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  • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
  • C07C2523/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with rare earths or actinides
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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  • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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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• 2017
  • 2017-10-20 FR FR1759927A patent/FR3072582B1/fr active Active
• 2018
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