• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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  • 优先权
    • 专利摘要:
    Procedure for direct methane biogas. The present invention relates to a process for obtaining a highly active, selective and stable catalyst and its use in direct biogas metanation in intensified reactors operating in a single stage with a high level of conversion. The developed catalyst comprises a ruthenium based formulation supported on cerium modified alumina. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2735300A1
    申请号:ES201830586
    申请日:2018-06-15
    公开日:2019-12-17
    发明作者:Yerga Rufino Manuel Navarro；Fierro Jose Luis Garcia；Toledo Noelia Mota；Lopez Rut Guil；Soto Dalia Liuzzi
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；
    IPC主号:
    专利说明:

    [0001]
    [0002]
    [0003]
    [0004] The present invention relates to a process for obtaining a highly active, selective and stable catalyst, and its use in direct biogas metanation in intensified reactors operating in a single stage with a high level of conversion. The developed catalyst comprises a ruthenium based formulation supported on cerium modified alumina.
    [0005]
    [0006] BACKGROUND OF THE INVENTION
    [0007]
    [0008] In the process of methane carbon dioxide (CO2) catalysts are used that selectively promote their hydrogenation towards the formation of methane. On an industrial level, there are two main uses of the methane reaction: to purify synthesis gas (elimination of traces of carbon oxides (CO / CO2) and for the manufacture of synthetic natural gas from synthesis gas (CRG process) .
    [0009]
    [0010] Nickel (Ni) or ruthenium (Ru) systems are the most commonly used elements as active phases in commercial methane catalysts due to their high activity and selectivity values for methane formation, with Ni being the most widely used at industrial level in methane reactions due to its excellent relationship between activity and cost; While Ru catalysts usually have greater intrinsic activity per unit mass and greater activity at a lower operating temperature than nickel, however, the main limitation of the use of Ru catalysts lies in their higher cost.
    [0011]
    [0012] Additionally, the concentration of nickel in commercial catalysts varies between 20 and 77% by weight while in Ru-based ones the concentration is around 0.5-5% by weight. This type of catalysts are active in CO2 methane in the temperature range between 250 and 430 ° C and pressures between 10 and 60 bar.
    [0013] On the other hand, the support used in the metanation catalysts aims to allow maximum exposure of the active metallic particles of Ni or Ru, and their stabilization against growth, by thermal sintering, under the reaction conditions. The support and mode of preparation of the catalysts have a significant influence on the morphology, size and stability of the metallic particles of Ni and Ru active in methanization.
    [0014]
    [0015] In this sense, the type of support used in the metanation catalysts has an important role in the behavior of the catalysts since it affects the active phase-support interactions, the dispersion of the active phases and therefore affects the activity, selectivity and stability of the catalysts. To date, different metal oxides have been studied as supports for methane catalysts (Al2O3, CeO2, SiO2, TiO2, SiC, perovskites, MgAl2O4, etc.). The most commonly used support in methane catalysts is aluminum oxide (Al2O3) due to the possibility it offers to obtain catalysts with a different surface and porosity (150-300 m2 / g) depending on the metal load and concentration of the biogas to be metallized .
    [0016]
    [0017] In addition to the method of preparation and support, activity promoters also modify the catalytic behavior of methane catalysts. The activity promoters studied are of two types: (1) electronic promoters of the active phases of Ni and Ru to modify their electronic mobility (Pt, Fe, Co, Mn, etc.) and, (2) structural promoters to modify the dispersion and thermal stability of the catalysts through changes in the texture, porous structure and mechanical strength of the catalysts (La, K, etc). It should be taken into account that the stability of methane catalysts (against thermal sintering, impurity poisoning or carbon formation) is another aspect that methane catalysts must meet.
    [0018]
    [0019] On the other hand, in recent years a new application of the methane reaction has emerged strongly within the Power to Gas processes that allows the generation of methane from hydrogen produced by electrolysis with renewable energies in combination of CO2 from of any origin, although the direct methane biogas (mixture in variable proportion of CO2 and H2) is particularly interesting. Although the developments and studies on catalysts of methane are very numerous in the scientific and patent literature, specific developments of catalysts applied to direct biogas metanation are scarce.
    [0020]
    [0021] DESCRIPTION OF THE INVENTION
    [0022]
    [0023] The direct methane biogas (mixing in variable proportion of CO2 and H2) implies specific conditions for the catalysts (higher level of activity and stability) with respect to the methane of pure CO2 currents, which make the direct application of the catalytic developments made For CO2 methane, they cannot be directly extrapolated for application to biogas methane.
    [0024]
    [0025] In this sense, and as an illustrative example, Example 8 of the present invention shows that the behavior of catalysts traditionally used for the methane of pure CO2 streams are not directly transferable to their behavior in the metalation of biogas streams. This example includes a comparison of the relative activities of three catalysts with different composition described in the state of the art for CO2 methane that exhibit different catalytic behavior when tested with pure CO2 streams and with biogas stream, which demonstrates that Behaviors and classifications of catalysts made from results obtained in the methane of pure CO2 currents are not directly extrapolated to methane biogas tests.
    [0026]
    [0027] In accordance with the invention, the catalyst is a solid comprising an active phase consisting of a metal located in group VIII of the periodic table and mixtures thereof, and a support of the group of inorganic oxides that is selected from alumina, silica, titania, or combinations thereof, modified with cerium or its compounds, which act as promoters in the biogas methane.
    [0028]
    [0029] In a preferred embodiment, the group VIII metal used as the active phase is ruthenium.
    [0030]
    [0031] In another preferred embodiment, the support is alumina, and more preferably it is gamma-alumina, characterized in that its specific surface area is greater than 200 m2 / g.
    [0032] In another preferred embodiment, the promoter is a cerium oxide, and more preferably it is CeO2 with a particle size of less than <200 nm.
    [0033]
    [0034] According to a preparation of the catalyst, it can comprise between 0.1 to 10% by weight of the active phase and between 5 to 30% by weight of the promoter.
    [0035]
    [0036] Preferably, the catalyst comprises between 0.1 to 5% by weight of the active phase and between 5 to 15% by weight of the promoter. In a preferred preparation the catalyst comprises 5% by weight of ruthenium and 10% by weight of cerium supported on alumina.
    [0037]
    [0038] A second aspect of the invention relates to the process for obtaining the catalyst with the characteristics described above, which comprises at least the following steps:
    [0039] a) Modify a support that is selected from alumina, silica, titania, or combinations thereof, with a solution of a cerium precursor through an incorporation methodology to achieve a cerium load of between 5 and 30% by weight ;
    [0040] b) Dry the modified support from stage a) at a temperature of between 20 and 40 ° C for a period of 12 to 36 hours, and subsequent heating in air to a temperature of between 500 and 700 ° C staying at this temperature for a period of 3 to 6 hours;
    [0041] c) Incorporate a metal of group VIII of the periodic table on the modified support from step b) with a solution of a precursor of said metal by means of an incorporation methodology to reach a metal load of between 0.1 to a 10% by weight;
    [0042] e) Dry the product obtained from step c) at a temperature of between 20 and 40 ° C for a period of time between 12h and 36h, without subsequent heat treatment; and f) Reduce the product obtained in step (e) by heating (2-15 ° C / min) under a flow rate of H2 / N2 to a temperature between 200 and 500 ° C, keeping at that temperature for a period of time between 30 minutes and 2 hours.
    [0043] In a preferred embodiment the support of step a) is alumina, and more preferably it is gamma-alumina, characterized in that its specific surface area is greater than 200 m2 / g.
    [0044]
    [0045] In another preferred embodiment the cerium incorporation methodology of step a) is selected from impregnation, impregnation to incipient moisture or precipitation, and more preferably impregnation to incipient moisture is employed.
    [0046]
    [0047] In another preferred embodiment, the cerium precursor is selected from Ce (NH4) 2 (NO3) a, Ce2 (C2O4) 3, Ce2 (SO4) 3 Ce (NO3) 3.6H2O, and more preferably is Ce (NO3) 3'6H2O.
    [0048]
    [0049] In another preferred embodiment, the cerium charge of the modified support after step a) is between 5 to 15% by weight, and more preferably 10% by weight.
    [0050]
    [0051] In another preferred embodiment the group VIII metal is incorporated into the modified support with cerium from step b) by means of an incorporation methodology that is selected from impregnation, impregnation to incipient moisture or reservoir reduction and more preferably impregnation to incipient moisture is employed.
    [0052]
    [0053] In a preferred embodiment, the group VIII metal used in step c) is ruthenium.
    [0054]
    [0055] In another more preferred embodiment, the ruthenium precursor in step c) is selected from [Ru (NH3) 6] Cl2, [Ru (NH3) 5Cl] Cl2, RuCh, Ru (NO) (NO3) 3, and more preferably is Ru (NO) (NO3) 3.
    [0056]
    [0057] In another preferred embodiment, the ruthenium charge of the product obtained after step c) is between 0.1 to 10% by weight, and more preferably 5% by weight.
    [0058]
    [0059] In another preferred embodiment, the H2 / N2 flow rate of step f) has a concentration range of between 2 and 20% vol of H2.
    [0060] The present invention also relates to the use of the catalyst with the properties described above, in a method for the direct methane biogas (mixture of CO2 and CH4 in variable proportions) in intensified reactors (microreactors) with high level of CO2 conversion ( > 90%). This application requires the catalyst additional requirements related to achieving high levels of conversion per unit volume of the catalyst for the treatment of high gaseous flows.
    [0061]
    [0062] In this scenario, a catalyst having an excellent level of activity in direct biogas metanation has been prepared by the process of the invention as demonstrated in Example 9 of the present invention, in which the relative levels of activity achieved are compared. with the catalyst versus nickel and ruthenium based catalysts representative of the state of the art for the methane of pure CO2 streams.
    [0063]
    [0064] The catalyst of the invention has also demonstrated high stability in biogas methane operating under conditions compatible with intensified reactors (GHSV = 20000-25000 h-1) for more than 250 hours with a conversion level greater than 95% without showing appreciable signs. deactivation It has also been tested at the pilot level in a millichannel reactor against a real biogas, achieving a production of CH4 that meets the specifications of the gas from unconventional sources to be introduced into the gas distribution network.
    [0065]
    [0066] Therefore, a third aspect of the present invention also relates to a method of direct biogas metanation in intensified reactors with a high level of conversion characterized in that it comprises a single stage in which the catalyst is contacted with the current of biogas at a pressure equal to or greater than 5 atm and a temperature greater than or equal to 175 ° C, and where the catalyst is characterized by comprising: i) at least one metal of group VIII of the periodic table and mixtures thereof, in a proportion of between 0.1 to 10% by weight; ii) a support from the group of inorganic oxides that is selected from alumina, silica, titania, or combinations thereof, modified with cerium or its compounds in a proportion of cerium of between 5 to 30% by weight, which act as promoters.
    [0067] In a preferred embodiment, the group VIII metal is ruthenium.
    [0068]
    [0069] In another preferred embodiment, the support is alumina, and more preferably it is gamma-alumina, characterized in that its specific surface area is greater than 200 m2 / g.
    [0070]
    [0071] According to a preparation of the catalyst, it can comprise from 0.1 to 5% by weight of the active phase and from 5 to 15% by weight of cerium.
    [0072]
    [0073] In a preferred preparation the catalyst comprises 5% by weight of ruthenium and 10% by weight of cerium.
    [0074]
    [0075] Throughout the description and the claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and features of the invention will be derived partly from the description and partly from the practice of the invention. The following examples are provided by way of illustration, and are not intended to be limiting of the present invention.
    [0076]
    [0077] EXAMPLES
    [0078]
    [0079] The invention will now be illustrated by tests carried out by the inventors, which demonstrates the effectiveness of the product of the invention.
    [0080]
    [0081] Example 1. Synthesis of Catalyst A
    [0082]
    [0083] Representative sample of the state of the art of catalysts for the pure CO2 based on Ru based on Al2O3. For the preparation of this catalyst, a commercial alumina support (y- Al2O3, Alfa-Aesar 251 m2 / g) was used. On the support particles the Ru was incorporated by impregnating to incipient moisture with an aqueous solution of the Ru precursor salt (Ru (NO) (NO3) 3) to reach a load of 5% (weight) of Ru. Subsequently, the catalyst was dried at room temperature for 12h. Before being used in the methane reaction, the catalyst is reduced in a stream of H2 / N2 (90/10 mol) for 2h at 350 ° C (with heating ramp of 2 ° C / min).
    [0084] Example 2. Synthesis of Catalyst B
    [0085]
    [0086] Representative sample of the state of the art of catalysts for the pure CO2-based metiation of Ni modified with Fe supported on Al2O3. For the preparation of this catalyst a commercial alumina support was used ( and -AI2O3, Alfa-Aesar 251 m2 / g). On the calcined support particles (in air at 650 ° C for 4 hours) the Ni was first incorporated by impregnating to incipient moisture with an aqueous solution of the Ni precursor salt (Ni (NO3) 26H2O) to reach a charge of 20% (weight) of Ni. The solid once impregnated was dried at room temperature for 12 hours. The impregnated and dried solid was subsequently calcined in a flask at 400 ° C under air flow for 4 hours with a heating ramp of 2 ° C / min. The promoter element Fe was incorporated on the calcined solid by impregnation to incipient moisture with aqueous solution of the precursor salt of Fe (Fe (NO3) 39H2O) to reach a Fe load allowing a Ni / Fe ratio = 1/3 (at / at). After impregnation, the sample was allowed to dry at room temperature for 12 hours. After drying, the samples were calcined in muffle at 400 ° C under air flow for 4 hours with a heating ramp of 2 ° C / min. Before the reaction the catalyst is reduced in a stream of H2 / N2 (90/10 mol) for 2h at 650 ° C (with heating ramp of 2 ° C / min).
    [0087]
    [0088] Example 3. Synthesis of Catalyst C
    [0089]
    [0090] Representative sample of the state of the art of catalysts for the pure CO2-based metiation of Ni modified with that supported in Al2O3 For the preparation of this catalyst a commercial alumina support ( and -AI203, Alfa-Aesar 251 m2 / g) was used. The La promoter element was incorporated on the support particles by impregnating the support with an aqueous solution of the precursor salt of La (La (NO3) 36H2O) to reach a load of 10% (weight) of La. The support impregnated Al2O3-La was dried at room temperature for 12 hours and calcined in air in a flask at 650 ° C for 4 hours with a heating ramp of 2 ° C / min. On the support particles Al2O3-La, Ni was incorporated by impregnating to incipient moisture with an aqueous solution of the precursor salt of Ni (Ni (NO3) 26H2O) to reach a 20% (weight) Ni load. The solid once impregnated was dried at room temperature for 12 hours. The impregnated solid and Dry was subsequently calcined in a flask at 400 ° C under air flow for 4 hours with a heating ramp of 2 ° C / min. Before the reaction the catalyst is reduced in a stream of H2 / N2 (90/10 mol) for 2h at 650 ° C (with heating ramp of 2 ° C / min).
    [0091]
    [0092] Example 4. Synthesis of Catalyst D
    [0093]
    [0094] Representative sample of the state of the art of catalysts for the pure CO2 based metanation based on Ni supported in Al2O3. For the preparation of this catalyst a commercial alumina support (y-Al2O3, Alfa-Aesar 251 m2 / g) was used. On the calcined support particles (in air at 650 ° C for 4 hours) the Ni was first incorporated by impregnating to incipient moisture with an aqueous solution of the Ni precursor salt (Ni (NO3) 26H2O) to reach a charge of 20% (weight) of Ni. The solid once impregnated was dried at room temperature for 12 hours. The impregnated and dried solid was subsequently calcined in a flask at 400 ° C under air flow for 4 hours with a heating ramp of 2 ° C / min. Before reaction the catalyst is reduced in a stream of H2 / N2 (90/10 mol) for 2h at 650 ° C (with heating ramp of 2 ° C / min).
    [0095]
    [0096] Example 6. Synthesis of Catalyst E
    [0097]
    [0098] Representative sample of a catalyst prepared by the process of the invention for biogas metanation. Commercial alumina particles (y-Al2O3, Alfa-Aesar 251 m2 / g) were used as support. The Ce promoter element was incorporated on the support particles by impregnating the carrier with incipient moisture with an aqueous solution of the precursor salt of Ce (Ce (NO3) 36H2O) to reach a load of 10% (weight) of Ce. The support impregnated Al2O3-Ce was dried at room temperature for 12 hours and calcined in air in a muffle at 650 ° C for 4 hours with a heating ramp of 2 ° C / min. With this preparation methodology, an optimal dispersion of cerium over the alumina surface is obtained. The Ru was incorporated onto the calcined Al2O3-Ce support particles by impregnation with incipient moisture with an aqueous solution of the Ru precursor salt (in this case Ru (NO) (NO3) 3) to reach a load of 5% (weight ) of Ru. After impregnation, the catalyst was dried at room temperature for 12 hours without prior calcination. Before the reaction the catalyst is reduced by a stream of H2 / N2 (90/10 mol) for 2h at 350 ° C (with heating ramp of 2 ° C / min).
    [0099]
    [0100] Example 7. Synthesis of Catalyst F
    [0101]
    [0102] This sample has been prepared to demonstrate that the catalyst preparation method, for the same composition, has a significant influence on its catalytic behavior for the biogas methane reaction and that the preparation method described in the state of the art (J. Rynkowski et al., React. Kinet. Catal. Lett, (200) 71 (1) 55-64) gives rise to catalysts with less activity. The preparation of this sample has been carried out according to the methodology already described, using commercial alumina particles as support ( and -AI2O3, 251 m2 / g). The promoter element Ce was incorporated on the support particles by impregnating to incipient moisture of the support with an aqueous solution of the precursor salt of Ce (Ce (NO3) 36H2O) to reach a load of 10% (weight) of Ce. Calcined Al2O3-Ce support particles Ru was incorporated by impregnating to incipient moisture with an aqueous solution of the Ru precursor salt (in this case RuCl3) to reach a load of 5% (weight) of Ru. After impregnation the catalyst was dried at room temperature for 12h and calcined in air at 370 ° C for 4h. Before the reaction the catalyst is reduced in a stream of H2 / N2 (90/10 mol) for 2h at 145 ° C (with heating ramp of 2 ° C / min).
    [0103]
    [0104] Example 8. Measures of activity in methane
    [0105]
    [0106] Catalysts A, B and C (catalysts representative of the state of the art) were tested in the methane reactions of pure CO2 and biogas streams that are collected in the following table, in order to demonstrate that the results and conclusions obtained at from the methane of pure CO2 they are not extrapolated to the methane CO2 in biogas (in the presence of CH4).
    [0107]
    [0108]
    [0109]
    [0110]
    [0111] The activity parameters obtained in the reaction conditions indicated in the previous table are summarized below.
    [0112]
    [0113]
    [0114]
    [0115]
    [0116] With the previous activity data it is demonstrated that the differences in the activity of catalysts derived from the pure CO2 methane tests cannot be extrapolated to the biogas CO2 methane tests (in the presence of CH4).
    [0117]
    [0118] Example 9. Biogas methane activity measurements under conditions compatible with intensified reactors for single stage methanization
    [0119]
    [0120] The catalysts A, D (catalysts representative of the state of the art) and the catalyst of the invention (E) were tested in the reactions under conditions of high spatial velocity (GHSV> 20,000 h-1) and high conversion (> 90%) compatible with intensified reactors for single stage methanization) with the aim of demonstrate that the results improve the activity of the catalyst of the invention.
    [0121]
    [0122] These catalysts were tested in the biogas methane reaction at a pressure and temperature that allowed to reach the conversion limit (90%) necessary for the application in intensified reactors that perform the metanation in a single stage. The conditions under which the trials were carried out are compiled in the following table.
    [0123]
    [0124]
    [0125]
    [0126]
    [0127] The activity parameters obtained in the above methane reactions on catalysts A, D, and E. are summarized below.
    [0128]
    [0129]
    [0130] The improvement in CO2 conversion of the catalyst of the invention against the formulations representative of the state of the art of commercial catalysts is demonstrated for use in intensified rectors that perform the biogas metanation in a single stage. Representative samples of commercial catalysts (samples A and B) are not able to reach the level of conversion (> 90%) necessary for the realization of single stage methane in intensified reactors (GHSV (> 20,000 h-1) ).
    [0131]
    [0132] Example 10. Measures of catalyst activity based on its method of obtaining
    [0133]
    [0134] Through this example it is demonstrated that for the same catalyst composition, its mode of preparation has a significant influence on its catalytic behavior for the biogas metanation reaction, and that the method of preparation of the invention has technical advantages in the activity for the biogas metaation with respect to the preparation method described in a document that anticipates its composition (J. Rynkowski et al., React. Kinet. Catal. Lett, (200) 71 (1) 55-64).
    [0135]
    [0136] The biogas tests were carried out under the same conditions as in the previous tests, that is:
    [0137]
    [0138]
    [0139] The comparison of the activity parameters obtained in the biogas methane reactions using catalyst of the invention (E) and catalyst F, prepared according to the method described in J. Rynkowski et al., React. Kinet Catal. Lett, (200) 71 (1) 55-64.
    [0140]
    [0141]
    [0142]
    [0143]
    [0144] The activity results of the previous table demonstrate a marked improvement in the activity in the conversion of CO2 (2.7 times higher), under conditions of biogas metanation, compared to the same catalyst formulation but prepared according to a method described in the state of the art
    权利要求:
    Claims (19)
    [1]
    1. Procedure for obtaining a catalyst comprising at least the following steps:
    a) Modify a support that is selected from alumina, silica, titania, or combinations thereof, with a solution of a cerium precursor through an incorporation methodology to achieve a cerium load of between 5 and 30% by weight ;
    b) Dry the modified support from stage a) at a temperature between 20 and 40 ° C for a period of 12 to 36 hours, and then heat in air to a temperature between 500 and 700 ° C staying at this temperature for a period of 3 to 6 hours; c) Incorporate a metal of group VIII of the periodic table on the modified support from step b) with a solution of a precursor of said metal by means of an incorporation methodology to reach a metal load of between 0.1 to a 10% by weight;
    e) Dry the product obtained from step c) at a temperature between 20 and 40 ° C for a period of time between 12 and 36 h; Y
    f) Reduce the product obtained in step (e) by heating under a flow rate of H2 / N2 to a temperature between 200 and 500 ° C, keeping at this temperature for a period of between 30 minutes and 2 hours.
    [2]
    2. Method according to claim 1, wherein the support of step a) is alumina.
    [3]
    3. Method according to the preceding claim, wherein the alumina is gamma-alumina, characterized in that its specific surface area is greater than 200 m2 / g.
    [4]
    4. Method according to any of the preceding claims wherein the support is modified with cerium by an incorporation methodology that is selected from impregnation, impregnation to incipient moisture or precipitation.
    [5]
    5. Procedure according to the previous claim where the incorporation of cerium is carried out by impregnation to incipient humidity.
    [6]
    Method according to any of the preceding claims, wherein the cerium precursor is selected from Ce (NH4) 2 (NO3) 6, Ce2 (C2O4) 3, Ce2 (SO4) 3 Ce (NO3) 3'6H2O.
    [7]
    7. Procedure according to the previous claim where the cerium precursor is Ce (NO3) 3'6H2O.
    [8]
    8. The method according to any of the preceding claims, wherein the cerium charge of the modified support after step a) is between 5 to 15% by weight.
    [9]
    9. Method according to the preceding claim wherein the cerium charge of the modified support is 10% by weight.
    [10]
    10. Method according to any of the preceding claims wherein the group VIII metal is incorporated on the modified support from step b) by means of an incorporation methodology that is selected from impregnation, impregnation to incipient moisture or reduction in deposit.
    [11]
    11. Procedure according to the previous claim where the incorporation of the Group VIII metal is carried out by impregnation to incipient moisture.
    [12]
    12. Method according to any of the preceding claims, wherein the group VIII metal used in step c) is ruthenium.
    [13]
    13. The method according to the preceding claim wherein the ruthenium precursor in step c) is selected from [Ru (NH3) 6] C l2, [Ru (NH3) 5C l] C l2, RuCl3, Ru (NO) (NO3 )3.
    [14]
    14. Method according to the preceding claim wherein the ruthenium precursor is Ru (NO) (NO3) 3.
    [15]
    15. Method according to any of claims 12 to 14, wherein the ruthenium load of the product obtained after step c) is between 0.1 to 10% by weight.
    [16]
    16. The method according to the preceding claim wherein the ruthenium charge is 5% by weight.
    [17]
    17. Catalyst obtained according to any of claims 1 to 16.
    [18]
    18. Use of the catalyst according to claim 17 for direct metagasation of biogas in an intensified reactor.
    [19]
    19. Method of metagasation of biogas in an intensified reactor characterized in that it comprises a single stage in which the catalyst according to claim 17 is brought into contact with a biogas stream at a pressure equal to or greater than 5 atm and a temperature greater than or equal to 175 ° C
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    同族专利:
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    ES2735300B2|2020-07-02|
    WO2019239000A3|2020-03-19|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP0503653A1|1991-03-12|1992-09-16|Nippon Oil Company, Limited|Catalysts for the high-temperature steam reforming of hydrocarbons|
    US9339797B2|2011-06-08|2016-05-17|Raphael Idem|Sulfur tolerant catalysts for hydrogen production by carbon dioxide reforming of methane-rich gas|
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    PCT/ES2019/070415| WO2019239000A2|2018-06-15|2019-06-14|Method for the direct methanation of biogas|
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