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    • 专利摘要:
    Heterogeneous catalyst with polymeric support. The present invention refers to a catalyst comprising a polymeric support and at least one active phase in powder coating said support. Furthermore, the present invention relates to the process for obtaining said catalyst and its use in heterogeneous catalysis reactions, preferably in the preferential oxidation reaction of CO in the presence of H2 . Therefore, the present invention falls within the area of catalysis. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2797001A1
    申请号:ES201930487
    申请日:2019-05-31
    公开日:2020-11-30
    发明作者:Lopez Agustin Bueno；Castello Dolores Lozano；Garcia Esther Bailon；Garnica Cristian Chaparro；Quinonero Arantxa Davo；Lopez Ivan Martinez
    申请人:Universidad de Alicante；
    IPC主号:
    专利说明:

    [0002] Heterogeneous catalyst with polymeric support
    [0004] The present invention refers to a catalyst that comprises a polymeric support and at least one active phase in powder coating said support. Furthermore, the present invention relates to the process for obtaining said catalyst and its use in heterogeneous catalysis reactions, preferably in the preferential oxidation reaction of CO in the presence of H2.
    [0006] Therefore, the present invention can be found in the area of catalysis.
    [0008] BACKGROUND OF THE INVENTION
    [0010] The catalysts used in heterogeneous catalysis usually consist of an inert support on which the phases with catalytic activity are deposited, known as active phases. The active phases can be noble and non-noble metals, metal oxides, crystalline solids with defined porous and acidic properties, etc. The supports can be particles of different sizes, meshes, pellets, monoliths with a cellular structure ("honeycomb"), etc. Monoliths with a cellular structure are gaining more and more relevance compared to other supports such as packed beds, pellets or sponges. One of these monoliths consists of a set of parallel channels of a size of the order of one millimeter through which the fluid circulates, and the active phases of the catalyst are supported on the walls of the channels. In addition, the monoliths as support for active phases are easily manipulable for installation or replacement, and do not generate preferential paths in the fluid [P. Avila et al., "Monolithic reactors for environmental applications: a review on preparation technologies", Chem. Eng. J., 109 (2005) 11-36 ] [S. Govender and others "Monoliths: a review of the basics, preparation methods and their relevance to oxidation", Catalysts, 7 (2017) 62].
    [0012] Monolithic supports are an alternative to packed-bed reactors in a multitude of applications, particularly in the preferential oxidation reaction of CO in the presence of H2 (CO-PROX). A relevant application of catalysts supported on monoliths is proton exchange membrane fuel cells (PEMFC) as power generators, where it is noted that catalysts supported on monoliths are more robust than catalysts in dust and have greater resistance to wear due to friction, as well as low pressure drops and good heat and mass transfer characteristics [G. Landi et al., "Optimization of the preparation method of CuO / CeO2 structured catalytic monolith for CO preferential oxidation in H2-rich streams", Appl. Catal. B Environ, 181 (2016) 727-737], [PS Barbato et al., “Structuring CuO / CeO2 catalyst as option to improve performance towards CO-PROX”, Top. Catal., 59 (2016) 1371-1382].
    [0014] For the preferential oxidation reaction of CO in the presence of H2 (CO-PROX), other types of active phase supports, such as ceramic sponges, have also been tested, since they also have low pressure drop and good heat transfer characteristics and mass [S. Lang and others; "Novel PtCuO / CeO2 / a-AhO3 sponge catalysts for the preferential oxidation of CO (PROX) prepared by means of supercritical fluid reactive deposition (SFRD)", J. Catal., 286 (2012) 78-87].
    [0016] In studies carried out on heterogeneous catalysts for the preferential oxidation reaction of CO in the presence of H2 (CO-PROX) with monolith support and cellular structure, it was shown that their use allows to overcome the intra-particle mass transfer limitations that generally occur with powdered catalysts with high CO conversion, providing better use of the active phase. In addition, it was determined that with the increase in cell density it is possible to load a greater amount of catalyst on the same volume of monolith and in turn allows the monolithic reactor to operate under more adiabatic conditions. [P. S. Barbato et al., "CuO / CeO2 based monoliths for CO preferential oxidation in H2-rich streams", Chem. Eng. J., 279 (2015) 983-993].
    [0018] However, monoliths with a cellular structure that are currently designed to be used in heterogeneous catalysis are limited, on the one hand, by the technology available for their manufacture and, on the other, by the techniques available to support the active phases of the catalyst [M. Navlani-García and others, “BETA zeolite thin films supported on honeycomb monoliths with tunable properties as hydrocarbon traps under cold-start conditions”, ChemSusChem, 6 (2013) 1467-1477] [V. Meille, “Review on methods to deposit catalysts on structured surfaces”, Appl. Catal. A Gen, 315 (2006) 1117]. Thus, for example, monoliths with a cellular structure are manufactured by extrusion and the active phases are subsequently incorporated, usually by immersion in a suspension (a process called "dip-coating" in English), where the homogeneity of the coating is questioned.
    [0019] Most of the monoliths that are currently used commercially are manufactured in refractory ceramic materials with high thermal and mechanical stability, such as cordierite or silicon carbide among others. The use of polymeric materials to manufacture catalyst supports could be extremely useful, since it is much easier and cheaper to manufacture complex structures in polymer than in refractory ceramic materials. However, catalytic supports made of polymer have not been implemented for two main reasons: the low thermal stability of polymers compared to ceramics and the difficulty of supporting active phases in polymeric supports. Thermal stability is not a total ban on the use of polymers, but a limitation to low-temperature catalytic applications, such as the CO-PROX reaction. Active phase anchoring, on the other hand, is an unsolved scientific-technical challenge.
    [0021] Therefore, it is necessary to develop new heterogeneous catalysts, particularly heterogeneous catalysts capable of being used in the preferential reaction of CO in the presence of H2.
    [0023] DESCRIPTION OF THE INVENTION
    [0025] In a first aspect, the present invention refers to a catalyst (hereinafter "the catalyst of the invention") characterized in that it comprises a polymeric support with a plurality of surfaces and at least one active phase, where the active phase covers at least one surface of the polymeric support.
    [0027] In the present invention, "polymeric catalyst support" is understood as that polymeric matrix with a plurality of surfaces on which the active phase of the catalyst is deposited, specifically the active phase in powder is located on at least one surface of the polymeric support. By the term "at least one surface of the polymeric support" is understood in the present invention as at least one outer face of said polymeric support.
    [0029] The active phase of the catalyst homogeneously coats at least one surface of the polymeric support, that is, the active phase homogeneously covers the entire extent of at least one surface of the polymeric support.
    [0031] In a preferred embodiment of the catalyst of the present invention, the polymeric support is preferably monolithic.
    [0032] In the present invention the monolithic polymeric support can have any geometry, for example a cube, a sheet, etc. That is, it can be, for example, a solid disk or a solid cylinder.
    [0034] The function of the support is to disperse, stabilize and provide good mechanical properties to the active phase.
    [0036] In another preferred embodiment of the catalyst of the present invention, the percentage by weight of the active phase in the catalyst is between 1% and 50%. More preferably, the percentage by weight of the active phase in the catalyst is between 2% and 15%. Even more preferably the percentage by weight of the active phase in the catalyst is between 3% and 6%.
    [0038] In a preferred embodiment of the catalyst of the present invention, the polymeric support comprises a plurality of channels. In this case it is a polymeric support with a cellular structure where the channels are smooth.
    [0040] In another preferred embodiment of the catalyst of the present invention, the plurality of channels comprises a plurality of irregularities.
    [0042] The term "channel" is understood in the present invention as a through hole that does not have to be linear and that can have different sections along its path.
    [0044] In the event that the polymeric support comprises channels, the term "at least one surface of the polymeric support" refers to the walls of said channels.
    [0046] In the event that the channels of the polymeric support comprise irregularities such as grooves, perforations, roughnesses, the term "at least one surface" of the polymeric support refers in turn to at least one of the walls of said irregularities. An example of Irregularity would be a prismatic slit. In the catalyst of the present invention, these slits are full of active phase and facilitate homogeneous distribution along the channels of the monolith, so their presence is an advantage for the catalyst of the present invention. since they increase the surface.
    [0048] In the catalyst of the present invention it is an advantage, especially in heterogeneous catalysis; when the active phase covers the walls of the plurality of channels of the polymeric support homogeneously and / or the walls of the plurality of channel irregularities. The homogeneity of the coating inside the channels prevents there are channels with an excess of active phase, which can block the channel and prevent the circulation of the gaseous reagent through it and that there are channels with an active phase defect that would be little efficient in accelerating the catalytic reaction. Both the excess and the deficiency of active phase in the channel walls represent a detriment to the overall efficiency of the monolithic catalyst.
    [0050] In a preferred embodiment of the catalyst of the present invention, the monolithic polymeric support is a polymeric resin that is photosensitive to ultraviolet (UV) light and therefore capable of being cured by UV radiation, whose thermal stability is directly related to the reaction to be catalyzed, that is, said resin is stable at the temperatures at which the reaction to be catalyzed is carried out. Said liquid or gel thermoset polymeric resin hardens when exposed to UV light, that is, when the curing process is carried out by exposure to UV light.
    [0052] In the present invention, "active phase" of the catalyst is understood as the phase directly responsible for the catalytic activity of a catalyst and is characterized in that it alone can carry out the reaction of interest under the established conditions. Examples of active phase are a metal, a metal oxide, or a combination thereof.
    [0054] Preferably, the catalyst of the present invention comprises at least one active phase of CuO supported on CeO2.
    [0056] Preferably, the catalyst of the present invention comprises a single active phase of CuO supported on CeO2.
    [0058] In another preferred embodiment of the catalyst of the present invention, the polymeric support of the catalyst also comprises C and / or SiO2, in a percentage by weight of between 0.3% and 3.5% by weight with respect to the total weight of the support. polymeric.
    [0060] The incorporation of these charges of C and / or SiO2 has two effects on the catalyst of the present invention. On the one hand, it slightly improves the thermal stability of the thermosetting polymeric resin and, on the other hand, it makes it possible to increase the amount of active phase that is incorporated into the resin. Thermosetting polymeric resins are usually hydrophobic, making impregnation with polar liquids difficult, as can be considered suspensions of active phases, and they have a very low specific surface that prevents them from dispersing the active phases. The incorporation of C or SiO2 contributes to alleviating these limitations by generating irregularities in the polymeric surface that facilitate contact with the liquid phase.
    [0062] Another aspect of the invention refers to a process for obtaining the catalyst of the present invention (hereinafter "the process of the present invention") comprising the following steps:
    [0064] a) shaping the polymeric support starting from a thermoset polymeric resin and curing said resin;
    [0066] b) coating at least one surface of the support obtained in step (a) with a suspension comprising at least one active phase,
    [0068] c) horizontally rotating the product obtained in step (b) and drying,
    [0070] d) heat treating the product obtained in step (c) in the presence of an inert atmosphere,
    [0072] e) heat treating the product obtained in step (d) in the presence of an oxidizing atmosphere.
    [0074] In a preferred embodiment of the process of the invention, step (a) of the process of the invention refers to shaping the polymeric support by 3D printing starting from a thermosetting polymeric resin and curing said resin.
    [0076] In another preferred embodiment of the process of the invention, the thermosetting polymeric resin of step (a) is photosensitive to UV light and is cured by exposure to UV light.
    [0078] Stage (b) of the process of the invention refers to the coating of at least one surface of the support obtained in stage (a), with a suspension comprising at least one active phase. Preferably this step (b) is carried out by immersion. In order to dip only one surface of the support with the suspension, it is possible to cover, for example, the outside of the support with Teflon tape.
    [0079] It should be noted that a person skilled in the art will know how to choose the appropriate liquid solvent to prepare the suspension comprising at least one active phase or several active phases. The solvent can be water, an alcohol, or a combination thereof. For the active CuO / CeO2 phase, for example, the solvent can be water.
    [0081] It should also be noted that step (b) can be carried out as many times as desired. In a preferred embodiment of the process of the present invention, step (b) is carried out more than once, that is, it is repeated more than once before proceeding to step (c).
    [0083] Stage (c) of the process of the invention refers to the horizontal rotation of the product obtained in stage (b) until it is dry. The purpose of this stage (c), in which the drying is carried out under dynamic conditions (rotation), is to ensure that the active phase continues to be homogeneously distributed during and after drying. If drying were carried out under static conditions, the active phase suspension would shift under the effect of gravity and homogeneity would be lost.
    [0085] Step (d) of the process of the invention refers to the heat treatment of the product obtained in step (c) in the presence of an inert atmosphere, that is, in the presence of N2, Ar or He, for example. Said treatment removes volatile substances from the polymeric support and softens the polymeric support, strengthening the bond between the active phase and the support.
    [0087] To eliminate excess active phase that could obstruct the channels of the support, a stream of compressed air can be used.
    [0089] Stage (e) of the process of the invention refers to the heat treatment of the product obtained in stage (d) in the presence of an oxidizing atmosphere. Since the heat treatment of step (c) can detrimentally trap the active phase inside the polymeric support, a subsequent heat treatment is carried out in the presence of an oxidizing atmosphere to improve the accessibility of the reactive gases with the active phases present in channels. Preferably, the heat treatment of step (e) is carried out in the presence of air, oxygen or a mixture of oxygen (O2) and nitrogen (N2).
    [0091] Another aspect of the present invention refers to the process for obtaining the catalyst of the present invention where the polymeric support with a plurality of surfaces comprises a plurality of channels and optionally a plurality of irregularities, comprising the following steps:
    [0093] a) shaping the polymeric support starting from a thermoset polymeric resin and curing said resin;
    [0095] b) coating at least one surface of the support obtained in step (a) with a suspension comprising at least one active phase,
    [0097] b ') coating each of the channels with the suspension used in step (b),
    [0099] c) horizontally rotate the product obtained in stage (b ') and dry,
    [0101] d) heat treating the product obtained in step (c) in the presence of an inert atmosphere,
    [0103] e) heat treating the product obtained in step (d) in the presence of an oxidizing atmosphere.
    [0105] Another aspect of the present invention refers to the process for obtaining the catalyst of the present invention
    [0107] • where optionally the polymeric support with a plurality of surfaces comprises a plurality of channels and optionally a plurality of irregularities
    [0108] • and where the polymeric support with a plurality of surfaces also comprises C and / or SiO2 in a percentage by weight of between 0.3% and 3.5% by weight relative to the total weight of the polymeric support.
    [0110] comprising the following stages:
    [0112] a1) mixing a thermosetting polymeric resin with C and / or SiO2, the percentage by weight of C and / or SiO2 being between 0.3% and 3.5% with respect to the total weight of the polymeric support; preferably the thermoset polymeric resin is photosensitive to UV light and cures by exposure to UV light,
    [0114] a2) shaping the catalyst support starting from the product obtained in step (a1) and curing said product,
    [0115] b) coating at least one surface of the support obtained in step (a) with a suspension comprising at least one active phase,
    [0117] optionally b ') coating each of the channels with the suspension used in step (b),
    [0119] c) horizontally rotating the product obtained in step (b) or (b ') and drying,
    [0121] d) heat treating the product obtained in step (c) in the presence of an inert atmosphere,
    [0123] e) heat treating the product obtained in step (d) in the presence of an oxidizing atmosphere.
    [0125] The last aspect of the present invention refers to the use of the catalyst of the invention in heterogeneous catalysis reactions.
    [0127] In the present invention, the term "Heterogeneous catalysis" is understood as that catalyst that takes place when the catalyst is in a phase (solid, liquid and gas) different from the reactants. Heterogeneous catalysts provide a surface on which it can take place The reaction For the reaction to occur, at least one reactant must contact the catalyst surface and be adsorbed on it.After the reaction, the products must desorb from the surface.
    [0129] The catalyst of the present invention can be used in catalytic applications that take place at a temperature lower than the degradation temperature of the polymer used in the support. If the degradation temperature of the polymer is around 300 ° C, the catalyst can be used in reactions that catalyze below that temperature.
    [0131] In a preferred embodiment, the invention refers to the use of the catalyst of the present invention, where at least one active phase is CuO / CeO2 or where the catalyst comprises a single active phase of CuO / CeO2, in the preferential oxidation reaction of CO in the presence of H2.
    [0133] Throughout the description and claims the word "comprise" 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 characteristics of the invention are they will emerge in part from the description and in part from the practice of the invention. The following examples and figures are provided by way of illustration, and are not intended to be limiting of the present invention.
    [0135] BRIEF DESCRIPTION OF THE FIGURES
    [0137] Figure 1: Scheme of the channels of a monolith designed with prismatic indentations along the channel walls. In figure (a) the design is visualized in two adjacent walls seen from the opposite vertex, while in figure (b) the section of a wall is shown where two of the grooves of the channel are identified.
    [0139] Figure 2: Photograph taken by SEM microscopy showing the homogeneous distribution of the powdered catalyst on the walls of the channels of a polymeric monolith.
    [0141] Figure 3: Chemical analysis carried out using the EDS technique showing the distribution of the chemical elements of the CuO / CeO2 catalyst deposited in the channels of the monolithic support, (a) Cu and (b) Ce.
    [0143] Figure 4: Shows the CO conversion profiles and selectivity to the CO2 product (%) of catalyst 0 (active phase CuO / CeO2 in powder; Figures 4a and 4b, respectively) and of catalyst 2 (monolith with active phase; Figures 4c and 4d, respectively for the CO-PROX reaction.
    [0145] Figure 5: Profiles of CO conversion and selectivity of CO towards the CO2 product (on the main axis) and temperature (on the secondary axis) for catalyst 2 in a 10-hour stability test.
    [0147] EXAMPLES
    [0149] The invention will be illustrated below by means of tests carried out by the inventors, which demonstrate the effectiveness of the product of the invention.
    [0151] Preparation of the polymeric support in the form of a monolith
    [0153] For the preparation of the support, a polymeric resin was used that exhibits thermal stability up to approximately 300 ° C, capable of being used in catalytic reactions of moderate temperature, such as the selective oxidation of CO in currents. rich in H2, known as Preferential CO Oxidation (CO-PROX), whose useful operating range does not exceed this limit of thermal stability.
    [0155] The support in the form of a monolith was prepared by 3D printing using a Project 1200 printer from a VisiJet® FTX Green photosensitive liquid resin from 3D Systems.
    [0157] For this monolithic support in particular, a design was implemented that presented prismatic indentations along each wall of the canal (See Figure 1). The monolith support is a cylinder 1 cm in diameter and 1.5 cm in length, and has 21 channels of square cross section (0.1 cm x 0.1 cm) parallel to each other.
    [0159] Preparation of the polymeric support in the form of a monolith comprising charges of C or SÍO2
    [0161] Different amounts of carbon (Vulcan XC72 from Cabot) and silica (Silica Fumed S5130 from SIGMA-ALDRICH) were dispersed by contacting the solid with the liquid resin for 5 minutes maintaining magnetic stirring and avoiding light to prevent curing of the resin.
    [0163] Procedure for preparing the active phase
    [0165] In this example, the material composed of copper oxide dispersed on cerium oxide, CuO / CeO2, was used as the active phase of the catalyst. For the preparation of the active phase, CeO2 was initially obtained from the calcination of Ce (NO3) 3-6H2O (99.5%, Alpha Aesar) using a muffle programmed at 5 ° C / min until reaching 500 ° C , maintaining said temperature for 4 hours. Subsequently, the addition of Cu was carried out by impregnation in incipient humidity of CeO2 with a solution of Cu (NO3) 2-2.5H2O (> 98%, Sigma-Aldrich) in distilled water. At this stage it is important to control the volume of solution with which the CeO2 surface is moistened, in order to obtain a homogeneous and continuous coating, without soaking it. The amount of dissolved Cu salt was calculated to arrive at a final composition of 6% by weight (w / w) of Cu in the active phase. After impregnation, the material obtained was placed in the muffle previously heated to 200 ° C, in order to avoid the migration of Cu to the surface of the catalyst and, consequently, reduce the sintering of the copper oxide during the treatment of decomposition of salt. The decomposition was carried out at 400 ° C with a ramp of 2 ° C / min for 2 hours. After the process described, the active phase is obtained CuO / CeO2 powder.
    [0167] Catalyst preparation procedure: Anchoring the active phase to the support
    [0169] The next stage is the impregnation of the monolith support with the CuO / CeO2 active phase in powder. For this stage, a suspension of the active CuO / CeO2 phase in H2O was prepared. In any case, before starting the dip coating, the external part of the monolith support was covered with Teflon tape and the channels were impregnated drop by drop with the corresponding suspension of the active phase CuO / CeO2 in H2O, ensuring that each channel comes into contact with the suspension of the active phase. Each monolithic support was kept immersed for a few seconds in the CuO / CeO2 active phase suspensions in H2O, which were constantly stirred to guarantee their homogeneity. Next, the samples obtained were left to dry for 24 hours at room temperature, rotating horizontally to obtain an adequate dispersion in the channels and finally, they were treated in a flow of N2 (100 ml / min) under a temperature program with a ramp of 5 ° C / min to 150 ° C for 2 hours, followed by a ramp of 2.5 ° C / min to 250 ° C for 2 hours. At the end of each heat treatment, the excess CeO2 that clogged the channels of the monolith was removed using a stream of compressed air. Finally, they were treated in air flow (100 ml / min) under a temperature program with a ramp of 5 ° C / min to 250 ° C for 2 hours.
    [0171] The monolithic polymeric support allows the accumulation of the active phase in its grooves, achieving a uniform distribution of the active phases, as seen in the image obtained by scanning electron microscopy (SEM) of Figure 2. The monolith support It is a cylinder 1 cm in diameter and 1.5 cm long, and has 21 channels of square cross section (0.1 cm x 0.1 cm) parallel to each other.
    [0173] The chemical analysis performed using the EDS technique (Hitachi S-3000N microscope with Bruker XFlash 3001 analyzer for EDS microanalysis) shows the distribution of the chemical elements of the CuO / CeO2 catalyst deposited in the channels of the monolith support. See Figure 3 (a) Cu and 3 (b) Ce. In addition, the homogeneous distribution of Cu was identified over the entire surface of CeO2 (Figure 3), which shows the adequate distribution of the active sites available to react.
    [0175] Table 1 shows, as an example, the amount of active phase anchored as a function of of the different proposed preparation variables: Composition of the resin (pure or doped), design of the channels (smooth or with slits) and number of impregnation stages.
    [0177] Table 1. Summary of the catalysts prepared based on the composition of the polymeric support, the design of the support channels and the percentage by weight of the active phase in the catalyst.
    [0179]
    [0182] * Cat = Catalyst
    [0184] Taking catalyst 1 as a reference, the results of table 1 show that the modification of the resin composition by adding charges of SiO2 and C (catalysts 4-6), the modification of the design of the smooth channels to include slits (catalysts 2-3, 6) and increasing the number of impregnation stages (catalyst 3) make it possible to increase the percentage by weight of the active phase in the catalyst.
    [0185] Oxidation reaction preference! of CO in the presence of H2 ( CO-PrOx)
    [0187] Catalytic activity tests were carried out with catalyst 2 for the preferential oxidation reaction of CO in the presence of H2 (CO-PrOx) and were compared with the results obtained with unsupported powdered CuO / CeO2 catalyst 0. The test conditions for the preferential oxidation reaction of CO in the presence of H2 (CO-PrOx) are 2% CO, 2% O2, 30% H2, and He balance up to 30 ml / min, 60 ml / min, 90 ml / min and 120 ml / min.
    [0189] When comparing the catalytic activity with a flow of 90 ml / min, it is observed that catalyst 0 reached a maximum conversion of 99.5% at approximately 170 ° C, while catalyst 2 reached its maximum conversion (98.5%) at a slightly higher temperature (207 ° C). The general behavior of the two catalysts 0 and 2 is therefore similar, presenting qualitatively very similar conversion and selectivity profiles (See Figure 4).
    [0191] Additionally, it stands out from catalyst 2, that after 10 hours of reaction in a flow of 60 ml / min, both the conversion (95%) and the selectivity (90%) remain stable, demonstrating good catalytic activity for long reaction times. (Figure 5).
    [0193] Therefore, it can be concluded that monolith-supported catalysts are more robust than powder catalysts and have greater resistance to friction wear, as well as low pressure drops and good heat and mass transfer characteristics.
    权利要求:
    Claims (22)
    [1]
    1. A catalyst characterized by comprising
    • a polymeric support with a plurality of surfaces and
    • at least one active phase,
    where the active phase covers at least one surface of the polymeric support.
    [2]
    2. The catalyst according to claim 1, wherein the polymeric support is monolithic.
    [3]
    3. The catalyst according to any of claims 1 or 2, wherein the percentage by weight of the active phase in the catalyst is between 1% and 50%.
    [4]
    4. The catalyst according to any one of claims 1 to 3, wherein the percentage by weight of the active phase in the catalyst is between 2% and 15%.
    [5]
    5. The catalyst according to any of claims 1 to 4, wherein the percentage by weight of the active phase in the catalyst is between 3% and 6%.
    [6]
    6. The catalyst according to any of claims 1 to 5, wherein the polymeric support comprises a plurality of channels.
    [7]
    7. The catalyst according to any of claim 6, wherein the plurality of channels comprises a plurality of irregularities.
    [8]
    8. The catalyst according to any one of claims 1 to 7, wherein the polymeric support is a thermoset polymeric resin photosensitive to ultraviolet light.
    [9]
    9. The catalyst according to any of claims 1 to 8, wherein at least one active phase is CuO / CeO2.
    [10]
    10. The catalyst according to any of claims 1 to 9 comprising a single active CuO / CeO2 phase.
    [11]
    11. The catalyst according to any of claims 1 to 10, wherein the polymeric support further comprises C and / or SiO2 in a percentage by weight of between 0.3% and 3.5% by weight with respect to the total weight of the polymeric support.
    [12]
    12. A process for obtaining a catalyst according to any of claims 1 to 11, characterized in that it comprises the following steps:
    a) shaping the polymeric support starting from a thermoset polymeric resin and curing said resin;
    b) coating at least one surface of the support obtained in step (a) with a suspension comprising at least one active phase,
    c) horizontally rotating the product obtained in step (b) and drying,
    d) heat treating the product obtained in step (c) in the presence of an inert atmosphere,
    e) heat treating the product obtained in step (d) in the presence of an oxidizing atmosphere.
    [13]
    The method according to claim 12, wherein step (a) is carried out by 3D printing.
    [14]
    The process according to claims 12 to 13, wherein the thermosetting polymeric resin of step (a) is photosensitive to UV light and is cured by exposure to UV light.
    [15]
    The method according to claim 12 to 14, wherein step (b) is repeated more than once before proceeding to step (c).
    [16]
    16. The process according to any of claims 12 to 15, wherein step (b) is carried out by immersion.
    [17]
    17. The process according to any one of claims 12 to 16, wherein the heat treatment of step (e) is carried out in the presence of air, oxygen or a mixture of oxygen and nitrogen.
    [18]
    18. A process for obtaining a catalyst according to any of claims 6 or 7 characterized in that it comprises all the steps of the process according to claims 12 to 17 and an additional step (b '), between stage (b) and stage (c), of coating each of the channels with the suspension used in stage (b).
    [19]
    19. The process according to claim 18, wherein the additional step (b ') is a dropwise impregnation of each of the channels.
    [20]
    20. A process for obtaining a catalyst according to claim 11, characterized in that it comprises all the steps of the process according to claims 12 to 19, wherein the step of shaping the polymeric support is in turn divided into:
    a1) mixing a thermosetting polymeric resin with C and / or SiO2, the percentage by weight of C and / or SiO2 being between 0.3% and 3.5% with respect to the total weight of the polymeric support; and
    a2) shaping the catalyst support starting from the product obtained in step (a1) and curing said product.
    [21]
    21. Use of the catalyst according to any of claims 1 to 11 in heterogeneous catalysis reactions.
    [22]
    22. Use of the catalyst according to any of claims 1 to 11 in the preferential oxidation reaction of CO in the presence of H2.
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    同族专利:
    公开号 | 公开日
    WO2020240058A1|2020-12-03|
    ES2797001B2|2021-05-25|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20180126298A1|2015-05-22|2018-05-10|Merck Patent Gmbh|Device for substance separation|
    CN108607565A|2018-04-19|2018-10-02|上海理工大学|A kind of CuO/CeO2Catalyst and its preparation method and application|
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    PCT/ES2019/070826| WO2020240058A1|2019-05-31|2019-12-04|Heterogeneous catalyst with polymeric support|
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