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    • 专利摘要:
    Monolithic catalyst manufacturing process and use thereof. The present invention relates to a process for manufacturing or forming catalysts based on lamellar double hydroxides (HDL) and sepiolite for use in the production of hydrogen by reforming ethanol with water vapor. The shaping process comprises: synthesis of the catalysts based on HDL and sepiolite in a pulverulent state; preparation of a homogeneous mixture of the pulverulent catalysts and a binder; shaping said mixture by simultaneous application of heat and pressure to obtain a piece or "green body"; pyrolysis treatment of said green body to obtain a brown body, and calcination of said brown body to obtain the catalytic monolith. The invention also relates to the monoliths prepared by this process and their use in the production of hydrogen from the reforming of ethanol with water vapor. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2703016A1
    申请号:ES201731077
    申请日:2017-09-06
    公开日:2019-03-06
    发明作者:Lara Antonio Chica；Costa Serra Javier Francisco Da；Ruiz Ruben Beneito；Abril Juan Carratalá
    申请人:Aiju Asociacion De Investig de la Industria Del Juguete Conexas Y Afines；Consejo Superior de Investigaciones Cientificas CSIC；Universidad Politecnica de Valencia；
    IPC主号:
    专利说明:

    [0001]
    [0002] Monolithic catalyst manufacturing process and use thereof
    [0003]
    [0004] The present invention relates to a manufacturing process (synthesis and shaping) of monolithic catalysts based on lamellar double hydroxides (HDL) and sepiolite for use in the production of hydrogen by reforming ethanol with steam. The present invention is therefore directed to the sector of preparation of catalysts and the energy sector.
    [0005]
    [0006] BACKGROUND OF THE INVENTION
    [0007] The most commonly used chemical reactors in the production of hydrogen by catalytic reforming are fixed-bed reactors. However, its use has certain drawbacks. One of these drawbacks is that it is not possible to simultaneously minimize the pressure drop and the diffusional limitations in the pores of the catalyst because these phenomena depend on the particle size of the catalyst in opposite manner. In other words, in the case of pressure drop, large particle sizes are needed, while to avoid diffusional limitations in the pores of the catalyst the particle sizes have to be small. Another drawback of fixed-bed reactors is the poor distribution of the flow they usually present.
    [0008]
    [0009] In the literature the use of structured catalysts has been proposed to solve these drawbacks. In these cases it is usual that the catalyst is forming a small film that lines the walls or channels of different types of monoliths, allowing the high flow of reagents while producing small pressure drops.
    [0010]
    [0011] In structured catalysts, the active phase may be dispersed within the structure that forms the monolith or may be coating it. In the latter case, the catalyst is deposited forming a thin layer on the walls of the previously manufactured monolithic structure. Taking into account the nature and final form, the structured catalysts can be classified into metal mesh catalysts, catalysts with simple geometric shapes (disks, cylinders, pellets, etc.), foams and monoliths of parallel longitudinal channels, corresponding to the so-called "honeycomb" (honeycomb).
    [0012]
    [0013] As for the honeycomb monoliths, there are 2 parameters that characterize them: i) the cell density (cpsi) that is usually expressed in cells per square inch and ii) the thickness of the wall, in the case of ceramic monoliths the value cell density ranges between 50 and 400 cpsi, while the value of the wall thickness is between 1 and 0.1 mm In the case of metal monoliths, values of 1600 cpsi are reached for cell density and between 100 and 20 pm of wall thickness.
    [0014]
    [0015] The use of catalysts formed in the form of monoliths in the reforming of ethanol presents important advantages, since they improve mass transport and heat exchange, cause low pressure drops, prevent blockage of the reactor and allow a more precise control of the conditions of reaction, leading to significant improvements in performance to hydrogen. In addition, they allow an easy scaling of the process and a homogeneous flow distribution. In the scientific literature you can find several studies related to the use of monoliths in the reaction of reforming ethanol with water vapor. One of these studies mentions the use of "honeycomb" monoliths based on Co / ZnO with Mn, (A. Casanovas et al., Chemical Engineering Journal, 154 (2009) 267-273) .In another study, "honeycomb" includes CeO2 in its composition together with noble metals such as Rh and Pd (E. López, et al, International Journal of Hydrogen Energy, 38 (2013) 4418-4428). In another paper (J. Llorca et al., Catalysis Today, 138 (2008) 187-192), they present the monolith preparation route, where the active phase is a mixture of zinc and cobalt oxides, has a strong influence both in the homogeneity and stability of the coatings of the catalyst in the structure, as well as in the yield of hydrogen in the reaction of reforming ethanol. Concretely, the conventional preparation by immersion coating of the monoliths results in non-homogeneous catalytic coatings with poor adhesion, requiring non-conventional coating methods. Therefore, the homogeneity and stability of the coatings is essential to achieve stable catalytic monoliths in the reaction of reforming ethanol with water vapor. The results that are considered optimal in the reaction of ethanol reforming consist of high conversions of ethanol, high yields to H2 and low selectivities of CO and CH4.
    [0016] At present, there are different techniques that allow to shape (or shape) materials that are in a pulverulent state whatever their starting nature (ceramics, clays, polymers, etc.), among them, the catalysts developed in the laboratory to obtain the They are called "monoliths." Among the techniques for shaping pulverulent materials are thermocompression, extrusion and additive manufacturing techniques, depending on the technique used, monoliths with geometric shapes of different complexity and with different designs can be obtained. agglomerate the materials, previous addition of a binder and by the simultaneous application of pressure and temperature, in discs or cylinders.The thermocompression is characterized by a very simple method and by the geometric simplicity of the monoliths that are manufactured. the materials in filaments or "pellets" and in monoliths "h oneycomb "previous preparation of extrudable pastes with very specific rheological properties through the incorporation of various additives (binders, lubricants, plasticizers, deflocculants, etc.). Although extrusion is more versatile and allows the formation of monoliths with forms more complex than thermocompression, the formulation of the pastes necessary for shaping is not trivial. The so-called additive manufacturing techniques, among which is Selective Laser Sintering (SLS), allow to obtain in a short time and without human intervention, pieces of great geometric complexity from models previously designed with computer software. The SLS technique is widely used in the development of preforms both in the ceramic field and with metals and has shown very promising results in the preparation of ceramic monoliths (ES2427715). Selective Laser Sintering is a technique in which a CO2 laser beam of micrometric precision is commissioned, under the orders given by software, to melt or sinter in a controlled manner the material, plane to plane, drawing the geometric shape of the Pre-designed preform. The Selective Laser Sintering technique has two variants: Direct and Indirect.
    [0017]
    [0018] In the Direct Selective Laser Sintering the material that is sintered is the base material itself, which must have a relatively low melting point that will depend on the nature of the material (polymeric material, metal).
    [0019]
    [0020] In Indirect Selective Laser Sintering, hereinafter referred to as "Indirect SLS", the sintering of the starting base material is carried out by the addition of sintering agents. These sintering agents are usually polymeric materials with a relatively low melting point so that when they melt they serve as a binding element of the starting base material. In the Indirect SLS, the choice of the sintering agent is critical in the success of forming. With any of the 3 techniques mentioned above (thermocompression, extrusion, SLS) is achieved that the catalyst is structural part of the monolith, avoiding the problems mentioned above with the conventional method of dip coating at the time of preparing the monoliths.
    [0021]
    [0022] DESCRIPTION OF THE INVENTION
    [0023]
    [0024] The present invention provides a simple, fast and inexpensive method for the preparation of monolithic systems based on double lamellar hydroxide (HDL) and sepiolite catalysts using the thermocompression technique for use, mainly, in the reaction of ethanol reforming with steam. Water.
    [0025]
    [0026] A first aspect of the present invention relates to a process for the preparation of monolithic catalysts based on lamellar double hydroxides (HDL) or on sepiolite (natural), both laminar compounds, by means of the thermocompression technique. Double layered hydroxides (HDLs) are synthetic structures formed by sheets of positively charged metal hydroxides that are stabilized with interlamellar anions. The forming process of these catalysts (HDLs and sepiolite), according to the present invention, is characterized by being respectful with the nature of the starting catalysts and does not require the incorporation of additives and solvents for processing, with the corresponding cost savings and reduction of risks for workers' health. The shaped catalysts obtained according to the process of the invention have a high mechanical strength and high density, which is especially advantageous in the formation of packed beds.
    [0027]
    [0028] Therefore, the invention provides a method for the production of monolithic catalysts characterized in that it comprises the following steps:
    [0029]
    [0030] i) preparation of a homogeneous mixture of a catalyst with a laminar structure selected from a double laminar hydroxide and sepiolite in powdery state, and a binder, where the binder is a phenolic or cellulosic resin,
    [0031] ii) compaction of the mixture obtained in step i) by simultaneous application of pressure equal to or greater than 800 Kg / cm2 and temperature between 80 and 200 ° C until forming a piece called "green body" (shaped piece),
    [0032] iii) pyrolysis treatment of said green body (piece formed in step ii)) in an inert atmosphere, at a temperature between 400 and 1000 ° C and a time between 1 and 6 hours. In this way a pyrolyzed piece is obtained, called "brown body", which contains a coal residue from the pyrolysis of the binder,
    [0033] iv) calcination of the "brown body" (pyrolyzed part in step iii)) by a heat treatment in a reactive atmosphere comprising O 2 to remove the carbon residue, a byproduct of pyrolysis, at a temperature comprised between 450-1500 ° C and times preferably between 1 and 6 hours.
    [0034]
    [0035] The double layered hydroxides in the pulverulent state include a divalent cation (M2 +) and aluminum (Al3 +) with M2 + / (Al3 ++ M2 +) ratios comprised between 0.20 and 0.33, where the divalent cation would be Mg2 +, Ca2 + or Zn2 +. In addition, the HDLs of this invention may comprise other elements such as those mentioned below:
    [0036] - one or combinations of two or more elements of groups VIIIB, IB, VIB and Nb, Ti, Zr, Mn, Re, Ga and Sn in percentages by weight between 0.5% and 30% with respect to the total weight of the catalyst synthesized in powdery state and can further comprise
    [0037] - one or combinations of two or more elements of groups IA, IIA and Ce and La in percentages by weight comprised between 0.1% and 10% with respect to the total weight of the catalyst synthesized in pulverulent state.
    [0038]
    [0039] The catalysts based on sepiolite in a pulverulent state may comprise, in addition to sepiolite (natural sepiolite):
    [0040] - one or combinations of two or more elements of groups VIIIB, IB, VIB and Nb, Ti, Zr, Mn, Re, Ga and Sn in percentages by weight between 0.5% and 30%, and can also comprise
    [0041] - one or combinations of two or more elements of groups IA, IIA and Ce and La in percentages by weight between 0.1% and 10%.
    [0042]
    [0043] In a preferred embodiment, prior to step i) of preparing the homogeneous mixture, the synthesis of the HDL-based catalysts is carried out in the pulverulent state by the precipitation of their corresponding metal salts.
    [0044]
    [0045] To do this, two aqueous solutions are prepared, one acidic and the other basic, as described below:
    [0046] Acid solution: Formed by the necessary amount of the metal cation M2 + and Al3 +, so that the ratio M2 + / (Al3 ++ M2 +) is between 0.20 and 0.33.
    [0047] Basic dissolution: Formed by the necessary amount of NaNO3 and NaOH or NaCO3 and NaOH to achieve the precipitation of the metals M2 + and Al3 +.
    [0048]
    [0049] Both solutions are mixed at room temperature under constant stirring to form a gel. Preferably they are added by means of an infusion pump, at a speed between 0.5 and 10 ml / min, more preferably between 1 and 2 ml / min. The gel formed during coprecipitation should have a pH value of 5.5 and 7.5, preferably between 6 and 6.5.
    [0050]
    [0051] The gel obtained, preferably deposited in a polypropylene bottle, is maintained at temperatures between 40 and 75 ° C, preferably for a time of 10 to 20 hours. Then, the gel is filtered, washed and dried at a temperature between 50 and 100 ° C, preferably for a time of 12 to 24 hours. Finally, it is calcined between 350 and 750 ° C, preferably for a time of 2 to 5 hours, thus obtaining a pulverulent material based on an HDL.
    [0052]
    [0053] Optionally, to the obtained HDL-based catalyst is added one or combinations of two or more elements of groups VIIIB, IB, VIB and Nb, Ti, Zr, Mn, Re, Ga and Sn in percentages by weight comprised between 0.5 % and 30%. The incorporation of this first series of elements can be carried out by wet impregnation, wet impregnation at pore volume, wet impregnation in rotavapor or precipitation using as precursors their corresponding chlorides, acetates, nitrates, carbonates or sulfates. After the incorporation of these elements a calcination is carried out at temperatures between 350-800 ° C during a time between 2 and 6 hours. Subsequently, optionally, one or combinations of two or more elements of groups IA, IIA, Ce and La are incorporated in percentages by weight comprised between 0.1% and 10%. The incorporation of this second series of elements can be carried out by wet impregnation, wet impregnation with pore volume, wet impregnation in rotavapor or precipitation using as precursors their corresponding chlorides, acetates, nitrates, carbonates or sulfates. After the incorporation of these elements, one is carried out at temperatures between 350-800 ° C for a time comprised between 2 and 6 hours.
    [0054]
    [0055] The introduction of both series of elements to the HDL-based material can also be carried out in its preparation stage, during precipitation, by incorporating the corresponding salts of the elements described in the two series in the acid solution. This avoids having to perform two of the aforementioned calcinations. In this way, the pulverulent catalyst based on HDL is obtained, which will later be formed by the thermocompression method.
    [0056]
    [0057] In another preferred embodiment, prior to step i) of preparing the homogeneous mixture, the preparation of the natural sepiolite-based catalyst is carried out, starting from natural sepiolite to which one or combinations of two or more are incorporated. elements of groups VIIIB, IB, VIB and Nb, Ti, Zr, Mn, Re, Ga and Sn in percentages by weight between 0.5% and 30%. The incorporation of this first series of elements can be carried out by precipitation, wet impregnation, wet impregnation at pore volume, wet impregnation in rotavapor or precipitation using as precursors their corresponding chlorides, acetates, nitrates, carbonates or sulfates. After the incorporation, calcination is carried out at temperatures between 350-800 ° C for a time comprised between 2 and 6 hours. Optionally, the resulting material is incorporated one or combinations of two or more elements of groups IA, IIA and Ce and La in percentages by weight comprised between 0.1% and 10%. The incorporation of this second series of elements can be carried out by wet impregnation, wet impregnation with pore volume, wet impregnation in rotavapor or precipitation using as precursors their corresponding chlorides, acetates, nitrates, carbonates or sulfates. After the incorporation a calcination is carried out temperatures between 350-800 ° C for a time between 2 and 6 hours. The incorporation of the two series of elements can be carried out sequentially, as described, or simultaneously, saving in this case one of the calcination stages. In this way, the catalyst based on sepiolite is obtained, which will later be formed by the thermocompression method.
    [0058]
    [0059] In a preferred embodiment, step i) comprises mixing a catalyst based on a double laminar hydroxide with a cellulosic resin.
    [0060]
    [0061] In another preferred embodiment, step i) comprises mixing a catalyst based on a double layered hydroxide with a phenolic resin.
    [0062]
    [0063] In another preferred embodiment, step i) comprises mixing a catalyst based on sepiolite and a phenolic resin.
    [0064]
    [0065] In another preferred embodiment, step i) comprises mixing a catalyst based on sepiolite with a cellulosic resin.
    [0066]
    [0067] In a preferred embodiment of the process of the invention, in step i) a phenolic resin is used as a binder. Preferably, the phenolic resin has a melting point of less than 150 ° C and a volatile content of less than 60% by weight with respect to said resin, with "volatile" being understood as the gaseous decomposition products that are released from the material when it is subjected to heating in an inert atmosphere up to high temperatures (900 ° C). In a more preferred embodiment, the phenolic resin belongs to the novolac family. The "novolacs" are phenol formaldehyde resins in which there is a molar excess of phenols or phenolic groups and in the presence of an acid catalyst their polymer chains are crosslinked forming a stable three-dimensional network.
    [0068]
    [0069] In another preferred embodiment of the process of the invention, a cellulosic resin is used as binder in step i). Preferably, the cellulosic resin has a melting point lower than 160 ° C and a volatile content greater than 90%. In a more preferred embodiment, the cellulosic resin is an alkyl hydroxyethyl cellulosic resin.
    [0070] In a preferred embodiment of the invention, the ratio between the amounts of starting base catalyst and binder to prepare the mixture is between 85/15 and 99/1 and more preferably the ratio is 95/5 or 98/2.
    [0071]
    [0072] In a preferred embodiment, the pressure applied in step ii) is at least 1000 Kg / cm2, preferably between 1000 and 5000 Kg / cm2 and / or the temperature is between 100 and 165 ° C.
    [0073]
    [0074] In another preferred embodiment, the pressure applied in step ii) is carried out in a hot plate hydraulic press.
    [0075]
    [0076] In another preferred embodiment, in step ii), the mixture is introduced into a cylindrical cavity mold prior to the application of the pressure in order to obtain a "green body" or piece shaped with a cylindrical or disk geometry shape.
    [0077]
    [0078] In a preferred embodiment, step iii) of pyrolysis is carried out at temperatures between 600 and 900 ° C. Preferably, the inert atmosphere used in step iii) is N2, Argon, Helium or mixtures thereof; more preferably, the inert atmosphere is N2.
    [0079]
    [0080] In a preferred embodiment, the thermal treatment of step iv) is carried out at a temperature between 600 and 1000 ° C. Preferably, the reactive atmosphere used in step iv) is selected from air, pure oxygen and mixtures of O2 and an inert gas (N2, Argon, Helium, etc.); more preferably the reactive atmosphere is air.
    [0081]
    [0082] The monolithic HDL or sepiolite catalyst is obtained by the procedure described above.
    [0083]
    [0084] A second aspect of the invention relates to a monolithic catalyst obtained by the process defined in the first aspect of the present invention. It is understood as "monolithic catalyst" that in which the catalyst has been incorporated during the manufacture of the monolith itself, and that has a well defined structure and geometry (discotic, cylindrical, spherical, "honeycomb", etc.) and is mechanically stable, allowing to be manipulated without it suffering any type of deterioration.
    [0085] A third aspect of the invention relates to the use of the monolithic catalysts obtained by the process described above in hydrogen production processes by reforming (for example with steam, partial oxidation, autothermal reforming, and reforming in the presence of CO2) of alcohols with a number of carbon atoms comprised between 1 and 6 ((C 1 -C 6) alcohols) and hydrocarbons with a carbon atom number comprised between 1 and 10 (hydrocarbons (C 1 -C 10)).
    [0086]
    [0087] More preferably, the third aspect of the invention relates to the use of the monolithic materials obtained by the process described above as catalysts in the reaction of reforming ethanol with steam. This reforming reaction allows obtaining hydrogen.
    [0088]
    [0089] Throughout the description and the claims the word "comprises" and its variants do not intend to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and characteristics of the invention will emerge partly from the description and partly 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.
    [0090]
    [0091] BRIEF DESCRIPTION OF THE FIGURES
    [0092]
    [0093] FIG. 1: Graph showing the conversion of ethanol, as a function of the reaction temperature, exhibited by the catalysts based on HDL in pulverulent state and in the form of monoliths made with cellulosic resin in a reforming reaction of ethanol with water vapor.
    [0094]
    [0095] FIG. 2: Graph showing the conversion of ethanol, as a function of the reaction temperature, exhibited by the catalysts based on sepiolite in pulverulent state and in the form of monoliths made with cellulosic resin in a reaction of reforming ethanol with water vapor.
    [0096]
    [0097] FIG. 3: Graph showing the selectivity to different reaction products of the pulverulent state catalysts and the catalytic monoliths of HDL with resin cellulose at different temperatures in the reformed ethanol with steam.
    [0098]
    [0099] FIG. 4: Graph showing the selectivity to different reaction products of the pulverulent state catalysts and of the sepiolite catalytic monoliths with cellulose resin at different temperatures in the steam ethanol reforming.
    [0100]
    [0101] FIG. 5: Graph showing the conversion of ethanol of the catalysts in pulverulent state and of the catalytic monoliths of HDL with phenolic resin at different temperatures in the reforming of ethanol with steam.
    [0102]
    [0103] FIG. 6: Graph showing the conversion of ethanol of the catalysts in pulverulent state and of the catalytic monoliths of sepiolite with phenolic resin at different temperatures in the reforming of ethanol with steam.
    [0104]
    [0105] FIG. 7: Graph showing the selectivity to different products of the pulverulent state catalysts and the catalytic monoliths of HDL with phenolic resin at different temperatures in the reforming of ethanol with water vapor.
    [0106]
    [0107] FIG. 8: Graph showing the selectivity to different products of the pulverulent state catalysts and the catalytic monoliths of sepiolite with phenolic resin at different temperatures in the reforming of ethanol with water vapor.
    [0108]
    [0109] EXAMPLES
    [0110] The invention will now be illustrated by means of tests carried out by the inventors, which highlights the effectiveness of the product of the invention.
    [0111]
    [0112] Synthesis of catalysts in pulverulent state:
    [0113]
    [0114] Example 1:
    [0115]
    [0116] In this example, the preparation of the HDL-based catalyst for its subsequent formation and use in the reforming of ethanol with steam is described.
    [0117]
    [0118] The preparation of the HDL-based catalyst is carried out by coprecipitation of its corresponding metal salts. This method consists of the Obtaining HDL from two aqueous solutions, one acidic and the other basic, prepared as follows:
    [0119]
    [0120] To prepare 20 g of catalyst, the acid solution must be formed by 39.33 g of Zn (NO3) 2-6H2O (Sigma-Aldrich, 98%), 13.36 g of Al (NO3) 3'9H2O (Sigma- Aldrich, 98%), 6.23 g (NO3) 3'6H2O (Sigma-Aldrich, 99%), 19.73 g of Co (NO3) 2'6H2O (Sigma-Aldrich, 98.5%) and 171 , 36 g of milliQ water.
    [0121]
    [0122] In the case of the basic solution, it should be formed by 28.33 g of NaNO3 (Sigma-Aldrich, 99%), 15.33 g NaOH (Sigma-Aldrich, 98%) and 206.34 g of milliQ water.
    [0123]
    [0124] Both solutions are added dropwise at room temperature by means of an infusion pump (Cole-Parmer 60.061) at a rate of 1 ml / min under constant agitation. The gel formed during coprecipitation has a pH = 6. This gel is deposited in a polypropylene bottle and kept in an oven at 60 ° C for 18 hours. After this time, the gel is filtered, washed and dried in an oven at 100 ° C overnight.
    [0125]
    [0126] Finally, it is calcined at 600 ° C in a flask for 3 hours, thus obtaining the oxides from the lamellar double hydroxides. With this procedure the pulverulent catalyst named as: HDL is obtained.
    [0127]
    [0128] Example 2:
    [0129] In this example, it describes the preparation of the sepiolite-based catalyst for its subsequent formation and use in the reforming of ethanol with steam.
    [0130]
    [0131] For the preparation of the sepiolite-based catalyst, natural sepiolite (Pangel S9), provided by the company TOLSA, was used. In this sample, Co was introduced by the precipitation method. For this, two solutions were prepared, one with 14.82 g of Co (NO3) 26H2O (Sigma-Aldrich, 98%) in one liter of milliQ water and the other with 20 g of sepiolite in 180 g of water milliQ. Both solutions were brought to pH = 2 with the addition of 60% Scharlau nitric acid, in order to achieve complete dissolution of the metals and suspension of the sepiolite. Then, maintaining the solution of the sepiolite in continuous agitation, the solution is added with the metal at a rate of 1 ml / min using the perfusion pump (KdScientific). Then a 1 M NaOH solution (Sigma-Aldrich, 98%) is added until a pH of 11 is reached. It is then filtered and dried to obtain the catalyst powder. It is then calcined at 600 ° C in a muffle for 3 hours. Finally, wet impregnation was carried out at pore volume to incorporate 10% by weight of La in the catalyst, using 6.23 g La (NO3) 36H2O (Sigma-Aldrich, 99%) dissolved in 3 mL of milliQ water, later it is dried in a stove of 100 ° C and it is again calcined in muffle at 600 ° C obtaining the catalyst that has been labeled as Sep.
    [0132]
    [0133] Manufacture of monoliths:
    [0134] Example 3:
    [0135] In this example, it describes the manufacturing of monolithic systems based on HDL and Sep catalysts with 2% binder and sintered (calcined) at 600 ° C.
    [0136]
    [0137] For the manufacture of the monoliths, we start with the pulverulent catalysts HDL and Sep prepared in Examples 1 and 2, respectively. As a binder, two types of resins have been selected: a phenolic resin of the novolac family (manufacturer "Georgia Pacific") and a cellulose resin, namely methyl-2-hydroxyethylcellulose (Aldrich 435015). For the preparation of the HDL or Sep monoliths, a binder: catalyst ratio of 2:98 by weight is used, which means that to form 10 g of catalyst, 204 mg of binder is necessary. Prior to mixing, the catalysts are subjected to an oven drying step at 110 ° C for 12 hours. Once dried, they are mixed homogeneously with the binder in the proportions mentioned above by means of a ball mill for 20 minutes. Once the homogeneous mixture of all the materials is achieved, it is introduced into the cavity of a steel mold suitable for thermoforming at high pressures and moderate temperatures in order to carry out the obtaining of the "green bodies" . The compaction of the material is carried out in a hydraulic press of hot plates "Liquidpes" by the application of a closing force on the mold and under a heating program that are detailed below:
    [0138]
    [0139]
    [0140]
    [0141]
    [0142]
    [0143] Once the process of thermocompression of the material has been completed, the green bodies are removed from the mold and subjected to a thermal treatment in an inert atmosphere of pure N 2 (99.999%) in order to decompose the binder of the materials' sinus. The heat treatment consists of a heating in several stages, which are carried out in isothermal mode (constant temperature) and not isothermal (under an increase in temperatures). The flow rate of N 2 used to make the pyrolysis is approximately 50 ml / min per gram of green body material to be pyrolyzed. The heating stages of the pyrolysis of the green bodies are shown below:
    [0144]
    [0145]
    [0146]
    [0147]
    [0148] Once the pyrolysis stage of the green bodies has been completed, the calcination stage of the brown bodies obtained is carried out in order to achieve the pure monolithic catalysts. To do this, the brown bodies are subjected to heating under an O 2 atmosphere (calcination). The flow rate of oxygen used in the calcination stage is 40 ml / min for each gram of monolith. The calcination process of the monoliths consists of different stages (isotherms and non-isotherms) and the conditions used are as follows:
    [0149]
    [0150]
    [0151] The monoliths of the catalysts obtained after the calcination process have a high mechanical strength, high density, high purity and do not present cracks. In this way, the samples named below were obtained:
    [0152] 1) 2.Res.Cel.HDL.600. HDL monolith with 2% cellulose resin calcined at 600 ° C.
    [0153] 2) 2.Res.Cel.Sep.600.Monolith of Sepiolite with 2% cellulose resin calcined at 600 ° C.
    [0154] 3) 2.Res.Fen.HDL.600.Monolith of HDL with 2% phenolic resin calcined at 600 ° C.
    [0155] 4) 2.Res.Fen.Sep.600.Monolith of Sepiolite with 2% phenolic resin calcined at 600 ° C.
    [0156]
    [0157] Example 4:
    [0158] In this example, the production of monolithic systems based on HDL and Sep catalysts with 2% binder and sintered at 1300 ° C is described.
    [0159]
    [0160] For the preparation of the monoliths, we start with the pulverulent catalysts of HDL and Sep prepared in Examples 1 and 2, respectively. As a binder, two types of resin have been selected: a phenolic resin of the novolac family (manufacturer "Georgia Pacific") and a cellulose resin, specifically methyl-2-hydroxyethylcellulose (Aldrich 435015). For the preparation of the monoliths of HDL or Sepiolite is based on a ratio of binder: catalyst 2:98 by weight, which means that to form 10 g of catalyst, 204 mg of binder is necessary. Prior to mixing, the catalysts are subjected to an oven drying step at 110 ° C for 12 hours. Once dried, they are mixed homogeneously with the binder in the proportions mentioned above by means of a ball mill for 20 minutes. Once the homogeneous mixture of all the materials is achieved, the thermocompression mold is loaded to carry out the obtaining of the "green bodies". The thermoforming of the material is carried out in a hydraulic press of hot plates "Liquidpes" by the application of a closing force on the mold and under a heating program that are detailed below:
    [0161]
    [0162]
    [0163]
    [0164]
    [0165] Once the process of thermoforming the material has been completed, the green bodies are removed from the mold and subjected to a thermal treatment in an inert atmosphere of pure N 2 (99.999%) in order to decompose the binder in the material's bosom. The heat treatment consists of a heating in several stages, which are carried out in isothermal mode (constant temperature) and not isothermal (under an increase in temperatures). The flow rate of N 2 used to make the pyrolysis is approximately 50 ml / min per gram of green body material to be pyrolyzed. The heating stages of the pyrolysis of the green bodies are shown below:
    [0166]
    [0167]
    [0168]
    [0169]
    [0170] Once the pyrolysis stage of the green bodies has been completed, the calcination stage of the brown bodies obtained is carried out in order to achieve the pure monolithic catalysts. To do this, the brown bodies are subjected to heating under an O 2 atmosphere (calcination). The flow rate of oxygen used in the calcination stage is 40 ml / min for each gram of monolith. The calcination process of the monoliths consists of different stages (isotherms and non-isotherms) and the conditions used are as follows:
    [0171]
    [0172]
    [0173]
    [0174]
    [0175]
    [0176] The monoliths of the catalysts obtained after the calcination process have a high mechanical strength, high density, high purity and do not present cracks. In this way, the samples named below were obtained:
    [0177] 1) 2.Res.Cel.HDL.1300.Monolith of HDL with 2% cellulose resin calcined at 1300 ° C.
    [0178] 2) 2.Res.Cel.Sep.1300.Monolith of Sepiolite with 2% cellulose resin calcined at 1300 ° C.
    [0179] 3) 2.Res.Fen.HDL.1300.Monolith of HDL with 2% phenolic resin calcined at 1300 ° C.
    [0180] 4) 2.Res.Fen.Sep.1300.Monolith of Sepiolite with 2% phenolic resin calcined at 1300 ° C.
    [0181]
    [0182] Example 5:
    [0183] In this example, it describes the manufacture of monolithic systems based on HDL and Sep catalysts with 5% binder and sintered at 600 ° C.
    [0184]
    [0185] For the preparation of the monoliths, the starting point is HDL catalyst or natural Sepiolite catalyst. As a binder, two types of resin have been selected: a phenolic resin of the novolac family (manufacturer "Georgia Pacific") and a cellulose resin, specifically methyl-2-hydroxyethylcellulose (Aldrich 435015). For the preparation of the monoliths of HDL or Sepiolite is based on a ratio of binder: catalyst 5:95 by weight, which means that to form 10 g of catalyst, 526 mg of binder is necessary. Prior to mixing, the catalysts are subjected to an oven drying step at 110 ° C for 12 hours. Once dried, they are mixed homogeneously with the binder in the proportions mentioned above by means of a ball mill for 20 minutes. Once the homogeneous mixture of all the materials is achieved, the thermocompression mold is loaded to carry out the obtaining of the "green bodies". The thermoforming of the material is carried out in a hydraulic press of hot plates "Liquidpes" by the application of a closing force on the mold and under a heating program that are detailed below:
    [0186]
    [0187]
    [0188]
    [0189] Once the process of thermoforming the material has been completed, the green bodies are removed from the mold and subjected to a thermal treatment in an inert atmosphere of pure N 2 (99.999%) in order to decompose the binder in the material's bosom. The heat treatment consists of a heating in several stages, which are carried out in isothermal mode (constant temperature) and not isothermal (under an increase in temperatures). The flow rate of N 2 used to make the pyrolysis is approximately 50 ml / min per gram of green body material to be pyrolyzed. The heating stages of the pyrolysis of the green bodies are shown below:
    [0190]
    [0191]
    [0192]
    [0193]
    [0194] Once the pyrolysis stage of the green bodies has been completed, the calcination stage of the brown bodies obtained is carried out in order to achieve the pure monolithic catalysts. To do this, the brown bodies are subjected to heating under an O 2 atmosphere (calcination). The flow rate of oxygen used in the calcination stage is 40 ml / min for each gram of monolith. The calcination process of the monoliths consists of different stages (isotherms and non-isotherms) and the conditions used are as follows:
    [0195]
    [0196]
    [0197]
    [0198] The monoliths of the catalysts obtained after the calcination process have a high mechanical resistance, high density, high purity and do not present cracks. In this way, the samples named below were obtained:
    [0199] 1) 5.Res.Cel.HDL.600.Monolith of HDL with 5% cellulose resin calcined at 600 ° C.
    [0200] 2) 5.Res.Cel.Sep.600.Monolith of Sepiolite with 5% cellulose resin calcined at 600 ° C.
    [0201] 3) 5.Res.Fen.HDL.600.Monolith of HDL with 5% phenolic resin calcined at 600 ° C.
    [0202] 4) 5.Res.Fen.Sep.600.Monolith of Sepiolite with 5% phenolic resin calcined at 600 ° C.
    [0203]
    [0204] Example 6:
    [0205] In this example, it describes the manufacture of monolithic systems based on HDL and Sep catalysts with 5% binder and sintered at 1300 ° C.
    [0206]
    [0207] For the preparation of the monoliths, the starting point is HDL catalyst or natural Sepiolite catalyst. As a binder, two types of resin have been selected: a phenolic resin of the novolac family (manufacturer "Georgia Pacific") and a cellulose resin, specifically methyl-2-hydroxyethylcellulose (Aldrich 435015). For the preparation of the monoliths of HDL or Sepiolite is based on a ratio of binder: catalyst 5:95 by weight, which means that to form 10 g of catalyst, 526 mg of binder is necessary. Prior to mixing, the catalysts are subjected to an oven drying step at 110 ° C for 12 hours. Once dried, they are mixed homogeneously with the binder in the proportions mentioned above by means of a ball mill for 20 minutes. Once the homogeneous mixture of all the materials is achieved, the thermocompression mold is loaded to carry out the obtaining of the "green bodies". The thermoforming of the material is carried out in a hydraulic press of hot plates "Liquidpes" by the application of a closing force on the mold and under a heating program that are detailed below:
    [0208]
    [0209]
    [0210]
    [0211] Once the process of thermoforming the material has been completed, the green bodies are removed from the mold and subjected to a thermal treatment in an inert atmosphere of pure N 2 (99.999%) in order to decompose the binder in the material's bosom. The heat treatment consists of a heating in several stages, which are carried out in isothermal mode (constant temperature) and not isothermal (under an increase in temperatures). The flow rate of N 2 used to make the pyrolysis is approximately 50 ml / min per gram of green body material to be pyrolyzed. The heating stages of the pyrolysis of the green bodies are shown below:
    [0212]
    [0213]
    [0214]
    [0215]
    [0216] Once the pyrolysis stage of the green bodies has been completed, the calcination stage of the brown bodies obtained is carried out in order to achieve the pure monolithic catalysts. To do this, the brown bodies are subjected to heating under an O 2 atmosphere (calcination). The flow rate of oxygen used in the calcination stage is 40 ml / min for each gram of monolith. The calcination process of the monoliths consists of different stages (isotherms and non-isotherms) and the conditions used are as follows:
    [0217]
    [0218]
    [0219]
    [0220] The monoliths of the catalysts obtained after the calcination process have a high mechanical resistance, high density, high purity and do not present cracks. In this way, the samples named below were obtained:
    [0221] 1) 5.Res.Cel.HDL.1300.Monolith of HDL with 5% cellulose resin calcined at 1300 ° C.
    [0222] 2) 5.Res.Cel.Sep.1300.Monolith of Sepiolite with 5% cellulose resin calcined at 1300 ° C.
    [0223] 3) 5.Res.Fen.HDL.1300.Monolith of HDL with 5% phenolic resin calcined at 1300 ° C.
    [0224] 4) 5.Res.Fen.Sep.1300.Monolith of Sepiolite with 5% phenolic resin calcined at 1300 ° C.
    [0225]
    [0226] Example 7:
    [0227]
    [0228] In this example, it describes the manufacture of monolithic systems based on HDL and Sep catalysts with 10% binder and sintered at 600 ° C.
    [0229]
    [0230] For the preparation of the monoliths, the starting point is HDL catalyst or natural Sepiolite catalyst. As a binder, two types of resin have been selected, a phenolic resin of the novolac family (manufacturer "Georgia Pacific") and a cellulose resin, in particular methyl-2-hydroxyethylcellulose (Aldrich 435015). For the preparation of the HDL or Sepiolite monoliths, a binder: catalyst ratio of 10:90 by weight is used, which means that to form 10 g of catalyst, 1.11 g of binder is necessary. Prior to mixing, the catalysts are subjected to an oven drying step at 110 ° C for 12 hours. Once dried, they are mixed homogeneously with the binder in the proportions mentioned above by means of a ball mill for 20 minutes. Once the homogeneous mixture of all the materials is achieved, the thermocompression mold is loaded to carry out the obtaining of the "green bodies". The thermoforming of the material is carried out in a hydraulic press of hot plates "Liquidpes" by the application of a closing force on the mold and under a Heating program that are detailed below:
    [0231]
    [0232]
    [0233]
    [0234]
    [0235] Once the thermoforming process of the material has been completed, the green bodies are removed from the mold and subjected to a thermal treatment in an inert atmosphere of pure N 2 (99.999%) in order to decompose the binder in the materials. The heat treatment consists of a heating in several stages, which are carried out in isothermal mode (constant temperature) and not isothermal (under an increase in temperatures). The flow rate of N 2 used to make the pyrolysis is approximately 50 ml / min per gram of green body material to be pyrolyzed. The heating stages of the pyrolysis of the green bodies are shown below:
    [0236]
    [0237]
    [0238]
    [0239]
    [0240] Once the pyrolysis stage of the green bodies has been completed, the calcination stage of the brown bodies obtained is carried out in order to achieve the pure monolithic catalysts. To do this, the brown bodies are subjected to heating under an O 2 atmosphere (calcination). The flow rate of oxygen used in the calcination stage is 40 ml / min for each gram of monolith. The calcination process of the monoliths consists of different stages (isotherms and non-isotherms) and the conditions used are as follows:
    [0241]
    [0242]
    [0243]
    [0244] The monoliths of the catalysts obtained after the calcination process have a high mechanical resistance, high density, high purity and do not present cracks. In this way, the samples named below were obtained:
    [0245] 1) 10.Res.Cel.HDL.600.Monolith of HDL with 10% cellulose resin calcined at 600 ° C.
    [0246] 2) 10.Res.Cel.Sep.600.Monolith of Sepiolite with 10% cellulose resin calcined at 600 ° C.
    [0247] 3) 10.Res.Fen.HDL.600.Monolith of HDL with 10% phenolic resin calcined at 600 ° C.
    [0248] 4) 10.Res.Fen.Sep.600.Monolith of Sepiolite with 10% phenolic resin calcined at 600 ° C.
    [0249]
    [0250] Example 8:
    [0251] In this example, it describes the manufacture of monolithic systems based on HDL and Sep catalysts with 10% binder and sintered at 1300 ° C.
    [0252]
    [0253] For the preparation of the monoliths, the starting point is HDL catalyst or natural Sepiolite catalyst. As a binder, two types of resin have been selected: a phenolic resin of the novolac family (manufacturer "Georgia Pacific") and a cellulose resin, specifically methyl-2-hydroxyethylcellulose (Aldrich 435015). For the preparation of the monoliths of HDL or Sepiolite is based on a ratio of binder: catalyst 10:90 by weight, which means that to form 10 g of catalyst, 1.11 g of binder is necessary. Prior to mixing, the catalysts are subjected to an oven drying step at 110 ° C for 12 hours. Once dried, they are mixed homogeneously with the binder in the proportions mentioned above by means of a ball mill for 20 minutes. Once the homogeneous mixture of all the materials is achieved, the thermocompression mold is loaded to carry out the obtaining of the "green bodies". The thermoforming of the material is carried out in a hydraulic press of hot plates "Liquidpes" by the application of a closing force on the mold and under a heating program that are detailed below:
    [0254]
    [0255]
    [0256]
    [0257] Once the process of thermoforming the material has been completed, the green bodies are removed from the mold and subjected to a thermal treatment in an inert atmosphere of pure N 2 (99.999%) in order to decompose the binder in the material's bosom. The heat treatment consists of a heating in several stages, which are carried out in isothermal mode (constant temperature) and not isothermal (under an increase in temperatures). The flow rate of N 2 used to make the pyrolysis is approximately 50 ml / min per gram of green body material to be pyrolyzed. The heating stages of the pyrolysis of the green bodies are shown below:
    [0258]
    [0259]
    [0260]
    [0261]
    [0262] Once the pyrolysis stage of the green bodies has been completed, the calcination stage of the brown bodies obtained is carried out in order to achieve the pure monolithic catalysts. To do this, the brown bodies are subjected to heating under an O 2 atmosphere (calcination). The flow rate of oxygen used in the calcination stage is 40 ml / min for each gram of monolith. The calcination process of the monoliths consists of different stages (isotherms and non-isotherms) and the conditions used are as follows:
    [0263]
    [0264]
    [0265]
    [0266] The monoliths of the catalysts obtained after the calcination process have a high mechanical resistance, high density, high purity and do not present cracks. In this way, the samples named below were obtained:
    [0267] 1) 10.Res.Cel.HDL.1300.Monolith of HDL with 10% cellulose resin calcined at 1300 ° C.
    [0268] 2) 10.Res.Cel.Sep.1300.Monolith of Sepiolite with 10% cellulose resin calcined at 1300 ° C.
    [0269] 3) 10.Res.Fen.HDL.1300.Monolith of HDL with 10% phenolic resin calcined at 1300 ° C.
    [0270] 4) 10.Res.Fen.Sep.1300.Monolith of Sepiolite with 10% phenolic resin calcined at 1300 ° C.
    [0271]
    [0272] Reformed ethanol with steam
    [0273] Example 9:
    [0274]
    [0275] In this example, the study of monolithic systems based on HDL and Sep catalysts, manufactured with resin of cellulose nature as a binder, in the reforming of ethanol with steam is described. The results obtained are compared with those of their corresponding unconformed catalysts, in a pulverulent state. The results obtained with the following catalysts are presented:
    [0276]
    [0277] 1) HDL. Catalyst based on HDL without shaping and calcined at 600 ° C.
    [0278] 2) Sep. Catalyst based on unformed sepiolite and calcined at 600 ° C.
    [0279] 3) 2.Res.Cel.HDL.600. HDL monolith made with 2% cellulose resin and calcined at 600 ° C.
    [0280] 4) 2.Res.Cel.Sep.600. Sepiolite monolith prepared with 2% cellulose resin and calcined at 600 ° C.
    [0281] 5) 5.Res.Cel.HDL.600. HDL monolith prepared with 5% cellulose resin and calcined at 600 ° C.
    [0282] 6) 5.Res.Cel.Sep.600. Sepiolite monolith prepared with 5% cellulose resin and calcined at 600 ° C.
    [0283] 7) 10.Res.Cel.HDL.600. HDL monolith prepared with 10% cellulose resin and calcined at 600 ° C.
    [0284] 8) 10.Res.Cel.Sep.600. Sepiolite monolith prepared with 10% cellulosic resin and calcined at 600 ° C.
    [0285] 9) 2.Res.Cel.HDL.1300. HDL monolith prepared with 2% cellulose resin and calcined at 1300 ° C.
    [0286] 10) 2.Res.Cel.Sep.1300. Sepiolite monolith prepared with 2% cellulose resin and calcined at 1300 ° C.
    [0287] 11) 5.Res.Cel.HDL.1300. HDL monolith prepared with 5% cellulose resin and calcined at 1300 ° C.
    [0288] 12) 5.Res.Cel.Sep.1300. Sepiolite monolith prepared with 5% cellulose resin and calcined at 1300 ° C.
    [0289] 13) 10.Res.Cel.HDL.1300. HDL monolith prepared with 10% cellulose resin and calcined at 1300 ° C.
    [0290] 14) 10.Res.Cel.Sep.1300. Sepiolite monolith prepared with 10% cellulose resin and calcined at 1300 ° C.
    [0291]
    [0292] The experiments were carried out in a fixed bed reactor at atmospheric pressure, Ethanol / Water ratio of 13 (mol / mol), WHSV of 0.757 h-1 and in a temperature range between 400 and 600 ° C.
    [0293]
    [0294] The activity results of the catalysts, expressed as% EtOH conversion as a function of the reaction temperature, are shown in Figures 1 and 2. As can be seen, the HDL-based catalysts are the most active. Among all the monoliths studied, those calcined at 600 ° C present the greatest activities, with values of ethanol conversion above 90%. Monoliths calcined at 1300 ° C are the least active. This lower activity is related to the high temperatures at which they have been manufactured (1300 ° C), which favor the sintering of the metallic particles of Co.
    [0295]
    [0296] At reaction temperatures of 500 ° C and above, the catalyst in the pulverulent state and the shaping and calcining at 600 ° C exhibit the same behavior, which indicates that the forming process used in this example it preserves the excellent catalytic properties exhibited by the catalyst in a pulverulent state.
    [0297]
    [0298] Among all the monoliths studied in this example it is worth mentioning the 2.Res.Cel.HDL.600, whose activity is superior to that of the sepiolitic catalysts and very similar to that of its corresponding unconformed catalyst, in a pulverulent state.
    [0299]
    [0300] As regards the distribution of the reaction products in Figures 3 and 4, the results are shown for the most active monoliths, manufactured at 600 ° C, and their corresponding catalysts in pulverulent state. As you can see the monolith that shows higher selectivities to H2 is 2.Res.Cel.HDL.600. In addition, this monolith also has a low CO production. It should be noted that these results improve those obtained by their reference catalyst, in a pulverulent state (HDL), as well as those obtained with sepiolitic catalysts. Therefore, the HDL-based catalyst manufactured with 2% cellulosic resin and calcined at 600 ° C would be a good candidate for industrial application in the production of hydrogen by steam reforming ethanol.
    [0301]
    [0302] Example 10:
    [0303]
    [0304] In this example, the study of monolithic systems based on HDL and Sep catalysts manufactured with phenolic resin as a binder in the reforming of ethanol with steam is described. The results obtained are compared with those of their corresponding unconformed catalysts, in a pulverulent state. The results obtained with the following catalysts are presented:
    [0305]
    [0306] 1) HDL. Catalyst based on HDL without shaping and calcined at 600 ° C.
    [0307] 2) Sep. Catalyst based on unformed sepiolite and calcined at 600 ° C.
    [0308] 3) 2.Res.Fen.HDL.600. HDL monolith with 2% phenolic resin and calcined at 600 ° C.
    [0309] 4) 2.Res.Fen.Sep.600. Sepiolite monolith with 2% phenolic resin and calcined at 600 ° C.
    [0310] 5) 5.Res.Fen.HDL.600. HDL monolith with 5% phenolic resin and calcined at 600 ° C.
    [0311] 6) 5.Res.Fen.Sep.600. Sepiolite monolith with 5% phenolic resin and calcined at 600 ° C.
    [0312] 7) 10.Res.Fen.HDL.600. HDL monolith with 10% phenolic resin and calcined at 600 ° C.
    [0313] 8) 10.Res.Fen.Sep.600. Sepiolite monolith with 10% phenolic resin and calcined at 600 ° C.
    [0314] 9) 2.Res.Fen.HDL.1300. HDL monolith with 2% phenolic resin and calcined at 1300 ° C.
    [0315] 10) 2.Res.Fen.Sep.1300. Sepiolite monolith with 2% phenolic resin and calcined at 1300 ° C.
    [0316] 11) 5.Res.Fen.HDL.1300. HDL monolith with 5% phenolic resin and calcined at 1300 ° C.
    [0317] 12) 5.Res.Fen.Sep.1300. Sepiolite monolith with 5% phenolic resin and calcined at 1300 ° C.
    [0318] 13) 10.Res.Fen.HDL.1300. HDL monolith with 10% phenolic resin and calcined at 1300 ° C.
    [0319] 14) 10.Res.Fen.Sep.1300. Sepiolite monolith with 10% phenolic resin and calcined at 1300 ° C.
    [0320]
    [0321] The experiments were carried out in a fixed bed reactor at atmospheric pressure, Ethanol / Water ratio of 13 (mono / mol), WHSV of 0.757 h-1 and in a temperature range between 400 and 600 ° C.
    [0322]
    [0323] The results of activity and selectivity as a function of the reaction temperature using this series of catalysts are shown in Figures 5, 6, 7 and 8.
    [0324]
    [0325] In this example it can be seen that the HDL-based catalysts are also the most active. Among all HDL monoliths, those calcined at 600 ° C present the highest activities, with values of ethanol conversion above 95%.
    [0326]
    [0327] Again, the monoliths calcined at 1300 ° C have lower activity, which is related to the high sintering that metallic particles of Co undergo at this temperature.
    [0328]
    [0329] The HDL monoliths made with 2% and 5% phenolic resin and those of sepiolite made with 5% phenolic resin and calcined at 600 ° C they have a high activity, similar to that of their corresponding catalyst in powder state, indicating that the forming process used in this example preserves the excellent properties exhibited by the unconformed catalyst .
    [0330]
    [0331] Among all the monoliths studied in this example include 2.Res.Cel.HDL.600, 5.Res.Cel.HDL.600 and 5.Res.Fen.Sep.600, which convert 100% of ethanol to low temperatures (400 ° C). In addition, it is worth highlighting the high activity of monolith 2.Res.Fen.Sep.600 at low temperatures (400 ° C), which even surpasses that of its corresponding catalyst without shaping, in a powdery state.
    [0332]
    [0333] As regards the distribution of the reaction products in Figures 7 and 8, the results are shown for the most active monoliths manufactured at 600 ° C, together with that of their corresponding pulverulent catalysts. As you can see the monolith that shows the highest selectivities to H2, in the whole range of temperatures studied, is 5.Res.Fen.HDL.600. In addition, this monolith also has one of the lowest CO production.
    [0334]
    [0335] Therefore, the HDL-based catalyst manufactured in 5% phenolic resin and calcined at 600 ° C would be a good candidate for industrial application in the production of hydrogen by steam reforming ethanol.
    [0336]
    [0337] Regarding the distribution of reaction products, only the results are shown for the most active monolithics prepared at 600 ° C and their corresponding reference catalysts, in a pulverulent state, because they present the best results. In Figure 7 and 8 it can be seen that the highest productions of hydrogen correspond to the monoliths 5.Res.Fen.HDL.600 and 5.Res.Fen.Sep.600. In addition, monolith 5.Res.Fen.HDL.600 have the lowest CO production. The results obtained with this last monolith even improve those obtained with its corresponding unconformed catalyst, in a pulverulent state.
    权利要求:
    Claims (27)
    [1]
    1. Method of manufacturing monolithic catalysts characterized by comprising the following stages:
    i) preparing a homogeneous mixture of a catalyst with a laminar structure selected from a double layered hydroxide and sepiolite in a pulverulent state, and a binder, where the binder is a phenolic or cellulosic resin,
    ii) compaction of the mixture obtained in step (i) by simultaneous application of pressure equal to or greater than 800 Kg / cm2 and temperature between 80 and 200 ° C to obtain a shaped part,
    iii) pyrolysis treatment of the shaped part in step ii) in an inert atmosphere, at a temperature between 400 and 1000 ° C and a time between 1 and 6 hours, so that a pyrolized part is obtained,
    iv) calcination of the pyrolyzed part obtained in step iii) by a heat treatment in a reactive atmosphere comprising O2 at a temperature of between 450-1500 ° C.
    [2]
    2. Process according to claim 1, wherein the double laminar hydroxide in the pulverulent state comprises a divalent cation (M2 +) and aluminum (Al3 +) with M2 + / (Al3 ++ M2 +) ratios comprised between 0.20 and 0.33, where the Divalent cation is selected from Mg2 +, Ca2 + and Zn2 +.
    [3]
    3. Method according to claim 2 wherein the catalyst based on a double laminar hydroxide in powdery state further comprises one or combinations of two or more elements of groups VIIIB, IB, VIB and, Nb, Ti, Zr, Mn, Re, Ga and Sn in percentages by weight of between 0.5% and 30% with respect to the total weight of the catalyst synthesized in pulverulent state.
    [4]
    4. Method according to claim 3, wherein the catalyst based on a double laminar hydroxide in pulverulent state further comprises one or combinations of two or more elements of groups IA, IIA and Ce and La in percentages by weight of between 0.1 % and 10% with respect to the total weight of the catalyst synthesized in pulverulent state.
    [5]
    Method according to any of the preceding claims 2-4 wherein, prior to step (i) of preparing a mixture, the synthesis of the catalyst based on a double laminar hydroxide in pulverulent state is carried out comprising:
    a) the preparation of an acid solution of the metallic cation M2 + and Al3 +, so that the ratio M2 + / (Al3 ++ M2 +) is between 0.20 and 0.33 and a basic solution formed by the necessary amount of NaNO3 and NaOH or NaCO3 and NaOH to achieve the precipitation of the metals M2 + and Al3 +
    b) mixing said acid and basic solutions prepared in the previous step to form a gel,
    c) maintenance of the gel formed in the previous stage at temperatures between 40 and 75 ° C for a time between 10 and 20 h,
    d) filtering, washing and drying the gel obtained in step c) at a temperature between 50 and 100 ° C, followed by calcining thereof at a temperature between 350 and 750 ° C.
    [6]
    6. Process according to any of the preceding claims, characterized in that step (i) comprises mixing a catalyst based on a double laminar hydroxide with a cellulosic resin.
    [7]
    7. Process according to any of the preceding claims, characterized in that step (i) comprises mixing a catalyst based on a double laminar hydroxide with a phenolic resin.
    [8]
    8. Process, according to claim 1, characterized in that the sepiolite-based catalyst in pulverulent state comprises, in addition to sepiolite, one or combinations of two or more elements of groups VIIIB, IB, VIB and Nb, Ti, Zr, Mn, Re , Ga and Sn in percentages by weight of between 0.5% and 30% with respect to the total weight of the catalyst synthesized in pulverulent state.
    [9]
    9. Process according to claim 8 wherein the catalyst based on sepiolite in pulverulent state further comprises one or combinations of two or more elements of groups IA, IIA and Ce and La in percentages by weight of between 0.1% and 10%. % with respect to the total weight of the catalyst synthesized in pulverulent state.
    [10]
    10. Process according to any of claims 1, 8-9, characterized in that step (i) comprises the mixture of a catalyst based on sepiolite and a phenolic resin.
    [11]
    Method according to any of the preceding claims 1-5, 7-10, characterized in that a phenolic resin with a melting point below 150 ° C and a volatile content of less than 60% is used as the binder in step (i). in weight with respect to said resin.
    [12]
    Method according to any of the preceding claims 1-6, 8-9 characterized in that in stage (i) a cellulosic resin with a melting point lower than 160 ° C and a volatile content higher than 90% is used as a binder. .
    [13]
    13. Process according to any of the preceding claims 1-6, 8-9, 12, characterized in that in the stage (i) an alkylhydroxyethylcellulose resin is used as binder.
    [14]
    14. Process according to any of the preceding claims, characterized in that, in step (i), the ratio between the amounts of catalyst in powder state and binder to prepare the mixture is between 85/15 and 99/1.
    [15]
    15. Process according to claim 14, characterized in that, in step (i), the ratio between the amounts of catalyst in the pulverulent state and of the binder is 95/5.
    [16]
    16. Process according to claim 14, characterized in that, in step (i), the ratio between the amounts of catalyst in the pulverulent and binder state is 98/2.
    [17]
    Method according to any of the preceding claims, characterized in that the pressure applied in step (ii) is at least 1000 Kg / cm2 and / or the temperature is between 100 and 165 ° C.
    [18]
    Method according to any of the preceding claims, characterized in that, in step (ii), the mixture is introduced into a cylindrical cavity mold prior to the application of the pressure so that the shaped part has a cylindrical geometry shape or disk.
    [19]
    Process according to any of the preceding claims, characterized in that the step (iii) of pyrolysis is carried out at temperatures between 600 and 900 ° C.
    [20]
    20. Process according to any of the preceding claims, characterized in that the step (iii) of pyrolysis is carried out in an inert atmosphere selected from N2, Argon, Helium and mixtures thereof.
    [21]
    21. Process according to any of the preceding claims, characterized in that the step (iii) of pyrolysis is carried out under an inert atmosphere of N2.
    [22]
    22. Method according to any of the preceding claims, characterized in that the thermal treatment of step (iv) is carried out at a temperature between 600 and 1000 ° C.
    [23]
    Method according to any of the preceding claims, characterized in that the thermal treatment of step (iv) is carried out in a reactive atmosphere selected from air, pure oxygen and mixtures of O2 and an inert gas.
    [24]
    Method according to any of the preceding claims, characterized in that the reactive atmosphere in which the heat treatment of stage (iv) is carried out is air.
    [25]
    25. Monolithic catalyst obtained by the process described in any of claims 1-24.
    [26]
    26. Use of the monolithic catalyst according to claim 25 to catalyze the reaction of reforming alcohols (C1-C6) or hydrocarbons (C1-C10).
    [27]
    27. Use according to claim 26 to catalyze the reaction of reforming ethanol with water vapor.
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    同族专利:
    公开号 | 公开日
    WO2019048726A1|2019-03-14|
    ES2703016B2|2019-10-21|
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    PCT/ES2018/070586| WO2019048726A1|2017-09-06|2018-09-06|Method for producing monolithic catalysts and use of same|
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