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WO2010006386A2 - Procédé catalytique de méthanation de co<sb>2</sb> - Google Patents

Procédé catalytique de méthanation de co<sb>2</sb> Download PDF

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Publication number
WO2010006386A2
WO2010006386A2 PCT/BE2009/000036 BE2009000036W WO2010006386A2 WO 2010006386 A2 WO2010006386 A2 WO 2010006386A2 BE 2009000036 W BE2009000036 W BE 2009000036W WO 2010006386 A2 WO2010006386 A2 WO 2010006386A2
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catalyst
advantageously
volume
hydrogen
reaction
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WO2010006386A3 (fr
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Patricio Ruiz
Marc Jacquemin
Nathalie Blangenois
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Universite Catholique de Louvain UCL
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Universite Catholique de Louvain UCL
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • 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
    • 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
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/24—Chromium, molybdenum or tungsten
    • C07C2523/28—Molybdenum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/42—Platinum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/44—Palladium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/46—Ruthenium, rhodium, osmium or iridium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/72—Copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/755—Nickel

Definitions

  • the present invention relates to the methanation of CO 2 in presence of a solid methanation catalyst.
  • the provisions of the Kyoto protocol in 1997 include a mean reduction of 5.2% of the greenhouse gas emissions of 39 developed countries for the period 2008-2012, in order to limit the increase of the planet's average temperature.
  • the methanation of CO and/or CO 2 by reacting CO and/or CO 2 with hydrogen in the presence of a catalyst is disclosed in GB 2160542. According to said document, for a feedstock CO + H 2 with a molar ratio CO/H 2 of 1 :4, the catalytic activity of the catalyst is void for temperature below 250 0 C.
  • EP0087771 discloses the hydrogenation of CO and/or CO 2 in presence of a catalyst having a mesh structure coated with an alloy of nickel.
  • Example 5 of said document relates to the methanation of CO 2 . According to said document, at reaction temperature below about 150°C, no methane is formed when reacting CO 2 with H 2 with a molar ratio CO 2 /H 2 of 1 :8. According to said document, the formation of methane starts really from temperature well above 230°C, temperature at which some other by-products are formed.
  • US 4847231 relates to a mixed ruthenium catalyst for the heterogeneous catalytic gas phase methane production from hydrogen and carbon dioxide at temperatures as low as 25 °C.
  • the catalyst is a Ruthenium catalyst comprising Ru and RuO x dispersed on a semiconducting oxides support, the catalytic support comprising from 1 to 15% by weight Ru, advantageously about 3-4%.
  • the catalyst is photoexcited so as to increase the reaction rate. When using dark conditions, it is stated that the conversion rate is 4 to 5 times lower. Ruthenium is very expansive, highly toxic and carcinogenic, whereby its use is not appropriate for large CO 2 methanation process. Furthermore, the catalyst has to be phot excited, whereby restraining its use for large volume of CO 2 .
  • US3962140 relates to a nickel-copper-molybdenum methanation catalyst of CO, the CO methanation reaction being operated at a temperature from 400 to 625°C. No reference is made in said document to the methanation of CO 2 at low temperature.
  • the invention relates thus to a process for selectively producing methane by reaction of a feed gas containing CO 2 , with hydrogen or hydrogen species in the presence of a solid methanation catalyst containing less than 0.2% by weight Ruthenium, advantageously less than 0.1% by weight Ruthenium, preferably substantially free of Ruthenium, in which the reaction is carried out at a temperature below 150°C and at a pressure comprised between 10 4 Pa and 100 10 5 Pa, whereby the atomic ratio C from the CO 2 of the feed gas/ hydrogen atom from the hydrogen or hydrogen species is comprised between 0.1 and 6, preferably between 0.1 and 4, most preferably between 1 and 2.5 According to an embodiment, the reaction is carried out in presence with an excess of hydrogen with respect to the stoechiometry, i.e.
  • the catalyst is selected so that, based on thermodynamics calculation, when contacting lKmol of a feed gas consisting of 10% by volume of H 2 , 10% by volume CO 2 and 80% by volume of He at a pressure of 1 10 5 Pa and at 25 0 C, without photoexitation, a conversion rate of more than 99.7 mole %, advantageously more than 99.8 mol%, preferably about 100 mol% of H 2 and a conversion rate of CO 2 greater than 24.5 mole %, advantageously more than 24.8 mol %, preferably about 25 mol% could theoretically be achieved, while the methanation conversion selectivity is greater than 99.5%, advantageously greater than 99.85%, preferably about 99.9%- 100%.
  • the feed gas containing the CO 2 comprises some oxygen and/or CO, namely: (a) O 2 with a CO 2 ZO 2 molar ratio comprised between 98:2 and 94:6, advantageously about 95:5, and/or
  • the catalyst comprises advantageously an alumina containing support with at least one metal selected from the group consisting of Cu, Ni, Mo, Rh, Pd, Pt, Zn, Ce, Zr, V, Nb, Cr 5 W, Mn, Fe, Co, Sn, Sb, Te, Ag, Au, and mixtures thereof, advantageously at least one metal selected from the group consisting of Cu, Ni, Mo, Rh, Pd, Pt, Zn, and mixtures thereof.
  • hydrogen is advantageously produced from green energy plants, such as wind turbines, photovoltaic cells or solar panels, barrage electricity generator, etc., combined with for example by the water electrolysis.
  • Hydrogen can also be produced by electrolysis by using electricity from a nuclear power plant, or can be a by-product of some chemical reaction, for example a byproduct of reformer of petrochemical plants.
  • the invention is thus also a process in which the CO 2 is stored in container, subsurface cavity, etc. at least partly as methane gas, the methanation reaction being carried advantageously after introducing CO 2 into said containers or subsurface cavities or tanks.
  • the alumina containing support is advantageously a gamma alumina, a zeolite or a hydrate aluminosilicate, said zeolite being for example natural zeolite or synthetic zeolite (Y, X, ZSM-5, etc.).
  • the zeolite is advantageously acid or a ZSM-5 or Y- zeolite.
  • the alumina support can also be porous materials comprising alumina such as materials having advantageously a mesoporosity or materials for which 50% of the open porosity is formed by mesopores.
  • the alumina containing support can be modified with one or more elements, such as Ti, Zr, Ce, etc., as well as mixtures of such elements.
  • the support can also be a silica and/or activated carbon containing support, advantageously a porous silica and/or activated carbon containing support, such as materials having advantageously a mesoporosity or materials for which 50% of the open porosity is formed by mesopores.
  • the silica and/or activated carbon containing support can be modified with one or more elements, such as Ti, Zr, Ce, etc., as well as mixtures of such elements.
  • the metal content of the catalyst is advantageously lower than 3% by weight.
  • the metal (advantageously Cu, Ni, Mo, Rh, Pd, Pt, Zn) content of the catalyst is higher than 3% by weight.
  • a high metal content advantageously Cu, Ni, Mo, Rh, Pd, Pt, Zn
  • the catalyst support comprises Al and/or Si and/or activated carbon, whereby the weight ratio of metal selected from the group consisting of Cu, Ni, Mo, Rh, Pd, Pt, Zn, Zr, Ce, V, Nb, Cr 5 W, Mn 5 Fe, Co 5 Sn, Sb, Te, Ag, Au, and mixtures thereof ( advantageously at least one metal selected from the group consisting of Cu 5 Ni 5 Mo, Rh 5 Pd, Pt 5 Zn and mixtures thereof) (expressed as metal)/ Al expressed as Al 2 O 3 or (expressed as metal) and/or Si expressed as SiO 2 or expressed as metal (for example Al expressed as Al 2 O 3 + Si expressed as SiO 2 ) and/or activated carbon expressed as C is advantageously lower than 4:100, preferably comprised between 0.3 and 3 : 100, for example 0.5:100; 1:100; 1.5 : 100; 2 : 100.
  • said activated carbon seems to be a cocatalyst and/or a promoter for the methanation reaction.
  • the catalyst may comprise one or more metals other than Cu, Ni, Mo, Rh, Pd, Pt, Zn, Zr, Ce, V, Nb, Cr 5 W, Mn 5 Fe, Co 5 Sn, Sb 5 Te 5 Ag, Au, advantageously one or more metals other than Cu, Ni, Mo, Rh 5 Pd, Pt and Zn 5 such as preferably Zr, Ce, V, Nb, Cr 5 W, Mn 5 Fe 5 Co 5 Sn, Sb, Te, Ag, Au and mixtures thereof.
  • said other metal/metals is then present in the catalytic portion of the catalyst in an amount of less than 20% , advantageously less than 10%, preferably less than 5% of the weight of the metal selected from the group consisting of Cu, Ni 5 Mo, Rh, Pd 5 Pt 5 Zn, Zr, Ce, V, Nb, Cr 5 W 5 Mn 5 Fe 5 Co 5 Sn 5 Sb 5 Te, Ag 5 Au 55 and mixtures thereof.
  • the other metal(s) is selected from the group Zr 5 Ce 5 V 5 Nb, Cr 5 W, Mn 5 Fe, Co 5 Sn, Sb, Te, Ag 5 Au and mixtures thereof
  • said other metal/metals is then present in the catalytic portion of the catalyst in an amount of less than 20% , advantageously less than 10%, preferably less than 5% of the weight of the metal selected from the group consisting of Cu, Ni, Mo, Rh, Pd, Pt, Zn and mixtures thereof.
  • metal(s) possibly present as co-catalyst mean : Lithium, beryllium, sodium, magnesium, potassium, calcium, scandium, titanium, gallium, rubidium, strontium, yttrium, , technetium, ruthenium, cadmium, indium, caesium, barium, lanthanum, hafnium, tantalum, rhenium, osmium, iridium, , mercury, thallium, and lead,.
  • the Al support preferably the Al-Si support is advantageously as taught in US2008/128324, the content of which is hereafter partly disclosed.
  • the metal compound(s) is/are supported advantageously on a high surface area inorganic oxide support.
  • a key component of the support seems to be a large pore molecular sieve such as X, Y, L, ZSM-X and omega zeolite with ZSM-5 and Y zeolite being preferred.
  • the catalyst is devoid of beta zeolite.
  • Modified, hydrothermally stabilized and ultra-stable Y-zeolites are highly preferred.
  • the preferred molecular sieve can be modified by ion exchanging to remove alkali ions with hydrogen ions or hydrogen ion precursors such as ammonium ions.
  • Suitable alkali ion contents are less than 1.0 weight %, preferably less than 0.5 weight %, for example between 0.1 and 0.4 weight%.
  • the desired molecular sieve can also be ion exchanged and/or hydrothermally treated and/or acid washed to increase the molar silica to alumina ratio.
  • Preferred silica to alumina mole ratios are at least 10 and preferably at least 25. Silica to alumina mole ratios of 30 and higher are most preferred.
  • the catalyst support can also comprise at least one inorganic oxide.
  • Suitable inorganic oxides include alumina, silica, titanium, zirconia, barium, cerium and their binary and tertiary combinations especially silica-alumina, silica-titania, silica-zirconia-titania, zirconia-ceria, zirconia-barium oxide, etc.
  • the support may optionally also contain an inorganic oxide binder.
  • a particularly suitable binder is alumina especially when peptized with an acid.
  • a most preferred binder alumina is a pseudo boehmite alumina Catapal ® currently available from the Sasol North America Inc.
  • alumina, silica, zeolite, activated carbon, mesoporous and amorphous component required in the catalyst and catalyst support suitable for use in the process of the invention are embodied into particles which contain both components.
  • Convenient methods for physically integrating the two components into individual particulates include comulling a wetted mixture of the components and then extruding the comulled material through a die having small openings therein of desired cross-sectional size and shape, e.g. circle, trilobal clover leaf, quadrolobal clover leafs, etc., breaking or cutting the extruded matter into appropriate lengths, drying the extrudates and then calcining at a temperature, e.g. 480°C or higher.
  • a material is produced that is suitable for use in high temperature chemical conversion reactions, and the material has e.g. trilobal or quadrolobal shapes, as shown for example in FIGS. 8 and 10, respectively, in U.S. Pat. No. 4,028,227 herein incorporated by reference in its entirety.
  • the amorphous components may be oxides of silica-alumina.
  • Other amorphous components useful in the process of the invention are silica, alumina, titania, zirconia, ceria, chromia and their binary and ternary combinations.
  • the amorphous oxides besides contributing to the catalytic properties of the catalyst support also serve as binders for the modified zeolites.
  • Alumina and other conventional amorphous, inorganic refractory oxide binder components may be desired.
  • an amorphous, inorganic refractory oxide component is used as a binder material to hold the zeolite, silica, alumina, activated carbon, mesoporous, amorphous oxides and other suitable components together in the catalyst support
  • other such components can also be incorporated into the co mulled mixture including for example, inorganic refractory oxide diluents, which may or may not possess some type of catalyst activity.
  • examples of such diluents include clays, alumina, silica-alumina and a heterogeneous dispersion of finely divided silica-alumina particles in an alumina matrix, the dispersion of which is described in detail in U.S. Pat. Nos.
  • zeolites used in the process of the invention usually have the original cations associated therewith replaced by a wide variety of other cations according to techniques well known in the art. Typical replacing cations would include hydrogen, ammonium and metal cations such as rare earths, including mixtures of the same. Of the replacing cations, particular preference is given to cations of ammonium and hydrogen.
  • Typical ion exchange techniques would be to contact the particular zeolite with a solution of a salt of the desired replacing cation or cations.
  • a salt of the desired replacing cation or cations can be employed, particular preference is given to chlorides, nitrates and sulphates.
  • the zeolite which may be used is the ultra-stable Y-zeolite.
  • the ultra-stable zeolites disclosed herein are well known to those skilled in the art. For example, they are described at pages 507-522 and pages 527 and 528 of the book Zeolite Molecular Sieves by Donald W. Breck, John Wiley & Sons, Inc. 1974 and are exemplified in U.S. Pat. Nos. 3,293,192 and 3,449,070. These two patents and the reference to Breck above are incorporated herein by reference.
  • the low soda, ultra stable zeolites are available commercially from W. R. Grace & Company, Zeolyst International and Tosoh Corporation among others.
  • the Y-zeolites have advantageously pore diameters in the range of 0.7 to 1.5 nm.
  • the preferred Y zeolite for use is a modified zeolite having a unit cell constant in the range 24.26 to 24.30 A.
  • the Y-zeolite useful in the process of the invention should have a molar SiO 2 to Al 2 O 3 ratio of at least 5 and preferably at least 10 and more preferably at least 25 and most preferably at least 30.
  • the methanation catalyst comprises:
  • a ⁇ - Al 2 O 3 containing support provided with Rh, optionally possibly with one or more catalytic elements selected from the group consisting of Cu, Ni, Mo, Rh, Pd, Pt, Zn, Zr, Ce, V, Nb, Cr 5 W, Mn 5 Fe, Co 5 Sn 5 Sb 5 Te 5 Ag, Au, and mixtures thereof, the metal Rh weight content of said ⁇ - Al 2 O 3 containing support being comprised between 1 and 5%, and
  • activated carbon particles having a BET surface area of more than 300m 2 /g, advantageously more than 500m 2 /g, a mesopore volume of more than 0.3cm 3 /g, advanatgeously more than 0.4cmVg, a micropore volume of more than 0.15cm 3 /g, advantageously more than 0.2cmVg, and an average (in volume) pore diameter comprised between lnm and 5nm, advantageously between 1.5nm and 3nm, said activated carbon particles being optionally provided with one or more catalytic elements selected from the group consisting of Cu 5 Ni, Mo, Rh, Pd 5 Pt 5 Zn 5 Zr, Ce, V, Nb, Cr 5 W, Mn 5 Fe, Co,Sn, Sb 5 Te, Ag, Au, whereby the weight ratio ⁇ - Al 2 O 3 containing support provided with Rh / activated carbon particles is comprised between 5:95 and 25:75, advantageously between 10:90 and 60:40, preferably
  • the reaction is advantageously carried out at a temperature comprised between -20°C and 75°C, preferably between -5°C and 30°C and at a pressure comprised between 10 4 Pa and 10 10 5 Pa 5 preferably between 0.5 10 5 Pa and 2 10 5 Pa 5 most preferably at about atmospheric pressure.
  • the water vapour formed during the methanation reaction of CO 2 is at least partly adsorbed and/or condensed, during the reaction.
  • hydrogen and/or hydrogen species are directed towards the solid methanation catalyst.
  • the feed gas is pretreated before contacting the solid methanation catalyst, so as to reduce the water content of said feed gas to less than 5% by volume, advantageously to less than 2% by volume, preferably to less than 1% by volume, most preferably less than 0.5% by volume.
  • the feed gas is pretreated before contacting the solid methanation catalyst so as to reduce the Oxygen content or the O species content in the feed gas to less than 10% by volume, advantageously to less than 5% by volume, advantageously to less than 2% by volume, preferably to less than 1% by volume, preferably less than 0.5% by volume, most preferably less than 0.1% by volume.
  • the feed gas has a nitrogen content of less than 10% by volume, advantageously less than 5% by volume, preferably less than 2% by volume.
  • the feed gas has an inert gas content, advantageously nitrogen, of more than 10% by volume, advantageously more than 15% by volume, preferably more than 20% by volume.
  • more than 98% by volume, advantageously more than 99% by volume of the feed gas consists of a) H 2 and/or CO 2 , b) N 2 and/or He, preferably N 2 , and possibly c) H 2 O.
  • more than 98% (preferably more than 99%) by volume of the feed gas consists of a) H 2 and/or CO 2 , and b) N 2 .
  • the process can be carried by contacting the solid methanation catalyst simultaneously with CO 2 and H 2 , or successively.
  • the feed gas will successively be a CO 2 containing feed gas (with no or substantially no H 2 ) and a H 2 containing feed gas (with no or substantially no CO 2 ).
  • the methanation OfCO 2 is operated according to a two-stage reaction pattern, whereby in a first stage, a feed gas comprising at least 5% by volume, advantageously at least 10% by volume, preferably at least 20% by volume CO 2 is contacting the solid methanation catalyst at a temperature below 150°C and at a pressure comprised between 10 4 Pa and 100 10 5 Pa, (the solid methanation catalyst has advantageously a high BET surface area for example of more than 75 nrVg, such as more than 100m 2 /g, more than 15OmVg, etc.) , whereby in said first stage CO 2 is at least partly dissociated at least into CO species (advantageously into CO species and into O species) onto the solid methanation catalyst, said CO species (advantageously CO species and O species) being adsorbed or attached to the methanation solid catalyst, while in a second stage, the so formed CO species (advantageously CO species and O species) present on the solid methanation catalyst are reacted
  • the so formed methane is then desorbed from the solid catalyst system, simultaneously or not with the water vapour.
  • the process has an intermediate reaction step for the hydrogen, according to which the H 2 gas is first adsorbed on the solid catalyst system, then dissociated into H species, said species being still adsorbed on the solid catalyst system whereby said H species are then reacting with CO species and O species present on the solid catalyst system for forming respectively CH 4 gas adsorbed on the solid catalyst system and water vapour adsorbed on the solid catalyst system, said methane and water vapour being finally desorbed from the solid catalyst system.
  • the feed gas comprising at least 5% by volume, advantageously at least 10% by volume, preferably at least 20% by volume CO 2 , contacting the solid methanation catalyst comprises less than 5% by volume, advantageously less than 2% by volume of hydrogen.
  • the solid methanation catalyst is contacted with hydrogen gas with a CO 2 volume content of less than 10% by volume, advantageously less than 5%, preferably less than 2%.
  • the solid methanation catalyst is selected so as to catalyse the dissociation of CO 2 at a temperature below 150°C and at a pressure comprised between 10 4 Pa and 100 10 5 Pa, as well as to catalyse the reaction of CO species and O species with hydrogen or hydrogen species at a temperature below 150°C and at a pressure comprised between 10 4 Pa and 100 10 5 Pa.
  • pressure are 0.5 10 5 Pa; 1 10 5 Pa ; 2 10 5 Pa; 5 10 5 Pa; 10 10 5 Pa, 15 10 5 Pa; 20 10 5 Pa; 30 10 s Pa; 50 10 5 Pa, and 75 10 5 Pa.
  • the pressure can be modified successively, for example a higher pressure will be used for favourizing the adsorption of CO 2 and/or H 2 , while a lower pressure (with respect to the pressure used for the adsorption step) will be used for the desorption of methane and water vapor.
  • a pressure which is at least 0.2 10 5 Pa, advantageously at least 0.5 10 5 Pa, preferably at least 1 10 5 Pa, or even more, lower than the pressure used for the adsorption step(s) Of CO 2 and/or H 2 .
  • the solid methanation catalyst can be further provided or associated with or more additives, such as rare earth elements, possibly as oxides, hydroxides, etc.
  • additives such as rare earth elements, possibly as oxides, hydroxides, etc.
  • rare earth additives cerium, lanthanum, praseodynium, their oxides, hydroxides and mixtures thereof can be cited.
  • the solid methanation catalyst can also be a mixture of two or more different solid methanation catalysts. In case of a mixture of catalysts, a first catalyst will advantageously be selected for favourizing the formation of at least CO species and O species from adsorbed CO 2 gas, while the second catalyst will be selected for favourizing the formation of H species from adsorbed H 2 gas.
  • the process can be carried out by using a tube reactor with cooling element(s) or face(s), so as to ensure a temperature of less than 150°C, advantageously of less than 100°C.
  • a portion of the reactor is cooled at a lower temperature than the temperature of another portion of the reactor.
  • said lower temperature will be sufficient for enabling water to be condensed and separated.
  • the condensation and separation of water can be quite easily be operated, whereby favouring the formation of dried methane.
  • the reactor comprised a porous envelope or membrane separating the volume or the flow of CO 2 from the volume or the flow ofH 2 , said porous envelope being provided or coated with solid methanation catalyst.
  • the pressure of hydrogen is higher than the pressure of CO 2 so that hydrogen flows into the envelope towards the volume or flow of CO 2 .
  • the pressure of hydrogen will be controlled with respect to the pressure of CO 2 , so as to adapt the passage of hydrogen substantially to the required amount for the methanation of CO 2 dissociated onto the solid methanation catalyst.
  • the reactor comprised a porous envelope or membrane separating the volume or the flow of CO 2 from the volume or the flow ofH 2 , said porous envelope being provided or coated with solid methanation catalyst.
  • the pressure OfCO 2 is higher than the pressure of hydrogen so that CO 2 flows into the envelope towards the volume or flow of hydrogen.
  • the pressure of CO 2 will be controlled with respect to the pressure of hydrogen, so as to adapt the passage of CO 2 substantially to the required amount for the methanation of hydrogen dissociated onto the solid methanation catalyst.
  • the process can be carried out by using other embodiments as batch reactor, two- step reactor, parallel reactor as indicated below
  • the process can be used for the treatment of CO 2 exhaust gases, after said gases have been cooled down, and possibly further treated.
  • the flue gases issuing from the calcination step of carbonate (calcium and/or magnesium) are treated (for example for removing dusts, cooled, advantageously dried and eventually purified (for example for removing some gases, such as N0 ⁇ , SOx, etc.), and then treated with hydrogen in presence of a methanation catalyst at a temperature below 150°C, advantageously below 100°C, preferably below 50°C.
  • the flue gases can also be industrial gases from cement production plant, from waste incineration plants, electricity production plant, refinery plants, chemical production plants, etc.
  • the reaction is carried out in a tubular reactor provided with a cooling envelope , whereby the catalyst in the form of particles fills at least a portion of the tubular reactor , whereby the reactor is advantageously provided and/or associated with one or more means for controlling the water removal and/or water condensation and/or with water adsorbing material, or - the reaction is carried out can be operated in a reactor having the form of a heat exchanger of the tube bundle type, with end headers, the one for distributing the gases to be reacted into the tubes, the other for collecting the reaction products, whereby catalyst is present inside the tubes or at least portions thereof, or - the reaction is at least partly carried out in a large subsurface cavity provided with a methanation catalyst and/or provided with one or more injection pipe(s) and/or tube(s) extending at least partly within the cavity, said pipe(s) and/or tube(s) or portion(s) thereof being provided with catalyst, or
  • the reaction is carried out at least partly as a pulse type reaction, i.e. a reaction in which the catalyst containing reactor is first fed with hydrogen gas, advantageously with a low CO 2 content, and then with CO 2 gas, advantageously with a low H 2 content, or a reaction in which the catalyst containing reactor is first fed with CO 2 gas, advantageously with a low H 2 content, and then with hydrogen gas, advantageously with a low CO 2 content, whereby said reaction is advantageously carried out in two or more reactors mounted in parallel, so that when one reactor is fed with hydrogen gas, another is fed with CO 2 gas, whereby enabling a substantially continuous methane production, or
  • the reaction is carried out in a reactor comprising a first chamber in which hydrogen is admitted, a second chamber in which whereby a CO 2 gas is introduced, and a porous membrane provided with a methanation catalyst and possibly with inner cooling pipe, said membrane separating the first chamber from the second chamber, whereby at least one chamber is provided with a means evacuating a methane containing gas.
  • a support such as an alumine support and/or a carbon support and/or an activated carbon support.
  • the metal deposit can be carried out by methods comprising impregnation step, sol-gel composition, coprecipitation or even by simple mechanical mixing.
  • Example 1 Catalyst I - NiMoO 4
  • the molybdenum solution was added drop by drop to the Nickel solution under stirring. Ammonia was added to maintain the pH to 6.
  • the solution was stirred for 4 hours at 60°C. A green precipitate was formed. Said green precipitate was filtered and cleaned with distilled water.
  • the fraction of the coated particles with a size comprised between 200 and 315 ⁇ m was kept for testing, the catalytic particles of said fraction had a BET surface area of 58 m 2 /g.
  • NiMoO 4 is present essentially as ⁇ - NiMoO 4 .
  • X ray Photoelectron Spectroscopy it appears that Ni and Mo are in a full oxidation state, the molybdenum being most probably present as molybdate and as MoO 3 crystal.
  • the fraction of catalysts (after being reduced under H 2 at 250°C) with a particle size comprised between 200 ⁇ m and 315 ⁇ m had the following properties : BET surface area: 59 m 2 /g Rh metallic content: about 1% by weight Average diameter of the pores (average in volume): 180 A Total porosity: 0.28 cmVg
  • the Rhodium present on the catalyst support is not crystalline Rh, nor Rh 2 O 3 .
  • ZSM-5 support in ammonia form was burned for 16 hours at 500°C, so as to convert said zeolite support in H - ZSM-5.
  • a solution of Cu(NO 3 ) 2 0.05M was prepared by dissolving 2.42g of Cu(NOs) 2 in 200ml of distilled water. The solution was stirred and heated at 50°C. 1Og of H- ZSM-5 support was added to the solution. An ionic exchange was carried out by stirring the solution at 25°C for 2hours. The precipitate was filtered and cleaned three times with distilled water. The so prepared catalyst was then dried at 120 0 C for 14hours. After said drying step, the catalyst was burned for 4 hours at 450°C.
  • the fraction of catalysts (after being reduced under H 2 at 300°C) with a particle size comprised between 200 ⁇ m and 315 ⁇ m had the following properties :
  • ZSM-5 support in ammonia form was burned for 16 hours at 500°C, so as to convert said zeolite support in H - ZSM-5.
  • a solution of Ni(NO 3 ) 2 was prepared by dissolving 2.91g of Ni(NOa) 2 -OH 2 O in 200ml of distilled water. The solution was stirred and heated at 50°C. 1Og of H- ZSM-5 support was added to the solution. An ionic exchange was carried out by stirring the solution at 25 0 C for 2hours. The precipitate was filtered and cleaned three times with distilled water. The so prepared catalyst was then dried at 12O 0 C for 14hours. After said drying step, the catalyst was burned for 4 hours at 450 0 C.
  • the fraction of catalysts (after being reduced under H 2 at 300°C) with a particle size comprised between 200 ⁇ m and 315 ⁇ m had the following properties:
  • Ni metallic content about 0.6% by weight
  • Oxygen is removed from the heating chamber by a flow of nitrogen up to an oxygen volume content of less than 0.5% in the atmosphere of the heating chamber.
  • Gas mixture of H 2 (5% by volume) / 95% by volume N 2 is then introduced in the heating chamber so as to reduce the palladium for 3 hours at 400 0 C.
  • the so reduced catalyst is then burned for 3 hours at 600 0 C under air in a muffle furnace.
  • the fraction of catalysts with a particle size comprised between 200 ⁇ m and 315 ⁇ m had the following properties :
  • Pd metallic content about 1.5% by weight Average diameter of the pores (average in volume): 180 A
  • Example 6 Catalyst VI : catalyst V with some CeO?
  • This catalyst was prepared by mixing powder of catalyst V with CeO 2 particles with a particle size of less than 315 ⁇ m.
  • the CeO 2 particles used for the various catalysts VI had the following weight average particle size :
  • the weight ratio catalyst V / CeO 2 as well as by modifying the average weight particle size of CeO 2 was the following :
  • Example 7 Catalyst VII - Rh (1%) on ⁇ - Al 7 O ⁇
  • Rh containing aqueous solution has been prepared by mixing 0.411 g RhCl 6 (NH 4 ) 4 .3H 2 O in 200ml demineralized water. 1Og of alumine 7-Al 2 O 3 is added to said 200ml Rh containing solution.
  • Said alumine has a particle size of about 3 ⁇ m, a BET surface area between 80 and 120m 2 , and a purity of more than 99.9% (on metal basis, for example a purity of more than 99.95%, such 99.97% or higher).
  • the alumine (without addition of Rhodium) or previous addition of rhodium has the following porosity characteristics :
  • the volume of mesopores (pores with a diameter comprised between 2nm and 50nm) is 0.2 cmVg, as fresh material or after a burning step
  • the volume of micropore (pores with a diameter below 2nm ) is 0.005 cmVg for the fresh material and 0.001 after burning.
  • the average pore diameter (in volume) is about 14.2nm for the fresh material and about 12.5nm after burning.
  • the impregnation of the alumine particles was carried out at 6O 0 C, under stirring for 18 hours. Thereafter, the mixture was evaporated at 30 0 C by using a rotary evaporator. After said water evaporation, the particles are air dried at 110°C for 24 hours, and then calcined or burned at 450°C in an air atmosphere for 2 hours. The solid particles were sieved so as to recover the fraction of particles with a particle size comprised between 200 ⁇ m and 315 ⁇ m. Said solid particles had a Rh content of 1% by weight.
  • the reduced catalyst was analyzed by spectroscopy, physisorption, BET analysis, etc . According to said analysis, a weight content of 1.1% was measured.
  • the surface area was about 7OmVg
  • the volume of mesopores pores with a diameter comprised between 2nm and 50nm
  • a volume of micropore pores with a diameter below 2nm
  • CO 2 and hydrogen was passed through the reduced catalyst, in order to determine possible porosity modification. No reduction of porosity was observed after passage of CO 2 and H 2 , alone or as a mix.
  • Rhodium containing catalyst after being burned had higher porosity than the pure alumine support after burning.
  • Examples 1 to 6 have been repeated, except that activated carbon was used as support, the activated carbon particles having a BET surface area (before the coating) of 100m7g, 150m7g, 20OmVg, 300m7g, 500m7g, 700m7g, 1000m7g and about 1200m7g.
  • Examples 1 to 6 have been repeated, except that the various catalysts have been mixed with activated carbon particles, said activated carbon particles with a particle size of less than 500 ⁇ m and having a BET surface area (before the coating) of 100m7g, 150m7g, 200m7g and 300m7g.
  • the weight ratio catalyst/activated carbon particles was 10, 2, 1, 0.5 and 0.1 (i.e. between the advantageous range of 1 : 20 and 20: 1.
  • Example 10 Catalyst VIII - Ni on activated carbon particles
  • Ni acetate Ni (CH 3 COO) 2 .4H 2 O
  • 20ml demineralized water Three Ni solutions were prepared. The quantity of Ni acetate added to the respective solution was determined for preparing Ni coated particles (after drying and reduction) with respectively 0.5% by weight Ni (with respect to the total weight), 1% by weight Ni, and 5% by weight.
  • Activated carbon particles in the form of particles with a size comprised between 500 and 800 ⁇ m, BET Surface area of about 1250 m 2 /g, volume of mesopores (pores with a diameter comprised between 2nm and 50nm) of about 0.5 cmVg, a volume of micropore (pores with a diameter below 2nm ) of 0.3 cmVg, and an average in volume pore diameter of 2.2nm ) were added respectively to the three Ni solutions. The solutions were stirred for 1 hour in a vial at 80°C under reflux.
  • the dried impregnated carbon particles are then submitted to a reduction step.
  • Said reduction step is carried out by using an aqueous solution of hydrazine (with a hydrazine content of about 25% by weight).
  • the reduction step of the Ni compound deposited on the activated carbon particles had no influence on the porosity, nor on the average pore diameter, said porosity and average pore diameter corresponding to the porosity and average pore diameter of the fresh activated carbon support.
  • the impregnated particles is mixed with 60 ml distilled water, under stirring, in a vial provided a condenser for reflux.
  • the solution is heated up to 80°C.
  • 10ml hydrazine solution was added.
  • Reduced Ni (0.5%)/ activated carbon (catalyst Villa) with a theoretical Ni content of 0.5% (weight) and a measured Ni content of 0.5% (weight) (Catalyst Vila).
  • Reduced Ni (1%)/ activated carbon (catalyst VIIIb) with a theoretical Ni content of 1% and a measured Ni content of 0.9% (Catalyst VIIb).
  • Reduced Ni (%)/ activated carbon (catalyst VIIIc) with a theoretical Ni content of 5% and a measured Ni content of 2.4% (Catalyst Vila).
  • Catalysts of examples 1 to 10 can be mixed together.
  • the catalyst particles can be simply be mechanically mixed, with or without a liquid medium, such as water, alcohol, solvents, pentane, tensio active compounds, etc., and mixtures thereof.
  • the mixture of catalyst particles can be crushed together if required.
  • the following method can be used for mixing together two different catalyst particles.
  • Solid catalyst A for example a Rhodium containing catalyst or an alumine catalyst, such as catalyst II or VII
  • solid catalyst B for example a Ni containing catalyst or an activated carbon catalyst, for example catalysts Villa and/or VIIIb and/or VIIIc
  • an organic medium such as n-pentane (HPLC grade, purity higher than 98% by weight, for example about 99%)
  • the quantity of catalyst A and catalyst B added to the liquid medium is selected in function of the desired ratio Catalyst A/Catalyst B.
  • the mixing is carried at a temperature below the evaporation temperature of the liquid medium (for example at a temperature comprised between 10°C and 25°C for pentane), possibly under pressure, by a first gentle mechanical mixing for a time comprised between 1 and lOminutes, followed by an ultrasound mixing for less than 2 minutes. Said steps are repeated several times if required.
  • the solution is then submitted to a gentle evaporation, for example at a temperature of about 30°C for pentane. The temperature will be selected for avoiding degradation of catalyst particles due to a too quick evaporation of the liquid.
  • the dried mixture of catalyst is sieved so as to recover the solid fraction 500 ⁇ m 800 ⁇ m.
  • the mixtures can be prepared by various methods, such as dry and wet mechanicla mixing..
  • Solid catalyst A for example a Rhodium containing catalyst or an alumine catalyst, such as catalyst II or VII
  • activated carbon particles having a surface area of more than 10OmVg, advantageously more than 500m 2 /g, preferably more than lOOO ⁇ vVg are added in an organic liquid medium, such as n-pentane (HPLC grade, purity higher than 98% by weight, for example about 99%)
  • the quantity of catalyst A and activated carbon particles added to the liquid medium is selected in function of the desired ratio Catalyst A/activated particles.
  • Said ratio Catalyst A/activated carbon particles is advantageously comprised between 1 :20 and 4:1, preferably between 1 :10 and 3:1, most preferably between 1:4 and 6:4, more specifically about 1.5:1 to 1:1.
  • the mixing is carried at a temperature below the evaporation temperature of the liquid medium (for example at a temperature comprised between 10°C and 25°C for pentane), possibly under pressure, by a first gentle mechanical mixing for a time comprised between 1 and lOminutes, followed by an ultrasound mixing for less than 2 minutes. Said steps are repeated several times if required.
  • the solution is then submitted to a gentle evaporation, for example at a temperature of about 30°C for pentane.
  • the temperature will be selected for avoiding degradation of catalyst particles due to a too quick evaporation of the liquid.
  • the dried mixture of catalyst is sieved so as to recover the solid fraction 500 ⁇ m - 800 ⁇ m.
  • - volume of mesopores (pores with a diameter comprised between 2nm and 50nm) of more than 0.3cmVg, advantageously more than 0.4cm 3 /g, for example about 0.5 cm7g,
  • a volume of micropores (pores with a diameter below 2nm ) of more than 0.15cm7g, advantageously more than 0.2 cmVg, for example 0.3 cmVg,
  • the following Mix XII have been prepared and are given as examples only.
  • the activated carbon particles used in the Mix XII disclosed in the following table has the characteristics of the activated particles used in example 10. Weight content (%) of catalyst and activated carbon
  • the catalyst of examples 1 to 4 was sieved so as to keep the fraction between 200 ⁇ m and 315 ⁇ m.
  • each of the catalysts selected from the catalyst of the group consisting of catalysts of examples 1 to 6 - fraction between 200 ⁇ m and 315 ⁇ m -, as well as mixtures thereof, were placed in a quartz reactor.
  • the catalyst was first reduced under H 2 for one hour, except for catalysts I,.
  • the temperature of reduction was 350°C for catalyst II, 250 0 C for catalysts III, 700 °C for catalysts IV and 300°C for catalysts V. .
  • the pressure of the reactor was kept at about atmospheric pressure (10 5 Pa).
  • the gas flowing outside of the reaction chamber were analysed so as to evaluate the formation of methane.
  • the analysis of reactants and reaction products was carried out by Mass spectrometry.
  • X ray Photoelectron Spectroscopy analyses were performed on the various catalysts after its preparation as well as after a reaction step. No major modifications, except a reoxidation of Rh were observed for the catalysts after its preparation and after its use, whereby said catalysts can be considered as being stable, and suitable for being used for a long time.
  • catalyst II enabled the highest methane formation, with a selectivity of about 100%. It seems thus that catalysts comprising Rh deposit on alumina containing support, advantageously on ⁇ -
  • Al 2 O 3 containing support for example Rh directly deposited on ⁇ - Al 2 O 3 support or particles, are particularly advantageous for catalysing the methanation of CO 2 at low temperature, such as at temperature comprised between 0°C and 50°C.
  • methanation rate methane formation rate
  • the gaseous medium consists of :
  • the reaction pressure was different from about atmospheric pressure.
  • the reaction pressure was 2 10 5 Pa, 5 10 5 Pa, 10 10 5 Pa and 20 10 5 Pa.
  • Higher pressure such as from 5 10 s Pa to 20 10 5 Pa seems interesting for a better methanation rate per gram of catalyst.
  • Tests were also made by using a zeolite support not coated or provided with Cu, Ni, Mo, Rh, Pd, Pt, Zn, Zr, Ce, V, Nb, Cr 5 W, Mn 5 Fe, Co 5 Sn, Sb, Te, Ag 5 Au 5 . No catalytic effect was observed for the zeolite support as such, as no methanation at all was achieved.
  • the methanation rate was estimated for the catalyst II with a reaction temperature of 25°C. It was observed that with said catalyst, it was possible to achieve a methanation rate (rate of formation of methane) higher than 0.1 10 3 ⁇ mol per gram of catalyst and per minute, advantageously higher than 0.32 10 ⁇ mol per gram catalyst and per minute, preferably equal to about or even higher than 0.45 10 ⁇ mol per gram and per minute , more preferably higher than 1.1 xl O 3 ⁇ mol per gram and per minute , with always a selectivity of about 100%. Pulse Tests with Catalysts VIL VIIIc and mixtures of catalysts
  • the catalyst Prior testing the catalyst, the catalyst has been treated for 1 hour with hydrogen gas for 1 hour at a temperature of 350°C.
  • the catalyst was deposited on inert glass beads.
  • a determined quantity of CO 2 is present in a closed loop circuit with a reactor containing the catalyst, said CO 2 being introduced in the reactor by a gas, such as helium or hydrogen.
  • a gas such as helium or hydrogen.
  • the pressure was varied from atmospheric pressure 10 5 Pa and 2.8 x 10 5 Pa.
  • the selectivity in methane was 100%.
  • the pressure of the gas carrier (mix hydrogen - helium) was 3 10 5 Pa.
  • the selectivity in methane was 100%.
  • the pressure of the gas carrier (mix hydrogen - helium) was 2 10 5 Pa, while the reaction temperature was 125°C.
  • the methane production (with a selectivity of 100%) corresponds to about a conversion of about 4% OfCO 2 (introduced in the reactor).
  • the catalyst VIIIc When replacing the catalyst VIIIc by not impregnated activated carbon particles, no methane production was observed.
  • the pressure of the gas carrier (mix hydrogen - helium) was 2 10 5 Pa, while the reaction temperature was 125°C.
  • the quantity of catalyst was always 0.300 mg.
  • the conversion selectivity in methane was 100%.
  • the activity of the catalyst mixtures is higher than the expected theoretical activity.
  • Catalyst VII has been mixed with activated carbon particles (see example 12 - Mix XII a to s) and tested. A similar synergistic effect was observed.
  • the Pulse tests A have been repeated, exept that the CO 2 gas was replaced by a gas mixture containing CO.
  • the reaction temperature was 125°C, while the pressure was 3 10 5 Pa.
  • the Pulse tests A have been repeated, exept that the CO 2 gas was replaced by a gas mixture containing oxygen.
  • the reaction temperature was 150°C, while the pressure was 3 10 Pa.
  • Pulse tests A have been repeated, except that the catalyst was submitted to a CO 2 flux for 30minutes, without hydrogen or oxygen.
  • the catalyst was submitted to methane pulses. Analysis of the gases from the reactor showed no variation in the methane content, and that methane was not reacting on the catalyst at said temperature and pressure.
  • Figure 1 is a schematic view of a tubular reactor 1 which is provided with a cooling envelope 2, said cooling envelope being adapted to maintain the temperature within the range 0°C - 60° C, for example lower than 25°C, such as 20°C, 10 0 C and about 0 0 C, within the reactor.
  • An appropriate coolant was used, such as water.
  • the catalyst in the form of particles was filling the inner tube 1 between two grids IA 5 IB for keeping the particles inside the tube reactor portion.
  • a feed gas containing CO 2 and H 2 is admitted into the reactor by the inlet 3 and the reaction product is exhausted by the outlet 4.
  • another gas such as an inert gas, like N 2 , He or other
  • the outlet gas contained, beside the not reacted CO 2 and H 2 , CH 4 ,some water vapour and the diluent.
  • the tubular reactor is provided with a water collecting system 8, in which water vapour is condensed, collected and evacuated from the reactor (collector 8).
  • the bottom of the reactor can be more cooled by the cooler 6 than the top part of the reactor (cooled by the heat exchanger 7), so as to generate for example a gradient of temperature in the reactor, if required.
  • the reaction can be carried out in presence of inert materials in order to dilute the catalyst and/or the reactor 1 can be provided with fins, so as to increase the reaction surface and so as to improve the heat exchange efficiency.
  • Said fins can possibly extend within the tube 1 and thus within the catalytic charge.
  • the water collecting system 8 is further provided with a cooling system 30 (shown in dashed lines in figure 2), so as to cause a further drop of water by condensation.
  • a cooling system 30 shown in dashed lines in figure 2
  • the temperature of the gas flowing within the catalytic charge will advantageously be higher than the temperature of the gas escaping said catalytic charge after being further cooled in the collector 8. Said water removal will facilitate the sucking of gas from the catalytic charge towards the collector 8.
  • the collector is provided with a pressure- reducer 8 A (shown in dashed lines) so as to reduce the pressure of gas flowing from the reactor into the collector, whereby favouring the water condensation.
  • a pressure- reducer 8 A shown in dashed lines
  • the reactor(s) are thus advantageously provided and/or associated with one or more means for controlling the water removal and/or water condensation, so as to produce methane gas with low water content.
  • the removal of water can be controlled by the use of water adsorbing material(s), the latter being advantageously of the type enabling the re-use thereof after a drying step.
  • FIG. 3 shows schematically a batch type reactor 31, at least the side walls thereof being provided with a catalyst layer 32, advantageously a porous catalyst layer, hi order to increase the catalyst present in the reactor, catalysts can be provided on the shaft and/or blades of the mixer, and/or can be present in one or more baskets inside the reactor, for example adjacent to the mixer or attached to the shaft of the mixer.
  • the reactor 31 is also provided with :
  • valves 34 for introducing CO 2 and one or more valves 36 for introducing H 2 into the reaction chamber of the reactor;
  • the reagents CO 2 and H 2 can be admitted separately or together as a reagent mixture. Possibly one or more diluent and/or inert gases can be co-admitted in the reactor.
  • the reaction can be carried out under pressure, and the time of reaction can be controlled so as to achieve the desired reaction rate of one or another reagent, with the selected selectivity (i.e. about 100% in methane production from CO 2 ).
  • reaction product gas is removed at least partly from the reaction chamber 37.
  • feed gas with reagents is admitted back into the reactor so as to increase the pressure in the reaction chamber 37.
  • the reaction chamber 37 can be provided with one or more systems for controlling the temperature within the reaction chamber.
  • This reactor can possibly simulate the form of a large container, possibly a large subsurface cavity provided with catalyst, for example in the injection pipe(s) and/or as tube(s) extending with the cavity, after a drilling operation. It enables thus the reaction to be carried out underground, and to re-extract thereafter methane from the cavity after a sufficient reaction time period.
  • the hydrogen and the catalyst and/or a natural product having as such or after treatment a catalytic methanation activity is injected together in the cavity (Possibly the cavity is selected so as to contain as such walls having a catalytic methanation activity or walls suitable to be rendered catalytic active for methanation after one or more treatment.
  • the cavity is selected so as to contain as such walls having a catalytic methanation activity or walls suitable to be rendered catalytic active for methanation after one or more treatment.
  • the reaction can be carried out in the cavity at temperature higher than the atmospheric temperature and at pressure higher than the atmospheric pressure. This can be the case where the CO 2 will be stocked underground.
  • the storage of CO 2 will be operated in cavity comprising or associated to compounds or products having a catalytic methanation activity and/or being able to be rendered at least partly catalytic active for methanation and/or suitable for promoting the catalytic methanation.
  • Figure 4 is a schematic view of a system for ensuring a pulse type reaction, i.e. a reaction in which the catalyst containing reactor 31 is first fed with hydrogen gas, advantageously with a low CO 2 content, and then with CO 2 gas, advantageously with a low H 2 content, or a reaction in which the catalyst containing reactor is first fed with CO 2 gas, advantageously with a low H 2 content, and then with hydrogen gas, advantageously with a low CO 2 content.
  • a pulse type reaction i.e. a reaction in which the catalyst containing reactor 31 is first fed with hydrogen gas, advantageously with a low CO 2 content, and then with CO 2 gas, advantageously with a low H 2 content, or a reaction in which the catalyst containing reactor is first fed with CO 2 gas, advantageously with a low H 2 content, and then with hydrogen gas, advantageously with a low CO 2 content.
  • Figure 4 is thus comprising two or more batch reactors 31 mounted in parallel, whereby enabling a substantially continuous methane production.
  • the catalyst 32 in the form of particles is placed on a porous layer, such as a grid 33.
  • Each batch reactor 31 can be provided with a recycling loop 40 with a recycling fan 41 for recycling at least partly gases flowing though the catalyst layer 32 (for example in powdery or particles form) back into the reactor 31 or towards another reactor 31.
  • the recycling loop 40 can possibly be provided with one or more cooling systems 49, and possibly with a gas dryer 48 (for example using moisture absorbing material, such as silica gel, preferably absorbing material suitable to be regenerated).
  • the opening of the exhaust valve 35 of one or more reactors 31 is for example controlled in function of the methane content or water vapour content, for example as soon as the methane content and/or water content in the reactor 31 exceed(s) a predetermined level, and/or as soon as a predetermined amount of water is removed from the reactor(s) 31.
  • Each reactor 31 can also be provided with means for liquid water removal system 37, and/or a cooling system if required.
  • a CO 2 (possibly mixed with an inert gas) feed line 60 is used for feeding the various reactors 31, while a hydrogen (possibly mixed with an inert gas) feed line 61 is used for feeding the various reactors 31.
  • Said lines are provided with the appropriate valves for ensuring the timely required feeding of the reactors with CO 2 and/or hydrogen.
  • All the reactors of the embodiment of figures 1 to 4 can be replaced by reactor of the fluid bed type or even a moving bed reactor.
  • the catalyst will be in a form suitable for being fluidized or for the moving bed reactor.
  • a recycling loop 40 can possibly be used.
  • Figure 5 is a schematic view of a portion of a reactor 50 comprising a porous catalytic membrane 56 defining an inner channel or room 52, in which CO 2 containing gas is fed, advantageously under a sufficient pressure for ensuring at least CO 2 to migrate within the porous membrane.
  • Hydrogen containing gas is fed in the outer channel or room 53 with respect to the catalytic membrane.
  • the pressure of CO 2 is higher than the pressure of hydrogen, the formation of methane and water vapour on the catalyst and/or in the catalyst will flow towards the outer channel or room 53.
  • CO 2 can be introduced into the outer channel 53, while hydrogen is introduced into the inner channel 52.
  • the reactor comprises a chamber 10 in which hydrogen is admitted via the inlet 11, a chamber 12 with an inlet 13 and an outlet 14, whereby a gas (comprising CO 2 , in pure form and/or in diluted form with one or more other gases, such as N 2 , He, CO, etc.) is flowing, a porous membrane 15 provided with inner cooling pipe 16 separating the chamber 10 from the chamber 12.
  • the porous membrane is provided with a methanation catalyst.
  • the porosity of the membrane is selected so that hydrogen can flow through said membrane towards the chamber, or vice versa (i.e. CO 2 pressure higher for causing the flow ofCO 2 within the membrane).
  • the pressure of Hydrogen in the chamber 10 is higher than the pressure of the gas in the chamber 12, so as to create a hydrogen flow into the membrane 15 (or vice versa if a flow of CO 2 is to be created towards the chamber 10). So as to control the flow of hydrogen, the pressure can be varied. According to a possible embodiment, the pressure of Hydrogen is varied between a low pressure for which there is no hydrogen flow into the membrane towards the chamber 12, and a high pressure for which hydrogen flows into the membrane towards the chamber 12.
  • the reactor is associated with a gas separator 20, for recovering methane from the gas exhausting the reactor.
  • the remaining gas contains a high CO 2 content and a low methane content (as well as advantageously a very low water vapour content) was then recycled back towards the inlet 13 of the reactor.
  • said remaining gas is advantageously further treated into a dryer 21 for removing water.
  • Fresh CO 2 with or without diluting gas is added to the dried remaining process gas.
  • This type of recycling can also be used in the other embodiment of reactor according to the invention, especially the reactor shown in the figures 1 to 5.
  • the reactor is further provided with a water removal system 21 from the reactor.
  • hydrogen is also mixed with one or more other gases, for example nitrogen, so as to avoid a too rich H 2 environment in the membrane.
  • gases for example nitrogen
  • the catalyst is advantageously deposited along the surface of the membrane directed towards the chamber 12 and/or directed towards the chamber 10.
  • the catalysts used in the examples were selected so that, based on thermodynamics calculation, when contacting lKmol of a feed gas consisting of 10% by volume of H 2 , 10% by volume CO 2 and 80% by volume of He at a pressure of 1 10 5 Pa and at 25°C, without photoexitation, a conversion rate of more than 99.7 mole %, advantageously more than 99.8 mol%, preferably about 100 mol% ofH 2 and a conversion rate of CO 2 greater than 24.5 mole %, advantageously more than 24.8 mol %, preferably about 25 mol% could theoretically be achieved, while the methanation conversion selectivity is greater than 99.5%, advantageously greater than 99.85%, preferably about 99.9%- 100%.

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Abstract

L’invention concerne un procédé de production sélective de méthane avec une sélectivité d’environ 100 % par réaction d’un gaz d’alimentation contenant du CO2, avec de l’hydrogène ou une espèce de l’hydrogène, en présence d’un catalyseur solide de méthanation qui contient moins de 0,2 % en poids de ruthénium. Selon l’invention, la réaction est réalisée à une température inférieure à 150 °C et à une pression comprise entre 104 Pa et 100 105 Pa, le rapport atomique entre le C du CO2 du gaz d’alimentation et l’atome d’hydrogène de l’hydrogène ou de l’espèce de l’hydrogène étant compris entre 0,1 et 6.
PCT/BE2009/000036 2008-07-15 2009-09-15 Procédé catalytique de méthanation de co<sb>2</sb> Ceased WO2010006386A2 (fr)

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WO2013053371A1 (fr) * 2011-10-12 2013-04-18 Solarfuel Gmbh Procédé destiné à préparer un produit gazeux riche en méthane et système approprié
CN103769106A (zh) * 2014-02-20 2014-05-07 厦门大学 原位生长碳纳米管促进的镍基甲烷化催化剂及其制备方法
DE102012112705A1 (de) 2012-12-20 2014-06-26 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Verfahren zur Herstellung von Methanol aus Kohlendioxid
CN105102125A (zh) * 2013-02-27 2015-11-25 托普索公司 稳定的包含过渡态氧化铝的催化剂载体和催化剂
JP2016515470A (ja) * 2013-03-28 2016-05-30 エージェンシー フォー サイエンス， テクノロジー アンド リサーチ メタン化触媒
CN106995735A (zh) * 2017-05-03 2017-08-01 江苏天楹环保能源成套设备有限公司 一种填埋气或沼气的处置系统
US9908104B2 (en) 2013-06-28 2018-03-06 Agency For Science, Technology And Research Methanation catalyst
JP2019108290A (ja) * 2017-12-18 2019-07-04 株式会社豊田中央研究所 メタンの製造装置及びそれを用いたメタンの製造方法
CN110252308A (zh) * 2019-06-21 2019-09-20 山东科技大学 一种活性金属在载体中呈原子级分散的负载型催化剂及其制备方法和用途
WO2020091969A1 (fr) * 2018-10-30 2020-05-07 Exxonmobil Chemical Patents Inc. Teneur en ions métalliques du groupe 1 de catalyseurs à tamis moléculaire microporeux
CN111729691A (zh) * 2020-05-14 2020-10-02 河南晋煤天庆煤化工有限责任公司 一种甲烷化镍基催化剂的钝化回收再利用方法
CN114768804A (zh) * 2022-04-10 2022-07-22 南京大学 一种固溶体光热催化材料的制备方法及应用
WO2022201061A1 (fr) * 2021-03-23 2022-09-29 Universidade Do Porto Réacteur d'adsorption cyclique pour la valorisation de mélanges de co2/ch4
CN115504846A (zh) * 2022-09-20 2022-12-23 中国工程物理研究院材料研究所 一种利用电离辐射催化二氧化碳合成气制备有机物的方法
JP2023018241A (ja) * 2021-07-27 2023-02-08 国立大学法人東海国立大学機構 循環型反応器を用いた無触媒の合成メタン製造技術
CN115970743A (zh) * 2023-03-03 2023-04-18 中国科学院山西煤炭化学研究所 一种zsm-5分子筛复合材料及其制备方法和应用、甲烷的制备方法
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EP2595942B2 (fr) † 2011-10-12 2017-03-01 ETOGAS GmbH Procédé destiné à préparer un produit gazeux riche en méthane et système approprié
RU2641306C2 (ru) * 2012-12-20 2018-01-17 Л'Эр Ликид, Сосьете Аноним Пур Л'Этюд Э Л'Эксплутасьон Просед Жорж Клод Способ получения метанола из диоксида углерода
DE102012112705A1 (de) 2012-12-20 2014-06-26 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Verfahren zur Herstellung von Methanol aus Kohlendioxid
WO2014096226A1 (fr) * 2012-12-20 2014-06-26 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Procédé de production de méthanol à partir de dioxyde de carbone
CN104903281A (zh) * 2012-12-20 2015-09-09 乔治·克劳德方法的研究开发空气股份有限公司 由二氧化碳生产甲醇的方法
US20150360209A1 (en) * 2013-02-27 2015-12-17 Haldor Topsøes Allé 1 Stabilized catalyst support and catalyst comprising transition aluminia
CN105102125A (zh) * 2013-02-27 2015-11-25 托普索公司 稳定的包含过渡态氧化铝的催化剂载体和催化剂
US9757714B2 (en) * 2013-02-27 2017-09-12 Haldor Topsoe A/S Methanation process using stabilized catalyst support comprising transition alumina
US9802872B2 (en) 2013-03-28 2017-10-31 Agency For Science, Technology And Research Methanation catalyst
JP2016515470A (ja) * 2013-03-28 2016-05-30 エージェンシー フォー サイエンス， テクノロジー アンド リサーチ メタン化触媒
US9908104B2 (en) 2013-06-28 2018-03-06 Agency For Science, Technology And Research Methanation catalyst
CN103769106A (zh) * 2014-02-20 2014-05-07 厦门大学 原位生长碳纳米管促进的镍基甲烷化催化剂及其制备方法
CN106995735A (zh) * 2017-05-03 2017-08-01 江苏天楹环保能源成套设备有限公司 一种填埋气或沼气的处置系统
JP2019108290A (ja) * 2017-12-18 2019-07-04 株式会社豊田中央研究所 メタンの製造装置及びそれを用いたメタンの製造方法
WO2020091969A1 (fr) * 2018-10-30 2020-05-07 Exxonmobil Chemical Patents Inc. Teneur en ions métalliques du groupe 1 de catalyseurs à tamis moléculaire microporeux
CN110252308A (zh) * 2019-06-21 2019-09-20 山东科技大学 一种活性金属在载体中呈原子级分散的负载型催化剂及其制备方法和用途
CN110252308B (zh) * 2019-06-21 2022-02-22 山东科技大学 一种活性金属在载体中呈原子级分散的负载型催化剂及其制备方法和用途
CN111729691A (zh) * 2020-05-14 2020-10-02 河南晋煤天庆煤化工有限责任公司 一种甲烷化镍基催化剂的钝化回收再利用方法
WO2022201061A1 (fr) * 2021-03-23 2022-09-29 Universidade Do Porto Réacteur d'adsorption cyclique pour la valorisation de mélanges de co2/ch4
JP2023018241A (ja) * 2021-07-27 2023-02-08 国立大学法人東海国立大学機構 循環型反応器を用いた無触媒の合成メタン製造技術
US12005427B2 (en) 2021-11-10 2024-06-11 Industrial Technology Research Institute Catalyst for methanation reaction and method for preparing methane
CN114768804A (zh) * 2022-04-10 2022-07-22 南京大学 一种固溶体光热催化材料的制备方法及应用
CN114768804B (zh) * 2022-04-10 2023-11-10 南京大学 一种固溶体光热催化co2转化反应的应用
CN115504846A (zh) * 2022-09-20 2022-12-23 中国工程物理研究院材料研究所 一种利用电离辐射催化二氧化碳合成气制备有机物的方法
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