EP3697530A1 - Method for converting a gas comprising carbon monoxide into methane by means of a catalytic material containing praseodymium and nickel on alumina - Google Patents

Method for converting a gas comprising carbon monoxide into methane by means of a catalytic material containing praseodymium and nickel on alumina

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Publication number
EP3697530A1
EP3697530A1 EP18800710.8A EP18800710A EP3697530A1 EP 3697530 A1 EP3697530 A1 EP 3697530A1 EP 18800710 A EP18800710 A EP 18800710A EP 3697530 A1 EP3697530 A1 EP 3697530A1
Authority
EP
European Patent Office
Prior art keywords
gas
catalytic material
weight
alumina
catalytic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP18800710.8A
Other languages
German (de)
French (fr)
Inventor
Arnaud LAHOUGUE
Emmanuel Rohart
Gaëlle GICQUEL
Sandra CAPELA
Yilmaz KARA
Stéphane FORTIN
Myriam DE SAINT JEAN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Enercat
Engie SA
Original Assignee
Enercat
Engie SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Enercat, Engie SA filed Critical Enercat
Publication of EP3697530A1 publication Critical patent/EP3697530A1/en
Pending legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
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    • 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
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    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
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    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
    • B01J8/003—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor in a downward flow
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
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    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1818—Feeding of the fluidising gas
    • B01J8/1827—Feeding of the fluidising gas the fluidising gas being a reactant
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C—CHEMISTRY; METALLURGY
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    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
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    • C07C1/0405—Apparatus
    • C07C1/042—Temperature controlling devices; Heat exchangers
    • C—CHEMISTRY; METALLURGY
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    • C07C1/0425—Catalysts; their physical properties
    • C07C1/043—Catalysts; their physical properties characterised by the composition
    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
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    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00115—Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
    • B01J2208/00132—Tubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Definitions

  • the present invention relates to a method and a device for converting a gas into methane.
  • Catalytic materials containing nickel oxide and alumina are known.
  • the contents of nickel oxides are generally high and vary depending on the process between 20 and 50%. These materials have catalytic performances considered sometimes insufficient, especially when the process temperatures are low, for example below 300 ° C.
  • thermodynamics are known.
  • Wan Azelee Wan Abu Bakar et al. "Nickel Oxide Based Supported Catalysts for the In-Situ Reactions of Methanation and Desulfurization in the Removal of Sour Gases from Simulated Natural Gas", Catalysis Letters, Kluwer Academy Publishers, NE , Volume 128, No. 1 -2, November 1, 2008,
  • WO 00/16901 is also known.
  • the present invention aims to remedy all or part of these disadvantages.
  • the present invention relates to a process for converting a gas to methane (CH 4 ), which comprises:
  • a catalytic material comprising praseodymium oxide (PreOn) combined with nickel oxide (NiO) and with alumina (Al2O3), the respective proportions of which are relative to to the total mass of these three compounds:
  • NiO 1 to 20% by weight
  • the inventors have discovered that the choice of the combination of the compounds of the catalytic material and the impact of the respective content of each of the elements ( ⁇ - ⁇ , NiO and Al2O3), ensures a good compromise performance / durability / cost, when this catalytic material is used for the conversion of carbon monoxide (CO) optionally in the presence of carbon dioxide (CO2), in a gaseous mixture rich in hydrogen (H2), in a gaseous mixture rich in methane (CH 4 ), for example containing mainly CO, CO2 and H2, and offering a high performance in conversion of the assembly consisting of CO and CO2 at low temperatures, for example at temperatures below 300 ° C.
  • This catalytic material has a wider temperature range of use than previously known catalytic materials. Due to the laws of thermodynamics, the conversion of CO and CO2 is increased, especially at low temperatures.
  • the catalytic material itself may be in pulverulent form, whose average grain size varies from 1 to 100 ⁇ , or in the form of beads of 100 ⁇ at 1 mm, preferably between 200 and 800 ⁇ and even more preferentially, between 200 and 600 ⁇ .
  • the catalyst formed by activation of the catalytic material which is the subject of the invention can be used in various other forms than beads, for example powder, foam (metallic or ceramic), coated on ceramic substrates (cordierite, mullite, etc.) or metallic, or ceramic filters, extruded different geometries (monolobe, trilobed ...), pellets.
  • the gas passing over the activated catalytic material further comprises carbon dioxide (CO2).
  • the proportion of carbon monoxide in the gas to the activated catalytic material is greater than five percent by volume on dry gas.
  • a gaseous mixture containing mainly CO, CO2 and H2 is passed, with an H2 content greater than that of CO and CO2.
  • the average temperature of the catalytic layer is less than 300 ° C. It is noted that, even if the fluidized bed makes it possible to have intensified exchanges, there remains near the reaction front a slight temperature peak related to very fast kinetics.
  • the method comprises a step of shaping the catalyst material in the form of beads, whose average size is between 100 and 1000 ⁇ .
  • the catalytic material prior to the activation step, has respective proportions, relative to the total mass of these three compounds, of:
  • AI2O3 70 to 94% by weight.
  • the catalytic material prior to the activation step, has respective proportions, relative to the total mass of these three compounds, of:
  • NiO 6 to 12% by weight
  • AI 2 O 3 76 to 88% by weight.
  • the alumina has a mesoporosity corresponding to a median pore diameter, determined by Hg intrusion porosimetry, of between 3 and 50 nm.
  • the alumina has a gamma structure.
  • the specific surface area SStel of the catalytic material is between 50 and 300 m 2 / g.
  • the specific surface area SStel of the catalytic material is between 100 and 250 m 2 / g.
  • the step of activating the catalytic material comprises a heat treatment in the presence of reducing agents.
  • the step of activating the catalytic material in the presence of reducing agents is carried out in a temperature range between 300 and 500 ° C and preferably between 400 and 500 ° C.
  • the method further includes
  • a thermal decomposition step in an atmosphere comprising oxygen and in a temperature range of between 350 and 500 ° C., for a period of between one hour and four hours.
  • the method comprises, before the step of passing the gas, a step of forming the gas comprising at least one of the following steps:
  • the gas passes through a catalytic layer of activated catalytic material.
  • the catalytic layer is preferably a fluidized bed by passing the gas through the catalytic material.
  • At least one heat exchange tube is immersed in the catalytic layer.
  • Each heat exchange tube makes it possible to control the temperature of the methanation reaction.
  • the particular catalytic material of the invention allows an effective conversion at medium temperature of the reaction medium of less than 300 ° C., which is favorable both to the speed of the reaction and to its yield.
  • the present invention relates to a catalyst preparation process, which comprises:
  • the present invention provides a device for converting a gas into methane (CH 4 ), which comprises:
  • a catalytic layer obtained by activating a catalytic material comprising praseodymium oxide (PreOn) combined with nickel oxide (NiO) and alumina (Al 2 O 3), the respective proportions of which are relative to the total mass of these three compounds:
  • NiO 1 to 20% by weight and Al 2 O 3: 60 to 98% by weight;
  • a means for passing a gas comprising at least carbon monoxide (CO) on the catalytic layer a means for passing a gas comprising at least carbon monoxide (CO) on the catalytic layer.
  • CO carbon monoxide
  • the catalytic material has respective proportions, with respect to the total mass of these three compounds, of:
  • NiO 6 to 12% by mass
  • AI 2 O 3 76 to 88% by weight.
  • the device comprises a fluidized bed comprising the catalytic layer.
  • the device comprises at least one heat exchange tube immersed in the catalytic layer.
  • FIG. 1 is a block diagram of a particular manufacturing process of the catalytic material which is the subject of the invention
  • FIG. 2 represents, in the form of a logic diagram, a particular embodiment of the process for preparing the catalytic material which is the subject of the invention
  • FIG. 3 represents a methanation unit implementing the method that is the subject of the invention.
  • the catalytic material used by the process which is the subject of the invention comprises praseodymium oxide ( ⁇ ) associated with nickel oxide (NiO) and with alumina (Al 2 O 3), the respective proportions of which are , in relation to the total mass of these three compounds:
  • NiO 1 to 20% by weight, preferably 3 to 15% by weight, and still more preferably 6 to 12% by weight;
  • - AI2O3 60 to 98% by weight, preferably 70 to 94% by weight and, more preferably, 76 to 88% by weight.
  • the alumina is mesoporous and, preferably, of gamma structure.
  • the preferential alumina mesoporosity domain corresponds to a median pore diameter, determined by Hg intrusion porosimetry, of between 3 and 50 nm, and preferably between 5 and 25 nm.
  • the specific surface SStel of the catalytic material is preferably between 50 and 300 m 2 / g, more preferably between 100 and 250 m 2 / g.
  • This conversion is also called methanation or Sabatier reaction and consists of a hydrogenation of CO and / or CO2 to produce a gas containing CH.
  • the conversion is carried out starting from a gaseous mixture containing mainly carbon monoxide (CO), carbon dioxide (CO2) and dihydrogen (H2), in particular with a hydrogen content (H2) higher than that of carbon monoxide (CO) and carbon dioxide (CO2).
  • the conversion can be carried out efficiently at a lower average temperature in the reaction medium at 300 ° C., unlike previously known catalysts.
  • the method of manufacturing the catalytic material comprises, as illustrated in FIG. 2:
  • a step 35 of surface deposition of the metal salts on an alumina-based support Al 2 O 3
  • a step 50 of activating the material obtained by heat treatment in the presence of reducing agents is a step 50 of activating the material obtained by heat treatment in the presence of reducing agents.
  • Step 30 consists of solubilizing separately or in mixture the raw materials of the precursor salts of nickel and praseodymium.
  • a surface deposition of these metal salts is carried out on an alumina-based support, generally alumina (Al2O3) or boehmite-type alumina hydrate (AIOOH).
  • a heat treatment is carried out under an atmosphere comprising oxygen, for example under air or under oxygen, which makes it possible to decompose the metal precursors and to obtain the alumina in a gamma or delta form when the The support used is initially boehmite alumina hydrate (AIOOH).
  • the surface deposition of nickel and praseodymium precursor salts is carried out on a support comprising alumina, preferably already in gamma or delta form, or on a hydrate carrier.
  • alumina preferably already in gamma or delta form, or on a hydrate carrier.
  • boehmite type alumina which leads to a gamma or delta-type alumina when dehydrated during the heat treatment step.
  • step 45 a catalyst is formed from the catalytic material obtained in step 40.
  • step 50 the catalyst is activated. This activation, by a heat treatment in the presence of reducing or chemical agents, partially or completely transforms the nickel oxide into nickel.
  • the activation stage of the catalytic material is preferably carried out in the presence of reducing agents, in a temperature range between 300 and 500 ° C. and preferably between 400 and 500 ° C.
  • the catalyst is used by passing a gas comprising carbon monoxide (CO) and hydrogen (H2) on the activated catalytic material, optionally in the presence of carbon dioxide.
  • a gas comprising carbon monoxide (CO) and hydrogen (H2)
  • a first example of a process comprises the co-impregnation of praseodymium salts and nickel salt on a support 20 (see FIG. 1), during a step 35 (see FIG. 2).
  • the support is, for example a boehmite-type alumina hydrate, or alumina (Al2O3) crystallized in a gamma or delta form.
  • the salts used may be chlorides, nitrates, acetates or sulphates.
  • Each of the aforementioned salts of Ni and Pr is solubilized simultaneously with stirring, to form a homogeneous solution (step 30) which is then brought into contact with the support (step 35).
  • the solution of these metal precursors is then absorbed into the porosity of the support.
  • the nickel salt takes the hydrated form Ni (NO3) 2, 6H2O and the praseodymium salt takes the form Pr (NO3) 3, 5H2O.
  • the volume of solution prepared is then less than or equal to the volume that can be absorbed by the support;
  • step 40 The impregnated supports then undergo a calcination (step 40) in order to thermally decompose the metal precursors, and to form the oxides of Ni and Pr.
  • the step calcination transforms the alumina hydrate into alumina.
  • a second example of a process for preparing the catalytic material consists of successive impregnations of the nickel salts and then of praseodymium or praseodymium and then nickel on alumina or on boehmite-type alumina hydrate.
  • the metal salts of nickel and praseodymium retained are solubilized separately.
  • the solution containing the salt of the first metal (nickel or praseodymium, respectively) is then impregnated onto the support as described in the first example of the process, dry or in excess of solution.
  • a calcination step then makes it possible to decompose the metal precursor to form an intermediate product and to transform the alumina hydrate into alumina, if appropriate.
  • the latter is then impregnated with the second solution containing the salt of the second metal (praseodymium or nickel, respectively) following the same steps again.
  • a third example of a process for preparing the catalytic material consists of co-precipitation of the nitro salts of praseodymium, nickel and alumina or alumina hydrate of the boehmite type, followed also by thermal decomposition.
  • a fourth example of a process for preparing the catalytic material consists of an atomization of a suspension containing salts of nickel, praseodymium and boehmite or alumina, followed by a step of calcination under air.
  • the suspension is sprayed into fine droplets by means of an atomization turbine, or by high-pressure injection through nozzles, in a vertical cylindrical chamber swept by a hot air flow. Evaporation of the water leads to the formation of a dry powder recovered in the lower part of the equipment.
  • This drying process makes it possible to shape a catalytic material with a targeted particle size, conditioned by the atomization parameters as well as by the characteristics of the equipment.
  • the oxide obtained at the end of the calcination step (step 40) is activated under a reducing gas (CO, H2, NH3, ...) which is pure or diluted with an inert gas (Ar, N2, He, ...), following a suitable temperature profile, for converting all or part of the nickel oxide (NiO) to dispersed metal Ni in a step 50.
  • the catalytic material is activated under flow of a gas containing hydrogen during a temperature profile comprising a rise in temperature of the ambient up to 400 ° C. with a ramp of 2 ° C / min, and a plateau of 4 hours at 400 ° C, preferably in the presence of reducing agents. More generally, the activation step is preferably carried out in a temperature range between 300 and 500 ° C and preferably between 400 and 500 ° C.
  • the catalytic material itself may be in pulverulent form, the average grain size of which varies from 1 to 100 ⁇ .
  • the catalytic material can be put into different forms (step 45): powder, foam (metallic or ceramic), coated on ceramic substrates (cordierite, mullite ...) or metallic or ceramic filters, extruded different geometries (single-layered, trilobed) %), balls, pellets ...
  • their average size is between 100 ⁇ and 1 mm, preferably between 200 and 800 ⁇ and, more preferably, between 200 and 600 ⁇ .
  • a step of use (step 55) of the catalytic material comprises the conversion of carbon monoxide (CO) to methane, in the presence of hydrogen (H2), optionally in the presence of carbon dioxide (CO2).
  • the gas to be converted comprises at least 5% CO (volume content on dry gas), more preferably at least 10% CO (volume content on dry gas), and even more preferably 15% CO (gas volume content). dry).
  • 15% of CO corresponds, for example, to the minimum CO content usually measured in a gas from gasification with steam.
  • FIG. 3 shows a fluidized bed reactor containing the catalyst and leading to the conversion of a gas containing at least carbon monoxide (CO) into methane (CH 4 ) during the passage of this gas over the catalyst, that is to say the catalytic material activated.
  • CO carbon monoxide
  • CH 4 methane
  • a fluidized bed can give a class of solids, here the catalyst, some properties of fluids, liquids or gases. It allows a strong interaction of catalyst particles and the gas that passes through it.
  • the principle of the fluidized bed is to inject under a bed of solid particles a gas under pressure. This gas lifts and disperses the solid particles. It allows more efficient catalysts. It is called “fluidized bed reactor” or FBR (fluidized bed reactor).
  • Particulate agitation and hydrodynamic stirring by gas bubble trains fluidized layers, volumes in which the solid particles are vigorously stirred. They can exchange heat and matter with great efficiency, by direct contact, with a large specific surface area, with gas or with a submerged heat exchanger for recovery or the elimination of the heat produced by the conversion reaction of the gas containing carbon monoxide into methane.
  • the fluidized layer then constitutes an open volume, practically isothermal, because of the high specific heat capacity of the solids relative to that of the gas, as well as by their renewal in contact with the exchange surfaces.
  • FIG. 3 which is not to scale, shows a schematic view of one embodiment of the reactor 100.
  • This reactor 100 comprises an enclosure 105 having a so-called “low” longitudinal end 107 and an end 106 opposite longitudinal so-called “high”.
  • the enclosure 105 is, for example, formed of a sealed and sealed volume.
  • the shape, internal and / or external, of the enclosure 105 is of no importance for the present invention as long as the enclosure is sealed.
  • the enclosure 105 has a tubular shape, that is to say a cylindrical shape, which can be oblong as shown in FIG.
  • the enclosure 105 comprises, near the lower end 107, a gas inlet 1 10 comprising carbon monoxide and hydrogen and, optionally, carbon dioxide.
  • the enclosure 105 comprises, near the upper end 106, an outlet 15 for methane or for a gas rich in methane.
  • An activated catalytic material 125 which is not consumable by the conversion reaction forms a catalytic layer which is preferably a fluidized bed through which the gas from the inlet 1 10 passes.
  • the inlet, 1 10 is, for example, an injection nozzle, a nozzle, a perforated tube, a piping network equipped with strainers. However, any fluid injection member usually used in a reactor can be used to make the inlet 1 10.
  • the outlet 1 15 is, for example, an opening formed in the enclosure 105 connected to a methane transport pipe .
  • the reactor 100 comprises heat exchange tubes (not shown) immersed in the enclosure 105 and traversed by a fluid having a temperature compatible with the nominal operating temperature inside the enclosure 105 when the operation of the reactor 100.
  • the fluid is at a lower temperature than the interior of the enclosure to allow the temperature maintenance of the reactor by removing excess heat related to the exothermicity of conversions implemented. This excess heat evacuated is preferentially valued.
  • the average temperature of the reaction medium 125 and / or the outlet temperature of the catalytic layer 1 may be less than 300 ° C.
  • the exothermic reaction tends to increase the temperature and, in preferred embodiments, the temperature of the reaction zone is controlled to maintain, on average, less than 300 ° C., which promotes thermodynamics while allowing the reaction. This gives a reaction whose yield is increased.
  • the pressure inside the enclosure 105 is between a bar (atmospheric pressure) and 70 bar, preferably between 1 bar and 20 bar, and more preferably between 1 bar and 10 bar. These pressures optimize conversion by minimizing upstream compression costs.
  • the fluidization / flow rate range is between once the minimum fluidization rate and sixteen times the minimum fluidization rate, preferably between two times and eight times the minimum fluidization speed, which optimizes the heat exchange.
  • the reactor may be preceded by a pyrolysis unit for hydrocarbon materials (biomass, waste, coal, etc.) or a pyro-gasification unit.
  • hydrocarbon materials biomass, waste, coal, etc.
  • a gasification unit for hydrocarbon materials biomass, waste, coal, etc.
  • a Water-Gas-Shift unit or a Reverse Water-Gas unit -Shift or a co-electrolysis unit of CO2 / H2O as described in the patent application EP 16757688.3, incorporated herein by reference.
  • the catalyst used by the process of the invention offers an activity at 250 ° C., superior to a technology on the market (reference technology having a composition of 50% nickel on alumina, without praseodymium), such as shows the following table:
  • Composition of the gas stream 12% CO, 8% CO2, 70% H 2 , 5% H2O, 5% CH.
  • Catalyst of the invention Catalyst of the market 95% CO conversion 25%
  • the catalyst To be active in methanation, the catalyst must undergo a reducing treatment which modifies the oxidation state of Ni and Pr.
  • the catalyst material has previously undergone a reducing treatment under a gas stream containing hydrogen at 450 ° C for a period of four hours.
  • the catalyst formed with the catalytic material is at least as efficient as the catalyst on the market for average temperatures in the reaction medium greater than 300 ° C.
  • the catalytic material therefore has a wider range of operating temperatures, from 220 to 400 ° C., preferably from 250 to 350 ° C.
  • the catalyst used by the process of the invention is that of its most preferred embodiments.
  • the conversion rates are defined by the ratios ([CO or CO2] input - [CO or CO2] output) / ([CO OR CO 2 ] input).
  • the invention thus applies particularly well to the field of conversion of carbon monoxide (CO), optionally in the presence of carbon dioxide (CO2) and a gaseous mixture rich in hydrogen, a mixture rich in methane (CH 4 ) and, in particular, low temperature conversions.
  • CO carbon monoxide
  • CO2 carbon dioxide
  • CH 4 methane
  • a catalytic material comprising praseodymium oxide (PreOn) combined with nickel oxide (NiO) and with alumina (Al2O3), the respective proportions of which are relative to to the total mass of these three compounds:
  • NiO 1 to 20% by weight

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Abstract

The invention relates to a method for converting a gas into methane (CH4) which includes: - a step of activating a catalytic material including praseodymium (Pr6O11) associated with nickel oxide (NiO) and alumina (Al2O3), the respective proportions of which are, relative to the total weight of these three compounds: - Pr6O11: 1 wt% to 20 wt%, - NiO: 1 wt% to 20 wt%, and - Al2O3: 60 to 98 wt%; and - a step of passing a gas including at least one carbon monoxide (CO) over the activated catalytic material.

Description

PROCÉDÉ DE CONVERSION D'UN GAZ COMPORTANT DU MONOXYDE DE CARBONE EN MÉTHANE À L'AIDE D'UN MATÉRIAU CATALYTIQUE CONTENANT DU PRASEODYME ET DU NICKEL SUR ALUMINE  PROCESS FOR CONVERTING A GAS COMPRISING CARBON MONOXIDE TO METHANE USING A CATALYTIC MATERIAL CONTAINING PRASEODYM AND NICKEL ON ALUMINA
DOMAINE TECHNIQUE DE L'INVENTION TECHNICAL FIELD OF THE INVENTION
La présente invention concerne un procédé et un dispositif de conversion d'un gaz en méthane.  The present invention relates to a method and a device for converting a gas into methane.
Elle s'applique au domaine de la conversion du monoxyde de carbone (CO), 5 éventuellement en présence de dioxyde de carbone (CO2), dans un mélange gazeux riche en hydrogène, en un mélange riche en méthane (CH4), sur un domaine élargi de températures et, en particulier, à basse température. It applies to the field of conversion of carbon monoxide (CO), optionally in the presence of carbon dioxide (CO2), in a gas mixture rich in hydrogen, a mixture rich in methane (CH 4 ), on a wide range of temperatures and, in particular, at low temperatures.
ÉTAT DE LA TECHNIQUE STATE OF THE ART
10 On connaît des matériaux catalytiques contenant de l'oxyde de nickel et de l'alumine. Les teneurs en oxydes de nickel sont généralement élevées et varient selon les procédés entre 20 et 50 %. Ces matériaux présentent des performances catalytiques jugées parfois insuffisantes, notamment lorsque les températures du procédé sont faibles, par exemple inférieures à 300 °C. De plus, la thermodynamique Catalytic materials containing nickel oxide and alumina are known. The contents of nickel oxides are generally high and vary depending on the process between 20 and 50%. These materials have catalytic performances considered sometimes insufficient, especially when the process temperatures are low, for example below 300 ° C. In addition, thermodynamics
15 montre que plus la température de réaction est faible, plus le taux de conversion en méthane est élevé et les réactifs en excès sont faibles. Les catalyseurs du marché étant principalement actifs pour des températures supérieures à 300°C, leur taux de conversion est limité par la thermodynamique. Enfin, les fortes teneurs en nickel impactent négativement le prix de revient de ces matériaux, et dans certains cas laShows that the lower the reaction temperature, the higher the conversion rate to methane and the excess reagents are low. Since catalysts on the market are mainly active at temperatures above 300 ° C, their conversion rate is limited by thermodynamics. Finally, the high nickel content has a negative impact on the cost price of these materials, and in some cases
20 gestion de l'élimination des charges usagées. 20 management of the disposal of used charges.
On connaît le document de Ahmad Waqar et Al. « Synthesis of lanthanide séries (La, Ce, Pr, Eu & Gd) promoted Ni/[gamma] - AI2O3 catalysts for methanation of CO2 at low température under atmospheric pressure" Catalysts Communications, Elsevier, Amsterdam, NL, vol. 100, 27 juin 2017, pages 121 -126, XP085145534, The document by Ahmad Waqar and Al is known. Synthesis of lanthanide series (La, Ce, Pr, Eu & Gd) promoted Ni / [gamma] -Al2O3 catalysts for methanation of CO2 at low temperature under atmospheric pressure "Catalysts Communications, Elsevier , Amsterdam, NL, vol 100, June 27, 2017, pages 121 -126, XP085145534,
25 ISSN: 1566-7367, DOI : 10.1016/J. Catcom.2017.06.044. ISSN: 1566-7367, DOI: 101016 / J. Catcom.2017.06.044.
On connaît aussi le document Wan Azelee Wan Abu Bakar et Al. : « Nickel Oxide Based Supported Catalysts for the In-Situ Reactions of Methanation and Desulfurization in the removal of Sour Gases from Simulated Natural Gas", Catalysis Letters, Kluwer Académie Publishers, NE, vol. 128, no. 1 -2, 1 1 novembre 2008, Also known is Wan Azelee Wan Abu Bakar et al.: "Nickel Oxide Based Supported Catalysts for the In-Situ Reactions of Methanation and Desulfurization in the Removal of Sour Gases from Simulated Natural Gas", Catalysis Letters, Kluwer Academy Publishers, NE , Volume 128, No. 1 -2, November 1, 2008,
30 pages 127-136, XP019671959, ISSN: 1572-879X. On connaît aussi le document Hezhi Liu et Al : « Effect of CeO2 addition on N1/AI2O3 catalysts for methanation of carbon dioxide with hydrogen", Journal of Natural Gas Chemistry., vol. 21 , no. 7, 1 novembre 2012, pages 703-707, XP055276014, US, CN ISSN: 1003-9953 (1 1 )60422-2. 30 pages 127-136, XP019671959, ISSN 1572-879X. Also known is Hezhi Liu et al: "Effect of CeO2 addition on N1 / Al2O3 catalysts for methanation of carbon dioxide with hydrogen", Journal of Natural Gas Chemistry, Vol 21, No. 7, November 1, 2012, pages 703 -707, XP055276014, US, CN ISSN: 1003-9953 (1 1) 60422-2.
On connaît aussi le document WO 00/16901 .  WO 00/16901 is also known.
On connaît enfin le document Mohd Hasmizan Razali : « CO2/H2 Methanation on Nickel Oxide based Catalysts dopes with Lanthanide Séries », Malaysian Journal of Analytical Sciences, vol. 9, no. 3, 1 janvier 2005  Finally, we know the document Mohd Hasmizan Razali: "CO2 / H2 Methanation on Nickel Oxide based Catalysts Dopes with Lanthanide Series", Malaysian Journal of Analytical Sciences, vol. 9, no. January 3, 2005
Chacun de ces documents se limite uniquement à la conversion du dioxyde de carbone en méthane.  Each of these documents is limited solely to the conversion of carbon dioxide to methane.
OBJET DE L'INVENTION OBJECT OF THE INVENTION
La présente invention vise à remédier à tout ou partie de ces inconvénients. À cet effet, selon un premier aspect, la présente invention vise un procédé de conversion d'un gaz en méthane (CH4), qui comporte : The present invention aims to remedy all or part of these disadvantages. For this purpose, according to a first aspect, the present invention relates to a process for converting a gas to methane (CH 4 ), which comprises:
- une étape d'activation d'un matériau catalytique comportant de l'oxyde de praséodyme (PreOn) associé à de l'oxyde de nickel (NiO) et à de l'alumine (AI2O3), dont les proportions respectives sont, par rapport à la masse totale de ces trois composés :  a step of activating a catalytic material comprising praseodymium oxide (PreOn) combined with nickel oxide (NiO) and with alumina (Al2O3), the respective proportions of which are relative to to the total mass of these three compounds:
- PreOn : 1 à 20 % en masse,  PreOn: 1 to 20% by weight,
- NiO : 1 à 20 % en masse et  NiO: 1 to 20% by weight and
- AI2O3 : 60 à 98 % en masse ; et  Al 2 O 3: 60 to 98% by weight; and
- une étape de passage d'un gaz comportant au moins du monoxyde de carbone (CO) sur le matériau catalytique activé.  - A step of passing a gas comprising at least carbon monoxide (CO) on the activated catalytic material.
Les inventeurs ont découvert que le choix de l'association des composés du matériau catalytique et l'impact de la teneur respective en chacun des éléments (ΡΓβΟ-π , NiO et AI2O3), assure un bon compromis performance / durabilité / coût, quand ce matériau catalytique est utilisé pour la conversion du monoxyde de carbone (CO) éventuellement en présence de dioxyde de carbone (CO2), dans un mélange gazeux riche en hydrogène (H2), en un mélange gazeux riche en méthane (CH4), par exemple contenant principalement du CO, CO2 et H2, et offrant une performance élevée en conversion de l'ensemble constitué du CO et du CO2 à basse température, par exemple à des températures inférieures à 300°C. Ce matériau catalytique présente un domaine de températures d'utilisation plus large que celui des matériaux catalytiques précédemment connus. Du fait des lois de la thermodynamique, la conversion du CO et du CO2 est augmentée, en particulier à basse température. The inventors have discovered that the choice of the combination of the compounds of the catalytic material and the impact of the respective content of each of the elements (ΡΓβΟ-π, NiO and Al2O3), ensures a good compromise performance / durability / cost, when this catalytic material is used for the conversion of carbon monoxide (CO) optionally in the presence of carbon dioxide (CO2), in a gaseous mixture rich in hydrogen (H2), in a gaseous mixture rich in methane (CH 4 ), for example containing mainly CO, CO2 and H2, and offering a high performance in conversion of the assembly consisting of CO and CO2 at low temperatures, for example at temperatures below 300 ° C. This catalytic material has a wider temperature range of use than previously known catalytic materials. Due to the laws of thermodynamics, the conversion of CO and CO2 is increased, especially at low temperatures.
Le matériau catalytique proprement dit peut-être sous forme pulvérulente, dont la taille moyenne des grains varie de 1 à 1 00 μηπ, ou sous forme de billes de 1 00 μηπ à 1 mm, préférentiellement entre 200 et 800 μηπ et encore plus préférentiellement, entre 200 et 600 μηι.  The catalytic material itself may be in pulverulent form, whose average grain size varies from 1 to 100 μηπ, or in the form of beads of 100 μηπ at 1 mm, preferably between 200 and 800 μηπ and even more preferentially, between 200 and 600 μηι.
On note que le catalyseur formé par activation du matériau catalytique objet de l'invention peut être utilisé sous différentes autres formes que des billes, par exemple poudre, mousse (métallique ou céramique), coaté sur substrats céramiques (cordiérite, mullite...) ou métalliques, ou encore filtres céramiques, extrudés de différentes géométries (monolobe, trilobé...), pellets.  It is noted that the catalyst formed by activation of the catalytic material which is the subject of the invention can be used in various other forms than beads, for example powder, foam (metallic or ceramic), coated on ceramic substrates (cordierite, mullite, etc.) or metallic, or ceramic filters, extruded different geometries (monolobe, trilobed ...), pellets.
Dans des modes de réalisation, le gaz passant sur le matériau catalytique activé comporte, de plus, du dioxyde de carbone (CO2).  In embodiments, the gas passing over the activated catalytic material further comprises carbon dioxide (CO2).
Dans des modes de réalisation, la proportion de monoxyde de carbone dans le gaz parvenant au matériau catalytique activé est supérieure à cinq pourcents en volume sur gaz sec.  In embodiments, the proportion of carbon monoxide in the gas to the activated catalytic material is greater than five percent by volume on dry gas.
Dans des modes de réalisation, au cours de l'étape de passage de gaz, on fait passer un mélange gazeux contenant principalement du CO, CO2 et H2, avec une teneur en H2 supérieure à celle du CO et du CO2.  In embodiments, during the gas passage step, a gaseous mixture containing mainly CO, CO2 and H2 is passed, with an H2 content greater than that of CO and CO2.
Dans des modes de réalisation, au cours de l'étape de passage de gaz, la température moyenne de la couche catalytique est inférieure à 300 °C. On note que, même si le lit fluidisé permet d'avoir des échanges intensifiés, il subsiste à proximité du front de réaction un léger pic de température lié à une cinétique très rapide.  In embodiments, during the gas passage step, the average temperature of the catalytic layer is less than 300 ° C. It is noted that, even if the fluidized bed makes it possible to have intensified exchanges, there remains near the reaction front a slight temperature peak related to very fast kinetics.
Dans des modes de réalisation, le procédé comporte une étape de mise en forme du matériau catalytique en forme de billes, dont la taille moyenne est comprise entre 1 00 et 1 000 μηι.  In embodiments, the method comprises a step of shaping the catalyst material in the form of beads, whose average size is between 100 and 1000 μηι.
Dans des modes de réalisation, avant l'étape d'activation, le matériau catalytique présente des proportions respectives, par rapport à la masse totale de ces trois composés, de :  In embodiments, prior to the activation step, the catalytic material has respective proportions, relative to the total mass of these three compounds, of:
- ΡΓΘΟΙ Ι : 3 à 15 % en masse,  - ΡΓΘΟΙ Ι: 3 to 15% by weight,
- NiO : 3 à 1 5 % en masse et  NiO: 3 to 15% by weight and
- AI2O3 : 70 à 94 % en masse. Dans des modes de réalisation, avant l'étape d'activation, le matériau catalytique présente des proportions respectives, par rapport à la masse totale de ces trois composés, de : AI2O3: 70 to 94% by weight. In embodiments, prior to the activation step, the catalytic material has respective proportions, relative to the total mass of these three compounds, of:
- ΡΓΘΟΙ Ι : 5 à 12 % en masse,  - ΡΓΘΟΙ Ι: 5 to 12% by weight,
- NiO : 6 à 12 % en masse et  NiO: 6 to 12% by weight and
- AI2O3 : 76 à 88 % en masse.  AI 2 O 3: 76 to 88% by weight.
Dans des modes de réalisation, l'alumine présente une mésoporosité correspondant à un diamètre médian des pores, déterminé par porosimétrie à intrusion de Hg, compris entre 3 et 50 nm.  In embodiments, the alumina has a mesoporosity corresponding to a median pore diameter, determined by Hg intrusion porosimetry, of between 3 and 50 nm.
Dans des modes de réalisation, l'alumine présente une structure gamma.  In embodiments, the alumina has a gamma structure.
Dans des modes de réalisation, la surface spécifique SStel du matériau catalytique est comprise entre 50 et 300 m2/g. In embodiments, the specific surface area SStel of the catalytic material is between 50 and 300 m 2 / g.
Dans des modes de réalisation, la surface spécifique SStel du matériau catalytique est comprise entre 100 à 250 m2/g. In embodiments, the specific surface area SStel of the catalytic material is between 100 and 250 m 2 / g.
Le compromis performance / durabilité / coût est ainsi encore amélioré.  The compromise between performance / durability / cost is thus further improved.
Dans des modes de réalisation, l'étape d'activation du matériau catalytique comporte un traitement thermique en présence d'agents réducteurs.  In embodiments, the step of activating the catalytic material comprises a heat treatment in the presence of reducing agents.
Dans des modes de réalisation, l'étape d'activation du matériau catalytique en présence d'agents réducteurs est réalisée dans un domaine de température entre 300 et 500°C et de préférence entre 400 et 500°C.  In embodiments, the step of activating the catalytic material in the presence of reducing agents is carried out in a temperature range between 300 and 500 ° C and preferably between 400 and 500 ° C.
Dans des modes de réalisation, le procédé comporte, de plus,  In embodiments, the method further includes
- une étape de solubilisation de sels précurseurs du nickel et du praséodyme, séparément ou en mélange,  a step of solubilizing precursor salts of nickel and praseodymium, separately or as a mixture,
- une étape de dépôt surfacique des sels métalliques sur un support à base d'alumine (AI2O3) et  a step of surface deposition of metal salts on an alumina-based support (Al 2 O 3) and
- une étape de décomposition thermique sous atmosphère comportant de l'oxygène et dans un domaine de température compris entre 350 et 500°C, sur une durée comprise entre une heure et quatre heures.  a thermal decomposition step in an atmosphere comprising oxygen and in a temperature range of between 350 and 500 ° C., for a period of between one hour and four hours.
Dans des modes de réalisation, le procédé comporte, avant l'étape de passage du gaz, une étape de constitution du gaz comportant au moins l'une des étapes suivantes :  In embodiments, the method comprises, before the step of passing the gas, a step of forming the gas comprising at least one of the following steps:
- pyrolyse de matières hydrocarbonées,  pyrolysis of hydrocarbon materials,
- pyro-gazéification de matières hydrocarbonées,  - pyro-gasification of hydrocarbon materials,
- gazéification de matières hydrocarbonées, - co-électrolyse de CO2/H2O, - gasification of hydrocarbon materials, co-electrolysis of CO2 / H2O,
- Water-Gas-Shift, et  - Water-Gas-Shift, and
- Reverse Water-Gas-Shift.  - Reverse Water-Gas-Shift.
Ces différentes étapes fournissent un gaz comportant du monoxyde de carbone.  These different steps provide a gas comprising carbon monoxide.
Dans des modes de réalisation, au cours de l'étape de passage du gaz sur le matériau catalytique activé, le gaz traverse une couche catalytique de matériau catalytique activé.  In embodiments, during the step of passing the gas over the activated catalytic material, the gas passes through a catalytic layer of activated catalytic material.
Dans des modes de réalisation, la couche catalytique est de préférence un lit fluidisé par le passage du gaz au travers du matériau catalytique.  In embodiments, the catalytic layer is preferably a fluidized bed by passing the gas through the catalytic material.
Dans des modes de réalisation, au moins un tube d'échange de chaleur est immergé dans la couche catalytique.  In embodiments, at least one heat exchange tube is immersed in the catalytic layer.
Chaque tube d'échange de chaleur permet de contrôler la température de la réaction de méthanation. Le matériau catalytique particulier de l'invention permet une conversion efficace à température moyenne du milieu réactionnel inférieure à 300 °C, favorable tant à la vitesse de la réaction qu'à son rendement.  Each heat exchange tube makes it possible to control the temperature of the methanation reaction. The particular catalytic material of the invention allows an effective conversion at medium temperature of the reaction medium of less than 300 ° C., which is favorable both to the speed of the reaction and to its yield.
Selon un deuxième aspect, la présente invention vise un procédé de préparation de catalyseur, qui comporte :  According to a second aspect, the present invention relates to a catalyst preparation process, which comprises:
- une étape de solubilisation de sels précurseurs du nickel et du praséodyme, séparément ou en mélange,  a step of solubilizing precursor salts of nickel and praseodymium, separately or as a mixture,
- une étape de dépôt surfacique des sels métalliques sur un support à base d'alumine (AI2O3),  a step of surface deposition of metal salts on an alumina-based support (Al 2 O 3),
- une étape de décomposition thermique sous atmosphère comportant de l'oxygène et  a step of thermal decomposition under an atmosphere comprising oxygen and
- une étape d'activation du matériau obtenu par traitement thermique en présence d'agents réducteurs.  a step of activating the material obtained by heat treatment in the presence of reducing agents.
Selon un troisième aspect, la présente invention vise un dispositif de conversion d'un gaz en méthane (CH4), qui comporte : According to a third aspect, the present invention provides a device for converting a gas into methane (CH 4 ), which comprises:
- une couche catalytique obtenue par activation d'un matériau catalytique comportant de l'oxyde de praséodyme (PreOn) associé à de l'oxyde de nickel (NiO) et à de l'alumine (AI2O3), dont les proportions respectives sont, par rapport à la masse totale de ces trois composés :  a catalytic layer obtained by activating a catalytic material comprising praseodymium oxide (PreOn) combined with nickel oxide (NiO) and alumina (Al 2 O 3), the respective proportions of which are relative to the total mass of these three compounds:
- PreOn : 1 à 20 % en masse,  PreOn: 1 to 20% by weight,
- NiO : 1 à 20 % en masse et - AI2O3 : 60 à 98 % en masse ; et NiO: 1 to 20% by weight and Al 2 O 3: 60 to 98% by weight; and
- un moyen de passage d'un gaz comportant au moins du monoxyde de carbone (CO) sur la couche catalytique.  a means for passing a gas comprising at least carbon monoxide (CO) on the catalytic layer.
Dans des modes de réalisation, le matériau catalytique présente des proportions respectives, par rapport à la masse totale de ces trois composés, de :  In embodiments, the catalytic material has respective proportions, with respect to the total mass of these three compounds, of:
- ΡΓΘΟΙ Ι : 5 à 12 % en masse,  - ΡΓΘΟΙ Ι: 5 to 12% by weight,
- NiO : 6 à 1 2 % en masse et  NiO: 6 to 12% by mass and
- AI2O3 : 76 à 88 % en masse.  AI 2 O 3: 76 to 88% by weight.
Dans des modes de réalisation, le dispositif comporte un lit fluidisé comportant la couche catalytique.  In embodiments, the device comprises a fluidized bed comprising the catalytic layer.
Dans des modes de réalisation, le dispositif comporte au moins un tube d'échange de chaleur immergé dans la couche catalytique.  In embodiments, the device comprises at least one heat exchange tube immersed in the catalytic layer.
Les avantages, buts et caractéristiques particulières de ce dispositif étant similaires à ceux du procédé de conversion objet de l'invention, ils ne sont pas rappelés ici.  Since the advantages, aims and particular characteristics of this device are similar to those of the conversion method which is the subject of the invention, they are not recalled here.
BRÈVE DESCRIPTION DES FIGURES BRIEF DESCRIPTION OF THE FIGURES
D'autres avantages, buts et caractéristiques de la présente invention ressortiront de la description qui va suivre, faite dans un but explicatif et nullement limitatif en regard du dessin annexé, dans lequel :  Other advantages, aims and features of the present invention will emerge from the description which follows, made for an explanatory and non-limiting purpose with reference to the appended drawing, in which:
- la figure 1 est un schéma fonctionnel d'un procédé de fabrication particulier du matériau catalytique objet de l'invention,  FIG. 1 is a block diagram of a particular manufacturing process of the catalytic material which is the subject of the invention,
- la figure 2 représente, sous forme de logigramme, un mode de réalisation particulier du procédé de préparation du matériau catalytique objet de l'invention et  FIG. 2 represents, in the form of a logic diagram, a particular embodiment of the process for preparing the catalytic material which is the subject of the invention and
- la figure 3 représente une unité de méthanation mettant en œuvre le procédé objet de l'invention.  FIG. 3 represents a methanation unit implementing the method that is the subject of the invention.
DESCRIPTION D'EXEMPLES DE RÉALISATION DE L'INVENTION DESCRIPTION OF EXAMPLES OF CARRYING OUT THE INVENTION
La présente description est donnée à titre non limitatif, chaque caractéristique d'un mode de réalisation pouvant être combinée à toute autre caractéristique de tout autre mode de réalisation de manière avantageuse. Toutes les teneurs sont, dans la description, exprimées en pourcentage massique pour les solides et les teneurs des gaz sont exprimées en pourcentage volumique sur gaz sec. This description is given in a nonlimiting manner, each feature of an embodiment being able to be combined with any other feature of any other embodiment in an advantageous manner. All the contents are, in the description, expressed in percentage by mass for the solids and the contents of the gases are expressed in percentage by volume on dry gas.
Le matériau catalytique mis en œuvre par le procédé objet de l'invention comporte de l'oxyde de praséodyme (ΡΓεΟη) associé à de l'oxyde de nickel (NiO) et à de l'alumine (AI2O3), dont les proportions respectives sont, par rapport à la masse totale de ces trois composés :  The catalytic material used by the process which is the subject of the invention comprises praseodymium oxide (ΡΓεΟη) associated with nickel oxide (NiO) and with alumina (Al 2 O 3), the respective proportions of which are , in relation to the total mass of these three compounds:
- PreOn : 1 à 20% en masse, préférentiellement 3 à 15 % en masse, et, encore plus préférentiellement, 5 à 12 % en masse ;  PreOn: 1 to 20% by weight, preferably 3 to 15% by weight, and still more preferably 5 to 12% by weight;
- NiO : 1 à 20% en masse, préférentiellement 3 à 15 % en masse, et, encore plus préférentiellement, 6 à 12 % en masse ; et  NiO: 1 to 20% by weight, preferably 3 to 15% by weight, and still more preferably 6 to 12% by weight; and
- AI2O3 : 60 à 98% en masse, préférentiellement, 70 à 94 % en masse et, encore plus préférentiellement, 76 à 88 % en masse.  - AI2O3: 60 to 98% by weight, preferably 70 to 94% by weight and, more preferably, 76 to 88% by weight.
Préférentiellement, l'alumine est mésoporeuse et, préférentiellement, de structure gamma. Le domaine de mésoporosité de l'alumine préférentiel correspond à un diamètre médian des pores, déterminé par porosimétrie à intrusion de Hg, compris entre 3 et 50 nm, et de préférence entre 5 et 25 nm.  Preferably, the alumina is mesoporous and, preferably, of gamma structure. The preferential alumina mesoporosity domain corresponds to a median pore diameter, determined by Hg intrusion porosimetry, of between 3 and 50 nm, and preferably between 5 and 25 nm.
La surface spécifique SStel du matériau catalytique est préférentiellement comprise entre 50 et 300 m2/g, plus préférentiellement, entre 100 à 250 m2/g. The specific surface SStel of the catalytic material is preferably between 50 and 300 m 2 / g, more preferably between 100 and 250 m 2 / g.
Les inventeurs ont découvert que le choix de cette association de composés et les teneurs respectives en chacun des éléments (PreOn , NiO et/ou AI2O3), assurent un bon compromis performance / durabilité / coût, notamment quand ce matériau catalytique est utilisé pour la conversion du monoxyde de carbone (CO), éventuellement en présence de dioxyde de carbone (CO2) dans un mélange gazeux riche en hydrogène (H2), en un mélange gazeux riche en méthane (CH4) et, en particulier, aux conversions à basse température, par exemple inférieures, en moyenne dans le milieu réactionnel, à 300 °C. The inventors have discovered that the choice of this combination of compounds and the respective contents of each of the elements (PreOn, NiO and / or Al 2 O 3), ensure a good compromise between performance / durability / cost, especially when this catalytic material is used for the conversion. carbon monoxide (CO), optionally in the presence of carbon dioxide (CO2) in a gaseous mixture rich in hydrogen (H2), in a gaseous mixture rich in methane (CH 4 ) and, in particular, in low temperature conversions , for example lower, on average in the reaction medium, at 300 ° C.
Cette conversion s'appelle aussi méthanation ou réaction de Sabatier et consiste en une hydrogénation du CO et/ou du CO2 pour produire un gaz contenant du CH .  This conversion is also called methanation or Sabatier reaction and consists of a hydrogenation of CO and / or CO2 to produce a gas containing CH.
Préférentiellement, la conversion est réalisée à partir d'un mélange gazeux contenant principalement du monoxyde de carbone (CO), du dioxyde de carbone (CO2) et du dihydrogène (H2), notamment avec une teneur en dihydrogène (H2) supérieure à celle du monoxyde de carbone (CO) et du dioxyde de carbone (CO2). La conversion peut être réalisée efficacement à une température inférieure moyenne, dans le milieu réactionnel, à 300°C, à la différence des catalyseurs connus antérieurement. Preferably, the conversion is carried out starting from a gaseous mixture containing mainly carbon monoxide (CO), carbon dioxide (CO2) and dihydrogen (H2), in particular with a hydrogen content (H2) higher than that of carbon monoxide (CO) and carbon dioxide (CO2). The conversion can be carried out efficiently at a lower average temperature in the reaction medium at 300 ° C., unlike previously known catalysts.
Pour préparer le matériau catalytique, on peut utiliser différents procédés. Dans des modes de réalisation, le procédé de fabrication du matériau catalytique comporte, comme illustré en figure 2 :  To prepare the catalytic material, various methods can be used. In embodiments, the method of manufacturing the catalytic material comprises, as illustrated in FIG. 2:
- une étape 30 de solubilisation de sels précurseurs du nickel et du praséodyme, séparément ou en mélange,  a step 30 of solubilizing precursor salts of nickel and praseodymium, separately or as a mixture,
- une étape 35 de dépôt surfacique des sels métalliques sur un support à base d'alumine (AI2O3),  a step 35 of surface deposition of the metal salts on an alumina-based support (Al 2 O 3),
- une étape 40 de décomposition thermique sous atmosphère comportant de l'oxygène et le cas échéant de déshydratation d'un hydrate d'alumine conduisant à une alumine sous forme gamma ou delta et  a step 40 of thermal decomposition under an atmosphere comprising oxygen and, if appropriate, dehydration of an alumina hydrate leading to an alumina in gamma or delta form and
- une étape 50 d'activation du matériau obtenu par traitement thermique en présence d'agents réducteurs.  a step 50 of activating the material obtained by heat treatment in the presence of reducing agents.
L'étape 30 consiste à solubiliser séparément ou en mélange les matières premières des sels précurseurs du nickel et du praséodyme. Au cours de l'étape 35, on réalise un dépôt surfacique de ces sels métalliques sur un support à base d'alumine, généralement de l'alumine (AI2O3) ou de l'hydrate d'alumine de type boehmite (AIOOH). Au cours de l'étape 40, on réalise un traitement thermique sous atmosphère comportant de l'oxygène, par exemple sous air ou sous oxygène, permettant de décomposer les précurseurs métalliques et d'obtenir l'alumine sous une forme gamma ou delta lorsque le support employé est initialement de l'hydrate d'alumine de type boehmite (AIOOH).  Step 30 consists of solubilizing separately or in mixture the raw materials of the precursor salts of nickel and praseodymium. During step 35, a surface deposition of these metal salts is carried out on an alumina-based support, generally alumina (Al2O3) or boehmite-type alumina hydrate (AIOOH). During step 40, a heat treatment is carried out under an atmosphere comprising oxygen, for example under air or under oxygen, which makes it possible to decompose the metal precursors and to obtain the alumina in a gamma or delta form when the The support used is initially boehmite alumina hydrate (AIOOH).
Dans les modes de réalisation du procédé décrits ci-dessous, le dépôt surfacique de sels précurseurs du nickel et du praséodyme se fait sur un support comportant de l'alumine, préférentiellement déjà sous forme gamma ou delta, ou sur un support en hydrate d'alumine de type boehmite, qui conduit à une alumine de forme gamma ou delta lorsqu'on la déshydrate au cours de l'étape de traitement thermique.  In the embodiments of the method described below, the surface deposition of nickel and praseodymium precursor salts is carried out on a support comprising alumina, preferably already in gamma or delta form, or on a hydrate carrier. boehmite type alumina, which leads to a gamma or delta-type alumina when dehydrated during the heat treatment step.
Dans le cas de la décomposition thermique sous air, elle se fait sur un domaine de températures de 300 à 800°C, préférentiellement de 400 à 600°C, et encore plus préférentiellement entre 350 et 500°C, préférentiellement pendant une durée comprise entre une heure et quatre heures. Au cours de l'étape 45, on met en forme un catalyseur à partir du matériau catalytique obtenu au cours de l'étape 40. Au cours de l'étape 50, on réalise une activation du catalyseur. Cette activation, par un traitement thermique en présence d'agents réducteurs ou chimique, transforme partiellement ou en totalité l'oxyde de nickel en nickel. L'étape d'activation du matériau catalytique est réalisée préférentiellement en présence d'agents réducteurs, dans un domaine de température entre 300 et 500°C et de préférence entre 400 et 500°C. In the case of thermal decomposition under air, it is carried out over a temperature range of 300 to 800 ° C., preferably 400 to 600 ° C., and even more preferably between 350 and 500 ° C., preferably for a period of time between an hour and four hours. In step 45, a catalyst is formed from the catalytic material obtained in step 40. In step 50, the catalyst is activated. This activation, by a heat treatment in the presence of reducing or chemical agents, partially or completely transforms the nickel oxide into nickel. The activation stage of the catalytic material is preferably carried out in the presence of reducing agents, in a temperature range between 300 and 500 ° C. and preferably between 400 and 500 ° C.
Au cours de l'étape 55, on utilise le catalyseur par passage d'un gaz comportant du monoxyde de carbone (CO) et de l'hydrogène (H2) sur le matériau catalytique activé, éventuellement en présence de dioxyde de carbone.  During step 55, the catalyst is used by passing a gas comprising carbon monoxide (CO) and hydrogen (H2) on the activated catalytic material, optionally in the presence of carbon dioxide.
Un premier exemple de procédé comporte la co-imprégnation de sels de praséodyme 15 et de sel de nickel 10 sur un support 20 (voir figure 1 ), au cours d'une étape 35 (voir figure 2). Le support est, par exemple un hydrate d'alumine de type boehmite, ou de l'alumine (AI2O3) cristallisée sous une forme gamma ou delta. Les sels utilisés peuvent être des chlorures, des nitrates, des acétates, ou encore des sulfates.  A first example of a process comprises the co-impregnation of praseodymium salts and nickel salt on a support 20 (see FIG. 1), during a step 35 (see FIG. 2). The support is, for example a boehmite-type alumina hydrate, or alumina (Al2O3) crystallized in a gamma or delta form. The salts used may be chlorides, nitrates, acetates or sulphates.
Chacun des sels précédemment cités de Ni et de Pr est solubilisé simultanément sous agitation, pour former une solution homogène (étape 30) qui est ensuite mise en contact avec le support (étape 35). La solution de ces précurseurs métalliques est alors absorbée dans la porosité du support.  Each of the aforementioned salts of Ni and Pr is solubilized simultaneously with stirring, to form a homogeneous solution (step 30) which is then brought into contact with the support (step 35). The solution of these metal precursors is then absorbed into the porosity of the support.
Par exemple, le sel de nickel prend la forme hydratée Ni(NO3)2, 6H2O et le sel de praséodyme prend la forme Pr(NO3)3, 5H2O.  For example, the nickel salt takes the hydrated form Ni (NO3) 2, 6H2O and the praseodymium salt takes the form Pr (NO3) 3, 5H2O.
Une telle imprégnation peut être réalisée :  Such impregnation can be achieved:
- à « sec » : le volume de solution préparé est alors inférieur ou égal au volume pouvant être absorbé par le support ; où  at "dry": the volume of solution prepared is then less than or equal to the volume that can be absorbed by the support; or
- en excès de solvant : dans ce cas, une phase de séchage est nécessaire. Les supports imprégnés subissent ensuite une calcination (étape 40) afin de décomposer thermiquement les précurseurs métalliques, et former les oxydes de Ni et de Pr. Dans le cas de l'utilisation de l'hydrate d'alumine de type boehmite, l'étape de calcination transforme l'hydrate d'alumine en alumine.  in excess of solvent: in this case, a drying phase is necessary. The impregnated supports then undergo a calcination (step 40) in order to thermally decompose the metal precursors, and to form the oxides of Ni and Pr. In the case of the use of the boehmite-type alumina hydrate, the step calcination transforms the alumina hydrate into alumina.
Un deuxième exemple de procédé de préparation du matériau catalytique consiste en des imprégnations successives des sels de nickel puis de praséodyme ou de praséodyme puis de nickel sur alumine ou sur hydrate d'alumine de type boehmite. Les sels métalliques de nickel et de praséodyme retenus, sont solubilisés séparément. La solution contenant le sel du premier métal (nickel ou praséodyme, respectivement) est alors imprégnée sur le support comme décrit dans le premier exemple de procédé, à sec ou en excès de solution. A second example of a process for preparing the catalytic material consists of successive impregnations of the nickel salts and then of praseodymium or praseodymium and then nickel on alumina or on boehmite-type alumina hydrate. The metal salts of nickel and praseodymium retained are solubilized separately. The solution containing the salt of the first metal (nickel or praseodymium, respectively) is then impregnated onto the support as described in the first example of the process, dry or in excess of solution.
Une étape de calcination permet ensuite de décomposer le précurseur métallique pour former un produit intermédiaire et de transformer l'hydrate d'alumine en alumine, le cas échéant. Ce dernier est alors imprégné par la seconde solution contenant le sel du second métal (praséodyme ou nickel, respectivement) en suivant de nouveau les mêmes étapes.  A calcination step then makes it possible to decompose the metal precursor to form an intermediate product and to transform the alumina hydrate into alumina, if appropriate. The latter is then impregnated with the second solution containing the salt of the second metal (praseodymium or nickel, respectively) following the same steps again.
Un troisième exemple de procédé de préparation du matériau catalytique consiste en une co-précipitation des sels nitrés de praséodyme, nickel et alumine ou hydrate d'alumine de type boehmite, suivie aussi d'une décomposition thermique.  A third example of a process for preparing the catalytic material consists of co-precipitation of the nitro salts of praseodymium, nickel and alumina or alumina hydrate of the boehmite type, followed also by thermal decomposition.
Un quatrième exemple de procédé de préparation du matériau catalytique consiste en une atomisation d'une suspension contenant des sels de nickel, praséodyme et de boehmite ou d'alumine, suivie d'une étape de calcination sous air.  A fourth example of a process for preparing the catalytic material consists of an atomization of a suspension containing salts of nickel, praseodymium and boehmite or alumina, followed by a step of calcination under air.
Lors du séchage par atomisation, la suspension est pulvérisée en fines gouttelettes au moyen d'une turbine d'atomisation, ou par injection à haute pression au travers de buses, dans une enceinte cylindrique verticale balayée par un flux d'air chaud. L'évaporation de l'eau conduit à la formation d'une poudre sèche récupérée dans la partie inférieure de l'équipement. Ce procédé de séchage permet de mettre en forme un matériau catalytique avec une granulométrie ciblée, conditionnée par les paramètres d'atomisation ainsi que par les caractéristiques de l'équipement.  During spray drying, the suspension is sprayed into fine droplets by means of an atomization turbine, or by high-pressure injection through nozzles, in a vertical cylindrical chamber swept by a hot air flow. Evaporation of the water leads to the formation of a dry powder recovered in the lower part of the equipment. This drying process makes it possible to shape a catalytic material with a targeted particle size, conditioned by the atomization parameters as well as by the characteristics of the equipment.
Dans tous les procédés de préparation du matériau catalytique précités, l'oxyde obtenu à l'issue de l'étape de calcination (étape 40) est activé sous un gaz réducteur (CO, H2, NH3, ...) pur ou dilué avec un gaz inerte (Ar, N2, He, ...), en suivant un profil de température adapté, pour transformer tout ou partie de l'oxyde de nickel (NiO) en Ni métallique dispersé au cours d'une étape 50.  In all the processes for the preparation of the catalytic material mentioned above, the oxide obtained at the end of the calcination step (step 40) is activated under a reducing gas (CO, H2, NH3, ...) which is pure or diluted with an inert gas (Ar, N2, He, ...), following a suitable temperature profile, for converting all or part of the nickel oxide (NiO) to dispersed metal Ni in a step 50.
En ce qui concerne le profil adapté, par exemple le matériau catalytique est activé sous flux d'un gaz contenant de l'hydrogène au cours d'un profil de températures comprenant une montée en température de l'ambiant jusqu'à 400°C avec une rampe de 2°C/min, et un palier de 4 heures à 400°C, préférentiellement en présence d'agents réducteurs. Plus généralement, l'étape d'activation est préférentiellement réalisée dans un domaine de température entre 300 et 500°C et de préférence entre 400 et 500°C. Le matériau catalytique proprement dit peut-être sous forme pulvérulente, dont la taille moyenne des grains varie de 1 à 100 μηπ. Le matériau catalytique peut être mis sous différentes formes (étape 45) : poudre, mousse (métallique ou céramique), coaté sur substrats céramiques (cordiérite, mullite...) ou métalliques ou encore filtres céramiques, extrudés de différentes géométries (monolobe, trilobé...), billes, pellets... With regard to the adapted profile, for example the catalytic material is activated under flow of a gas containing hydrogen during a temperature profile comprising a rise in temperature of the ambient up to 400 ° C. with a ramp of 2 ° C / min, and a plateau of 4 hours at 400 ° C, preferably in the presence of reducing agents. More generally, the activation step is preferably carried out in a temperature range between 300 and 500 ° C and preferably between 400 and 500 ° C. The catalytic material itself may be in pulverulent form, the average grain size of which varies from 1 to 100 μηπ. The catalytic material can be put into different forms (step 45): powder, foam (metallic or ceramic), coated on ceramic substrates (cordierite, mullite ...) or metallic or ceramic filters, extruded different geometries (single-layered, trilobed) ...), balls, pellets ...
Dans le cas des billes, par exemple sphériques ou oblongues, préférentiellement, leur taille moyenne est entre 100 μηπ et 1 mm, préférentiellement entre 200 et 800 μηπ et, encore plus préférentiellement, entre 200 et 600 μηπ.  In the case of balls, for example spherical or oblong, preferably, their average size is between 100 μηπ and 1 mm, preferably between 200 and 800 μηπ and, more preferably, between 200 and 600 μηπ.
Une étape d'utilisation (étape 55) du matériau catalytique comporte la conversion du monoxyde de carbone (CO) en méthane, en présence d'hydrogène (H2), éventuellement en présence de dioxyde de carbone (CO2).  A step of use (step 55) of the catalytic material comprises the conversion of carbon monoxide (CO) to methane, in the presence of hydrogen (H2), optionally in the presence of carbon dioxide (CO2).
De préférence, le gaz à convertir comporte au moins 5% de CO (teneur volumique sur gaz sec), plus préférentiellement au moins 10% de CO (teneur volumique sur gaz sec), et encore plus préférentiellement 15 % CO (teneur volumique sur gaz sec).  Preferably, the gas to be converted comprises at least 5% CO (volume content on dry gas), more preferably at least 10% CO (volume content on dry gas), and even more preferably 15% CO (gas volume content). dry).
15 % de CO (teneur volumique sur gaz sec) correspond, par exemple, à la teneur en CO minimum usuellement mesurée dans un gaz issu de gazéification à la vapeur.  15% of CO (volume content on dry gas) corresponds, for example, to the minimum CO content usually measured in a gas from gasification with steam.
On observe, en figure 3, un réacteur en lit fluidisé contenant le catalyseur, et conduisant à la conversion d'un gaz comportant au moins du monoxyde de carbone (CO) en méthane (CH4), lors du passage de ce gaz sur le catalyseur, c'est-à-dire le matériau catalytique activé. FIG. 3 shows a fluidized bed reactor containing the catalyst and leading to the conversion of a gas containing at least carbon monoxide (CO) into methane (CH 4 ) during the passage of this gas over the catalyst, that is to say the catalytic material activated.
On rappelle qu'un lit fluidisé permet de donner à une catégorie de solides, ici le catalyseur, certaines propriétés des fluides, liquides ou gaz. Il permet une forte interaction de particules de catalyseur et du gaz qui le traverse. Le principe du lit fluidisé est d'injecter sous un lit de particules solides un gaz sous pression. Ce gaz soulève et disperse les particules solides. Il permet des catalyses plus efficaces. On parle de « réacteur à lit fluidifié », ou FBR (de l'anglais : fluidized bed reactor).  It is recalled that a fluidized bed can give a class of solids, here the catalyst, some properties of fluids, liquids or gases. It allows a strong interaction of catalyst particles and the gas that passes through it. The principle of the fluidized bed is to inject under a bed of solid particles a gas under pressure. This gas lifts and disperses the solid particles. It allows more efficient catalysts. It is called "fluidized bed reactor" or FBR (fluidized bed reactor).
L'agitation particulaire et le brassage hydrodynamique par des trains de bulles gazeuses, font, des couches fluidisées, des volumes dans lesquels les particules solides sont vigoureusement agitées. Elles peuvent y échanger de la chaleur et de la matière avec une grande efficacité, par contact direct, à grande surface spécifique, avec le gaz ou avec un échangeur immergé en vue de la valorisation ou de l'élimination de la chaleur produite par la réaction de conversion du gaz comportant du monoxyde de carbone en méthane. La couche fluidisée constitue alors un volume ouvert, pratiquement isotherme, du fait de la forte capacité thermique massique des solides par rapport à celle du gaz, ainsi que par leur renouvellement au contact des surfaces d'échange. Particulate agitation and hydrodynamic stirring by gas bubble trains, fluidized layers, volumes in which the solid particles are vigorously stirred. They can exchange heat and matter with great efficiency, by direct contact, with a large specific surface area, with gas or with a submerged heat exchanger for recovery or the elimination of the heat produced by the conversion reaction of the gas containing carbon monoxide into methane. The fluidized layer then constitutes an open volume, practically isothermal, because of the high specific heat capacity of the solids relative to that of the gas, as well as by their renewal in contact with the exchange surfaces.
On observe, sur la figure 3, qui n'est pas à l'échelle, une vue schématique d'un mode de réalisation du réacteur 100. Ce réacteur 100 comporte une enceinte 105 présentant une extrémité 107 longitudinale dite « basse » et une extrémité 106 longitudinale opposée dite « haute ». L'enceinte 105 est, par exemple, formée d'un volume fermé et étanche. La forme, interne et/ou externe, de l'enceinte 105 est sans importance pour la présente invention tant que l'enceinte est rendue étanche. Par exemple, l'enceinte 105 présente une forme tubulaire, c'est-à-dire une forme cylindrique, pouvant être oblongue comme représenté en figure 3.  FIG. 3, which is not to scale, shows a schematic view of one embodiment of the reactor 100. This reactor 100 comprises an enclosure 105 having a so-called "low" longitudinal end 107 and an end 106 opposite longitudinal so-called "high". The enclosure 105 is, for example, formed of a sealed and sealed volume. The shape, internal and / or external, of the enclosure 105 is of no importance for the present invention as long as the enclosure is sealed. For example, the enclosure 105 has a tubular shape, that is to say a cylindrical shape, which can be oblong as shown in FIG.
L'enceinte 105 comporte, à proximité de l'extrémité basse 107, une entrée 1 10 de gaz comportant du monoxyde de carbone et de l'hydrogène et, éventuellement de dioxyde de carbone. L'enceinte 105 comporte, à proximité de l'extrémité haute 106, une sortie 1 15 pour méthane ou pour un gaz riche en méthane. Un matériau catalytique activé 125, non consommable par la réaction de conversion forme une couche catalytique qui est de préférence un lit fluidisé à travers lequel passe le gaz provenant de l'entrée 1 10.  The enclosure 105 comprises, near the lower end 107, a gas inlet 1 10 comprising carbon monoxide and hydrogen and, optionally, carbon dioxide. The enclosure 105 comprises, near the upper end 106, an outlet 15 for methane or for a gas rich in methane. An activated catalytic material 125 which is not consumable by the conversion reaction forms a catalytic layer which is preferably a fluidized bed through which the gas from the inlet 1 10 passes.
L'entrée, 1 10 est, par exemple, une buse d'injection, une tuyère, un tube perforé, un réseau de tuyauterie équipé de crépines. Toutefois, tout organe d'injection de fluide habituellement utilisé dans un réacteur peut être utilisé pour réaliser l'entrée 1 10. La sortie 1 15 est, par exemple, une ouverture formée dans l'enceinte 105 reliée à une canalisation de transport de méthane.  The inlet, 1 10 is, for example, an injection nozzle, a nozzle, a perforated tube, a piping network equipped with strainers. However, any fluid injection member usually used in a reactor can be used to make the inlet 1 10. The outlet 1 15 is, for example, an opening formed in the enclosure 105 connected to a methane transport pipe .
Dans des variantes, le réacteur 100 comporte des tubes d'échange de chaleur (non représentés) immergés dans l'enceinte 105 et traversés par un fluide présentant une température compatible avec la température de fonctionnement nominale à l'intérieur de l'enceinte 105 lors du fonctionnement du réacteur 100. Le fluide est à une température moins élevée que l'intérieur de l'enceinte pour permettre le maintien en température du réacteur en évacuant un excès de chaleur lié à l'exothermicité des conversions mises en œuvre. Cet excès de chaleur évacué est préférentiellement valorisé. La température moyenne du milieu réactionnel 125 et/ou la température de sortie de la couche catalytique 1 15 peuvent être inférieures à 300°C. La réaction exothermique a tendance à faire augmenter la température et, dans des modes de réalisation préférentiels, on contrôle la température de la zone réactionnelle, pour la maintenir, en moyenne, inférieure à 300°C, ce qui favorise la thermodynamique tout en permettant la réaction. On obtient ainsi une réaction dont le rendement est augmenté. In variants, the reactor 100 comprises heat exchange tubes (not shown) immersed in the enclosure 105 and traversed by a fluid having a temperature compatible with the nominal operating temperature inside the enclosure 105 when the operation of the reactor 100. The fluid is at a lower temperature than the interior of the enclosure to allow the temperature maintenance of the reactor by removing excess heat related to the exothermicity of conversions implemented. This excess heat evacuated is preferentially valued. The average temperature of the reaction medium 125 and / or the outlet temperature of the catalytic layer 1 may be less than 300 ° C. The exothermic reaction tends to increase the temperature and, in preferred embodiments, the temperature of the reaction zone is controlled to maintain, on average, less than 300 ° C., which promotes thermodynamics while allowing the reaction. This gives a reaction whose yield is increased.
Préférentiellement, la pression à l'intérieur de l'enceinte 105 se trouve entre un bar (pression atmosphérique) et 70 bar, de préférence entre 1 bar et 20 bar, et, plus préférentiellement entre 1 bar et 10 bar. Ces pressions optimisent la conversion en minimisant les coûts de compression amont.  Preferably, the pressure inside the enclosure 105 is between a bar (atmospheric pressure) and 70 bar, preferably between 1 bar and 20 bar, and more preferably between 1 bar and 10 bar. These pressures optimize conversion by minimizing upstream compression costs.
Préférentiellement, la plage de fluidisation / débit se trouve entre une fois la vitesse minimale de fluidisation et seize fois la vitesse minimale de fluidisation, de préférence entre deux fois et huit fois la vitesse minimale de fluidisation, ce qui optimise l'échange de chaleur.  Preferably, the fluidization / flow rate range is between once the minimum fluidization rate and sixteen times the minimum fluidization rate, preferably between two times and eight times the minimum fluidization speed, which optimizes the heat exchange.
En ce qui concerne la provenance du CO, du CO2, voire de l'hydrogène, le réacteur peut être précédé d'une unité de pyrolyse de matières hydrocarbonées (biomasse, déchets, charbon, ...) ou une unité de pyro-gazéification de matières hydrocarbonées (biomasse, déchets, charbon, ...) ou une unité de gazéification de matières hydrocarbonées (biomasse, déchets, charbon, ...) ou une unité de Water- Gas-Shift ou une unité de Reverse Water-Gas-Shift ou une unité de co-électrolyse de CO2/H2O, comme décrit dans la demande de brevet EP 16757688.3, incorporée ici par référence. On rappelle que le Water-Gas-Shift (WGS) est un moyen d'ajuster les teneurs en CO et le Reverse Water-Gas-Shift est un moyen de produire du CO à haute température à partir d'un mélange H2 + CO2 = CO + H2O (inverse de la réaction de Water-Gas-Shift (WGS).  Regarding the source of CO, CO2 or even hydrogen, the reactor may be preceded by a pyrolysis unit for hydrocarbon materials (biomass, waste, coal, etc.) or a pyro-gasification unit. hydrocarbon materials (biomass, waste, coal, etc.) or a gasification unit for hydrocarbon materials (biomass, waste, coal, etc.) or a Water-Gas-Shift unit or a Reverse Water-Gas unit -Shift or a co-electrolysis unit of CO2 / H2O, as described in the patent application EP 16757688.3, incorporated herein by reference. Water-Gas-Shift (WGS) is a way to adjust CO contents and Reverse Water-Gas-Shift is a way to produce high temperature CO from H2 + CO2 = CO + H2O (inverse of the Water-Gas-Shift reaction (WGS).
A titre d'exemple le catalyseur mis en œuvre par le procédé de l'invention offre une activité à 250 °C, supérieure à une technologie du marché (Technologie de référence ayant une composition 50 % de nickel sur alumine, sans praséodyme) comme le montre le tableau suivant :  By way of example, the catalyst used by the process of the invention offers an activity at 250 ° C., superior to a technology on the market (reference technology having a composition of 50% nickel on alumina, without praseodymium), such as shows the following table:
Conditions de test : température 250 °C, pression atmosphérique, vitesse volumétrique horaire VVH = 10 000 h"1. Test conditions: temperature 250 ° C, atmospheric pressure, hourly volumetric velocity VVH = 10,000 h "1 .
Composition du flux gazeux : 12 % CO, 8 % CO2, 70 % H2, 5 % H2O, 5 % CH . Composition of the gas stream: 12% CO, 8% CO2, 70% H 2 , 5% H2O, 5% CH.
Catalyseur de l'invention Catalyseur du marché Conversion CO 95 % 25 %Catalyst of the invention Catalyst of the market 95% CO conversion 25%
Conversion CO2 7,5 % 0 % CO2 conversion 7.5% 0%
Pour être actif en méthanation, le catalyseur doit subir un traitement réducteur qui modifie l'état d'oxydation du Ni et du Pr. Dans l'exemple présenté ici, le matériau catalyseur a subi au préalable un traitement réducteur sous un flux gazeux contenant de l'hydrogène à 450°C pendant une durée de quatre heures.  To be active in methanation, the catalyst must undergo a reducing treatment which modifies the oxidation state of Ni and Pr. In the example presented here, the catalyst material has previously undergone a reducing treatment under a gas stream containing hydrogen at 450 ° C for a period of four hours.
On note que le catalyseur formé avec le matériau catalytique est au moins aussi performant que le catalyseur du marché pour les températures moyennes, dans le milieu réactionnel, supérieures à 300 °C.  It is noted that the catalyst formed with the catalytic material is at least as efficient as the catalyst on the market for average temperatures in the reaction medium greater than 300 ° C.
Le matériau catalytique présente donc un domaine de températures d'utilisation plus large, de 220 à 400 °C, préférentiellement de 250 à 350 °C.  The catalytic material therefore has a wider range of operating temperatures, from 220 to 400 ° C., preferably from 250 to 350 ° C.
Dans ce test comparatif, le catalyseur mis en œuvre par le procédé de l'invention est celui de ses modes de réalisation les plus préférentiels.  In this comparative test, the catalyst used by the process of the invention is that of its most preferred embodiments.
Les taux de conversion sont définis par les ratios ([CO ou CO2]entrée - [CO ou CO2]sortie) / ([CO OU CO2]entrée). The conversion rates are defined by the ratios ([CO or CO2] input - [CO or CO2] output) / ([CO OR CO 2 ] input).
L'invention s'applique ainsi particulièrement bien au domaine de la conversion du monoxyde de carbone (CO), éventuellement en présence de dioxyde de carbone (CO2) et d'un mélange gazeux riche en hydrogène, en mélange riche en méthane (CH4) et, en particulier, aux conversions à basse température. The invention thus applies particularly well to the field of conversion of carbon monoxide (CO), optionally in the presence of carbon dioxide (CO2) and a gaseous mixture rich in hydrogen, a mixture rich in methane (CH 4 ) and, in particular, low temperature conversions.
REVENDICATIONS
1 . Procédé de conversion d'un gaz en méthane (CH4), caractérisé en ce qu'il comporte : 1. Process for converting a gas into methane (CH 4 ), characterized in that it comprises:
- une étape d'activation d'un matériau catalytique comportant de l'oxyde de praséodyme (PreOn) associé à de l'oxyde de nickel (NiO) et à de l'alumine (AI2O3), dont les proportions respectives sont, par rapport à la masse totale de ces trois composés :  a step of activating a catalytic material comprising praseodymium oxide (PreOn) combined with nickel oxide (NiO) and with alumina (Al2O3), the respective proportions of which are relative to to the total mass of these three compounds:
- PreOn : 1 à 20 % en masse,  PreOn: 1 to 20% by weight,
- NiO : 1 à 20 % en masse et  NiO: 1 to 20% by weight and
- AI2O3 : 60 à 98 % en masse ; et  Al 2 O 3: 60 to 98% by weight; and
- une étape de passage d'un gaz comportant au moins du monoxyde de carbone (CO) sur le matériau catalytique activé. - A step of passing a gas comprising at least carbon monoxide (CO) on the activated catalytic material.
2. Procédé selon la revendication 1 , dans lequel le gaz passant sur le matériau catalytique activé comporte, de plus, du dioxyde de carbone (CO2). The method of claim 1, wherein the gas passing over the activated catalytic material further comprises carbon dioxide (CO2).
3. Procédé selon l'une des revendications 1 ou 2, dans lequel la proportion de monoxyde de carbone dans le gaz parvenant au matériau catalytique activé est supérieure à cinq pourcents volumique sur gaz sec. 4. Procédé selon l'une des revendications 1 à 3, dans lequel, au cours de l'étape de passage de gaz, on fait passer un mélange gazeux contenant principalement du CO, CO2 et H2, avec une teneur en H2 supérieure à celle du CO et du CO2. 3. Method according to one of claims 1 or 2, wherein the proportion of carbon monoxide in the gas to the catalytic material activated is greater than five percent by volume on dry gas. 4. Method according to one of claims 1 to 3, wherein, during the gas passage step, is passed a gas mixture containing mainly CO, CO2 and H2, with an H2 content greater than that CO and CO2.
5. Procédé selon l'une des revendications 1 à 4, dans lequel, au cours de l'étape de passage de gaz, la température moyenne de la couche catalytique est inférieure à5. Method according to one of claims 1 to 4, wherein, during the gas passage step, the average temperature of the catalytic layer is less than
300 °C. 300 ° C.
6. Procédé selon l'une des revendications 1 à 5, qui comporte une étape de mise en forme du matériau catalytique en forme de billes, dont la taille moyenne est comprise entre 100 et 1000 μηι. 6. Method according to one of claims 1 to 5, which comprises a shaping step of the catalyst material in the form of beads, whose average size is between 100 and 1000 μηι.

Claims

7. Procédé selon l'une des revendications 1 à 6, dans lequel, avant l'étape d'activation, le matériau catalytique présente des proportions respectives, par rapport à la masse totale de ces trois composés, de : 7. Method according to one of claims 1 to 6, wherein, before the activation step, the catalytic material has respective proportions, with respect to the total mass of these three compounds, of:
- ΡΓΘΟΙ Ι : 3 à 15 % en masse,  - ΡΓΘΟΙ Ι: 3 to 15% by weight,
- NiO : 3 à 15 % en masse et  NiO: 3 to 15% by weight and
- AI2O3 : 70 à 94 % en masse.  AI2O3: 70 to 94% by weight.
8. Procédé selon l'une des revendications 1 à 7, dans lequel, avant l'étape d'activation, le matériau catalytique présente des proportions respectives, par rapport à la masse totale de ces trois composés, de : 8. Method according to one of claims 1 to 7, wherein, before the activation step, the catalytic material has respective proportions, with respect to the total mass of these three compounds, of:
- ΡΓΘΟΙ Ι : 5 à 12 % en masse,  - ΡΓΘΟΙ Ι: 5 to 12% by weight,
- NiO : 6 à 12 % en masse et  NiO: 6 to 12% by weight and
- AI2O3 : 76 à 88 % en masse. 9. Procédé selon l'une des revendications 1 à 8, dans lequel, l'alumine présente une mésoporosité correspondant à un diamètre médian des pores, déterminé par porosimétrie à intrusion de Hg, compris entre 3 et 50 nm.  AI 2 O 3: 76 to 88% by weight. 9. Method according to one of claims 1 to 8, wherein the alumina has a mesoporosity corresponding to a median pore diameter, determined by Hg intrusion porosimetry, between 3 and 50 nm.
10. Procédé selon l'une des revendications 1 à 9, dans lequel, l'alumine présente une structure gamma. 10. Process according to one of claims 1 to 9, wherein the alumina has a gamma structure.
1 1 . Procédé selon l'une des revendications 1 à 10, dans lequel, la surface spécifique SStel du matériau catalytique est comprise entre 50 et 300 m2/g. 12. Procédé selon l'une des revendications 1 à 1 1 , dans lequel, la surface spécifique SStel du matériau catalytique est comprise entre 100 à 250 m2/g. 1 1. Process according to one of Claims 1 to 10, in which the specific surface area SStel of the catalytic material is between 50 and 300 m 2 / g. 12. Method according to one of claims 1 to 1 1, wherein the SStel specific surface of the catalytic material is between 100 to 250 m 2 / g.
13. Procédé selon l'une des revendications 1 à 12, dans lequel, l'étape (50) d'activation du matériau catalytique comporte un traitement thermique en présence d'agents réducteurs. 13. Method according to one of claims 1 to 12, wherein the step (50) of activation of the catalytic material comprises a heat treatment in the presence of reducing agents.
14. Procédé selon la revendication 13, dans lequel l'étape d'activation du matériau catalytique en présence d'agents réducteurs est réalisé dans un domaine de température entre 300 et 500°C et de préférence entre 400 et 500°C. 14. The method of claim 13, wherein the step of activating the catalytic material in the presence of reducing agents is carried out in a temperature range between 300 and 500 ° C and preferably between 400 and 500 ° C.
15. Procédé selon l'une des revendications 1 à 14, qui comporte, de plus, 15. Method according to one of claims 1 to 14, which comprises, in addition,
- une étape (30) de solubilisation de sels précurseurs du nickel et du praséodyme, séparément ou en mélange,  a step (30) of solubilizing precursor salts of nickel and praseodymium, separately or as a mixture,
- une étape (35) de dépôt surfacique des sels métalliques sur un support à base d'alumine (AI2O3) et  a step (35) of surface deposition of the metal salts on an alumina-based support (Al2O3) and
- une étape (40) de décomposition thermique sous atmosphère comportant de l'oxygène et dans un domaine de température compris entre 350 et 500°C, sur une durée comprise entre une heure et quatre heures. 16. Procédé selon l'une des revendications 1 à 15, qui comporte, avant l'étape de passage du gaz, une étape de constitution du gaz comportant au moins l'une des étapes suivantes :  a thermal decomposition step (40) in an atmosphere comprising oxygen and in a temperature range of between 350 and 500 ° C., for a period of between one hour and four hours. 16. Method according to one of claims 1 to 15, which comprises, before the step of passing the gas, a gas forming step comprising at least one of the following steps:
- pyrolyse de matières hydrocarbonées,  pyrolysis of hydrocarbon materials,
- pyro-gazéification de matières hydrocarbonées  - pyro-gasification of hydrocarbon materials
- gazéification de matières hydrocarbonées,  - gasification of hydrocarbon materials,
- co-électrolyse de CO2/H2O,  co-electrolysis of CO2 / H2O,
- Water-Gas-Shift, et  - Water-Gas-Shift, and
- Reverse Water-Gas-Shift. 17. Procédé selon l'une des revendications 1 à 16, dans lequel, au cours de l'étape de passage du gaz sur le matériau catalytique activé, le gaz traverse une couche catalytique de matériau catalytique activé.  - Reverse Water-Gas-Shift. 17. Method according to one of claims 1 to 16, wherein, during the step of passing the gas on the catalytic material activated, the gas passes through a catalytic layer of catalytic material activated.
18. Procédé selon la revendication 17, dans lequel, au cours de l'étape de passage du gaz sur le matériau catalytique activé, le gaz traverse un lit fluidisé de matériau catalytique activé. 18. The method of claim 17, wherein, during the step of passing the gas over the activated catalytic material, the gas passes through a fluidized bed of catalytic material activated.
19. Procédé selon l'une des revendications 17 ou 18, qui comporte une étape de refroidissement de la couche catalytique par au moins un tube d'échange de chaleur immergé dans la couche catalytique. 19. Method according to one of claims 17 or 18, which comprises a step of cooling the catalytic layer by at least one heat exchange tube immersed in the catalytic layer.
20. Procédé de préparation de catalyseur, caractérisé en ce qu'il comporte : Process for the preparation of a catalyst, characterized in that it comprises:
- une étape (30) de solubilisation de sels précurseurs du nickel et du praséodyme, séparément ou en mélange, - une étape (35) de dépôt surfacique des sels métalliques sur un support à base d'alumine (AI2O3), a step (30) of solubilizing precursor salts of nickel and praseodymium, separately or as a mixture, a step (35) of surface deposition of the metal salts on an alumina-based support (Al2O3),
- une étape (40) de décomposition thermique sous atmosphère comportant de l'oxygène et  a step (40) for thermal decomposition under an atmosphere comprising oxygen and
- une étape (50) d'activation du matériau obtenu par traitement thermique en présence d'agents réducteurs. a step (50) of activating the material obtained by heat treatment in the presence of reducing agents.
21. Dispositif de conversion d'un gaz en méthane (CH4), caractérisé en ce qu'il comporte : 21. Device for converting a gas into methane (CH 4 ), characterized in that it comprises:
- une couche catalytique obtenue par activation d'un matériau catalytique comportant de l'oxyde de praséodyme (PreOn) associé à de l'oxyde de nickel (NiO) et à de l'alumine (AI2O3), dont les proportions respectives sont, par rapport à la masse totale de ces trois composés : a catalytic layer obtained by activating a catalytic material comprising praseodymium oxide (PreOn) combined with nickel oxide (NiO) and alumina (Al 2 O 3), the respective proportions of which are relative to the total mass of these three compounds:
- PreOn : 1 à 20 % en masse,  PreOn: 1 to 20% by weight,
- NiO : 1 à 20 % en masse et  NiO: 1 to 20% by weight and
- AI2O3 : 60 à 98 % en masse ; et  Al 2 O 3: 60 to 98% by weight; and
- un moyen de passage d'un gaz comportant au moins du monoxyde de carbone (CO) sur la couche catalytique. 22. Dispositif selon la revendication 21 , dans lequel le matériau catalytique présente des proportions respectives, par rapport à la masse totale de ces trois composés, de :  a means for passing a gas comprising at least carbon monoxide (CO) on the catalytic layer. 22. Device according to claim 21, wherein the catalytic material has respective proportions, with respect to the total mass of these three compounds, of:
- PreOn : 5 à 12 % en masse,  - PreOn: 5 to 12% in mass,
- NiO : 6 à 12 % en masse et  NiO: 6 to 12% by weight and
- AI2O3 : 76 à 88 % en masse.  AI 2 O 3: 76 to 88% by weight.
23. Dispositif selon l'une des revendications 21 ou 22, qui comporte un lit fluidisé comportant la couche catalytique. 24. Dispositif selon l'une des revendications 21 à 23, qui comporte au moins un tube d'échange de chaleur immergé dans la couche catalytique. 23. Device according to one of claims 21 or 22, which comprises a fluidized bed comprising the catalytic layer. 24. Device according to one of claims 21 to 23, which comprises at least one heat exchange tube immersed in the catalytic layer.
EP18800710.8A 2017-10-20 2018-10-22 Method for converting a gas comprising carbon monoxide into methane by means of a catalytic material containing praseodymium and nickel on alumina Pending EP3697530A1 (en)

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AUPP607198A0 (en) * 1998-09-21 1998-10-15 University Of Queensland, The Process and catalysts for the methanation of oxides of carbon
US9757714B2 (en) * 2013-02-27 2017-09-12 Haldor Topsoe A/S Methanation process using stabilized catalyst support comprising transition alumina
CN103933994B (en) * 2014-04-18 2015-12-02 昌邑凯特新材料有限公司 A kind of for CO and CO 2the preparation method of the high-temperature methanation catalyst of methane is produced with hydrogen reaction

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