction (XRD) patterns for the high area yttrium oxide, 5 wt% nickel oxide -high area yttrium oxide and the 30 wt% nickel oxide- high area yttrium oxide precursor of this Example, respectively.
  • XRD X-ray diffraction
  • the activity of the 30 wt% nickel/high area yttrium oxide catalyst was evaluated as a function of reaction time to determine not only the stability but also the extent of catalyst coking.
  • a gaseous feed consisting of 19% methane, 17% carbon dioxide, 30% carbon monoxide and 34% hydrogen was passed over a catalyst sample at a flow rate such as to give a space velocity of 10,000 h "1 and at a temperature of 400°C.
  • a plot of the concentration of each species in the gas phase as a function of reaction time is displayed in Figure 16. Not only was the catalytic activity stable but no coke deposition was noted on the catalyst bed following reaction.
  • a portion of the oxygen ion conductor lanthanum-strontium-gallium-magnesium oxide (La 0 9 Sr 0 1 Gao .8 Mgo .2 ⁇ 3-x ) was impregnated with an amount of aqueous solution of nickel nitrate sufficient to give a loading of 5 wt% Ni on the oxide, followed by drying the sample at 110°C, and calcination in air at 500°C for 2 hours.
  • the methanation activity was evaluated in the same manner as outlined in Example 1.
  • a plot of the concentration of each species in the gas phase as a function of reaction temperature is displayed in Figure 17. This catalyst displayed excellent activity for methanation at relatively high temperatures (450°C or higher).
  • Comparative Example 1 A 10 wt% nickel/silica catalyst was made by impregnating silica (Cab-O-Sil M5, 200 nrg "1 , Cabot Corporation, Boston, Mass. U.S.A.) with an appropriate amount of aqueous solution of nickel nitrate, followed by drying the sample at 110°C, and calcination in air at 500°C for 2 hours. The methanation activity was evaluated in the same manner as outlined in Example 1. A plot of the concentration of each species in the gas phase as a function of reaction temperature is displayed in Figure 18. Visual inspection of the catalyst bed following reaction showed the presence of large black coke particles which indicated the presence of substantial concentrations of coke which would lead to poisoning of the catalyst during industrial use.
  • silica Cab-O-Sil M5, 200 nrg "1 , Cabot Corporation, Boston, Mass. U.S.A.
  • a 30 wt% nickel/silica catalyst was made by impregnating silica (Cab-O-Sil M5, 200 m 2 g " ') with an appropriate amount of aqueous solution of nickel nitrate, followed by drying the sample at 1 10°C, and calcination in air at 500°C for 2 hours.
  • the methanation activity was evaluated in the same manner as outlined in Example 1.
  • a plot of the concentration of each species in the gas phase as a function of reaction temperature is displayed in Figure 19. Visual inspection of the catalyst bed following reaction showed the presence of large black coke particles which indicated the presence of substantial concentrations of coke which would lead to poisoning of the catalyst during industrial use.
  • a 4 wt% ruthenium/silica catalyst was made by impregnating silica (Cab-O-Sil 5 M5, 200 nrg "1 ) with an appropriate amount of aqueous solution of ruthenium chloride, followed by drying the sample at 1 10°C, and calcination in air at 600°C for 2 hours.
  • the methanation activity was evaluated in the same manner as outlined in Example 1.
  • a plot of the concentration of each species in the gas phase as a function of reaction temperature is displayed in Figure 20. This catalyst did not display sufficient methanation activity o under the applied conditions, in contrast to the catalysts of the present invention.
  • Comparative Example 4 A 30 wt% nickel/magnesium oxide catalyst was made by impregnating commercially available magnesium oxide with an appropriate amount of aqueous solution of nickel nitrate, followed by drying the sample at 1 10°C, and calcination in air at 500°C 5 for 2 hours. The methanation activity was evaluated in the same manner as outlined in Example 1. A plot of the concentration of each species in the gas phase as a function of reaction temperature is displayed in Figure 21. This catalyst did not display sufficient methanation activity under the applied conditions, in contrast to the catalyst of the present invention. o Comparative Example 5
  • a highly heat resistant solid catalyst for methanation of hydrogen and carbon monoxide as described in US patent No. 4,331,544 was made as follows. 10.033 grams of aluminium nitrate and 5.029 grams magnesium nitrate were dissolved in 25 mL of purified water. Approximately 25 mL of ammonium hydroxide solution was added to the aforementioned solution while under vigorous stirring in order to form a precipitate. The precipitate was filtered and washed thoroughly with distilled water and then dried at 1 10°C. Finally, the material was calcined in a muffle furnace in air at 500°C for 4 hours.
  • a catalyst for evaluation was made by impregnating the magnesium oxide-aluminium oxide carrier with an appropriate amount of nickel nitrate such that the loading of nickel was 20 wt%.
  • the catalyst was pretreated by drying at 110°C and calcination at 500°C for 2 hours.
  • the methanation activity was evaluated in the same manner as outlined in Example 1.
  • a plot of the concentration of each species in the gas phase as a function of reaction temperature is displayed in Figure 22. Although, the activity was reasonable, albeit not as good as that recorded for the catalysts described in this invention, coking of the catalyst bed was again noted thus this catalyst is not suitable for industrial application.
  • Comparative Example 6 A catalyst similar to that described in comparative example 5 was synthesized, the only difference being that a mixture of nickel nitrate and ammonium molybdate was impregnated on the magnesium oxide-aluminium oxide support such that the weight ratio of NiO-MoO 3 carrier was 20:25:55.
  • the methanation activity was evaluated in the same manner as outlined in Example 1. A plot of the concentration of each species in the gas phase as a function of reaction temperature is displayed in Figure 23. Significantly, this catalyst did not display sufficient methanation activity under the applied conditions in contrast to the catalyst of the present invention.
  • Comparative Example 7 A nickel containing catalyst claimed to exhibit high thermal stability and excellent resistance to carbon deposition according to EP 0 044 117 was made as follows. An aqueous solution containing 2.518 grams of lanthanum nitrate, 11.809 grams of aluminium nitrate and 22.903 grams of nickel nitrate was prepared, and to this was added under vigorous stirring a solution of sodium bicarbonate. The resultant pale green suspension was filtered and washed thoroughly with distilled water. The precipitate was dried at 1 10°C and then calcined in a muffle furnace at 450°C for 1 hour.
  • the formed nickel-lanthanum-aluminium oxide catalyst had a Ni/Al atomic ratio of 2.5 and a lanthanum content of 0.05, expressed as the atomic fraction La/(Ni+Al+La).
  • the methanation activity was evaluated in the same manner as outlined in Example 1. A plot of the concentration of each species in the gas phase as a function of reaction temperature is displayed in Figure 24. Significantly, this catalyst did not display sufficient methanation activity under the applied conditions in contrast to the catalyst of the present invention.

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Abstract

L'invention a trait à des catalyseurs utiles pour transformer des oxydes de carbone en méthane et/ou en d'autres hydrocarbures, et à des précurseurs de ces catalyseurs. Les précurseurs de catalyseurs contiennent un ou plusieurs oxydes réfractaires sélectionnés dans le groupe constitué par des oxydes de terre rare et des pérovskites contenant une terre rare. Le précurseur contient du nickel ou des cations de nickel en quantité suffisante pour que le catalyseur, qui peut être obtenu par réduction, soit capable de réduire au moins partiellement un oxyde de carbone en un produit d'hydrocarbure. Des procédés de préparation de ces catalyseurs et de ces précurseurs de catalyseurs sont également décrits, ainsi que des procédés de transformation d'oxydes de carbone en méthane et/ou en d'autres hydrocarbures.
EP99948603A 1998-09-21 1999-09-21 Procedes et catalyseurs de methanation d'oxydes de carbone Withdrawn EP1173277A4 (fr)

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AUPP6071A AUPP607198A0 (en) 1998-09-21 1998-09-21 Process and catalysts for the methanation of oxides of carbon
PCT/AU1999/000804 WO2000016901A1 (fr) 1998-09-21 1999-09-21 Procedes et catalyseurs de methanation d'oxydes de carbone

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