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    • 专利摘要:
    Direct synthesis of cu-cha through the combination of a complex of cu and tetraethylammonium, and applications in catalysis. The present invention relates to a process for the direct synthesis of a material with zeolitic cha structure in its silicoaluminate form containing copper atoms which may comprise, at least, the following steps: (I) preparation of a mixture containing at least one water source, a copper source, a polyamine, a source of tetravalent element y, a source of trivalent element x, the cation tetraethylammonium as the sole adeo and a source of alkaline or alkaline earth cations (a), and where the synthesis mixture has the following molar composition: Y2: a x2 o3: b < : f polyamine. (II) crystallization of the mixture obtained in (I) in a reactor. (III) recovery of the crystalline material obtained in (II). (Machine-translation by Google Translate, not legally binding)
    公开号:ES2589059A1
    申请号:ES201530606
    申请日:2015-05-05
    公开日:2016-11-08
    发明作者:Avelino Corma Canós；Manuel Moliner Marin；Nuria MARTIN GARCIA
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；Universidad Politecnica de Valencia；
    IPC主号:
    专利说明:

    DIRECT SYNTHESIS OF Cu-CHA THROUGH THE COMBINATION OF A CU AND TETRAETHYLAMMON COMPLEX, AND APPLICATIONS IN CATALYSIS

    D E S C R I P C I O N
     5
    Technical field
    The present invention relates to a method of direct synthesis of zeolite CHA in its silicoaluminate form with copper atoms, using the specific combination of the tetraethylammonium cation (TEA) as the directing agent of organic structure (ADEO) and a copper complex, with high synthesis yields. The present invention also relates to the use as a catalyst of the zeolitic material synthesized in accordance with the present synthesis procedure.
    Background
    Zeolites are microporous materials formed by TO4 tetrahedra (T = Si, Al, B, P, Ti, Ge ...), interconnected by oxygen atoms, creating pores and cavities of 15 size and uniform shape in the molecular range (3-15 TO). These zeolitic materials have found important applications such as catalysts, adsorbents or ion exchangers.
    These materials are used as catalysts in numerous chemical processes, where the use of a certain zeolite with specific physical-chemical properties 20 for a given chemical process will depend directly on the nature of the reagents and products involved in the process (such as size, shape , hydrophobicity ...) and also the reaction conditions. On the one hand, the nature of the reagents and products will affect the diffusion of these molecules in the pores and cavities of the zeolite, and consequently, the choice of the zeolite with a suitable pore topology for the products involved in the reaction is essential. On the other hand, the zeolite must be chemically and structurally stable under the required reaction conditions.
    Nitrogen oxides (NOx), emitted mainly by automobiles during the consumption of fossil fuels, have become a serious environmental problem, since they are one of the largest air pollutants. In this sense, the selective catalytic reduction (RSC) of NOx with ammonia has been shown as an efficient way to control such unwanted emissions.
    Among the more than 200 zeolitic structures accepted by the International Association of Zeolites (IZA), those small pore zeolites and large cavities containing copper atoms in extra-net positions, possess excellent catalytic activity for selective catalytic reduction (RCS) NOx, in addition to high hydrothermal stability (Bull, et al., US Patent 7601662, 2009; Moliner, et al., 5 WO2013 / 159825, 2013). Within all known small pore zeolites, the chabacita (CHA code assigned by the IZA) has received special attention. This material is formed by a three-way system of small pores (8A) interconnected by large cavities, and also has double 6-member rings (DA6). 10
    The zeolite CHA in its silicoaluminate form containing Cu atoms, is an excellent catalyst in the selective catalytic reduction (RCS) of NOx using ammonia as a reducing agent in the presence of oxygen. The incorporation of Cu species, conventionally, is carried out by post-synthetic ion exchange treatments of the previously synthesized and calcined zeolite. This procedure requires several steps, such as hydrothermal synthesis of silicoaluminate, calcination of the material to eliminate ADEO, transformation to the ammonium form, ion exchange of the metal, and finally, calcination to obtain the final zeolite with the desired metal. All these steps contribute to increase the total cost in obtaining the catalytic material. twenty
    In recent years, the direct synthesis of silicoaluminate with CHA structure containing copper atoms has been described using as sole ADEO an organometallic complex formed by copper and a polyamine, in order to introduce cationic copper species into the CHA cavities after calcining the sample in air (Chem. Commun, 2011, 47, 9783; Chin. J. Catal. 2012, 33, 92). However, the 25 Si / Al molar ratios obtained in the final solids are low (Si / Al ~ 4-7). These low Si / Al ratios can present catalyst deactivation problems due to irreversible desaluminization processes under the conditions required for the NOx RCS (presence of steam and high temperatures). In addition, these Si / Al ratios in the final solids are smaller than those introduced in the synthesis gels, in particular the difference is greater when studying high Si / Al ratios (for example, to obtain a Si / Al ratio in the final solid of 7.6, a theoretical ratio in the gel of 17 is required, see example Cu-ZJM-1-35 in Table 1 of Chem. Commum. 2011, 47, 9783). These differences between the Si / Al ratios indicate that part of the Si species introduced in the synthesis medium 35 remain in solution and are not capable of being incorporated into solids.
    final, resulting in low solid yields (less than 50% when Si / Al ratios greater than 7) are used. On the other hand, by means of this synthesis procedure, it is also not possible to control the amount of copper incorporated in the zeolite, always obtaining values greater than 9% by weight. In general, it is widely recognized in the literature that the higher the copper content in the zeolitic samples, the lower the hydrothermal stability the catalyst has (Chem. Commun., 2012,48, 8264). In short, this synthesis methodology does not allow controlling the Si / Al ratio and the Cu content in the catalysts, properties that are very important for their activity and stability.
    The preferred ADEO for the synthesis of zeolite CHA in its silicoaluminate form is the cation N, N, N-tri-methyl-1-adamantamonium (TMAdA) (Zones, U.S. Patent 4544538, 1985, assigned to Chevron). Recently, the use of benzyltrimethylammonium (BzTMA) as an efficient ADEO for the synthesis of the silicoaluminate form of CHA has also been described (Miller et al., U.S. Patent 8007764, 2011, assigned to Chevron). fifteen
    Taking into account the ability of the TMAdA and BzTMA cations to direct the formation of CHA, the direct synthesis of the CHA structure in its silicoaluminate form containing Cu atoms has recently been described, using specific mixtures of said ADEOs with a copper complex (Trukhan et al., US Patent 2011/0076229, 2011; and Moliner et al., WO2014 / 090698, 2014). These descriptions 20 allow directing the synthesis of these materials in greater Si / Al ranges, but have certain disadvantages. The methodology described by Trukhan et al. it always requires the combined use of two organic molecules, selected from TMAdA, BzTMA, and tetramethylammonium, in addition to the organometallic copper complex formed by the addition of ammonia with a copper salt (Trukhan et al., U.S. Patent 25 2011/0076229). In order to avoid the use of several ADEOs combined and also avoid the use of ammonia in the preparation of the material, which is extremely caustic and dangerous, in Moliner et al. The direct synthesis of the CHA structure in its silicoaluminate form with copper atoms using a single organic molecule (TMAdA) is described next to a copper complex formed by a commercial linear polyamine (tetraethylenepentamine, TEPA) and a copper salt. However, the TMAdA cation has a high cost, greatly increasing the process of obtaining the desired material, and limiting the possible commercial applications of this zeolite.
    Therefore, in spite of the advances shown in the direct synthesis of the CHA material in its silicoaluminate form containing copper atoms, there is still a need on the part of the industry to reduce the preparation costs of this material using other cheaper ADEOs for its preparation.
    Description of the Invention 5
    The present invention relates to a new method of direct synthesis of the CHA zeolitic structure in its silicoaluminate form containing Cu atoms inside. This new procedure requires the combination of an organometallic copper complex with a commercial and economic ADEO, such as tetraethylammonium (ASD) capable of directing the crystallization of the CHA zeolitic structure. 10 Following this synthesis methodology, it is possible to synthesize the CHA zeolitic structure in its silicoaluminate form containing copper atoms in its interior directly with high synthesis yields, avoiding the steps required to achieve said material by means of traditional post-synthetic exchange procedures with The metal ion. fifteen
    The present invention also relates to the use of materials with zeolitic structure CHA in its silicoaluminate form containing synthesized copper atoms obtained according to the described methodology, as active catalysts for, for example, the selective catalytic reduction (RCS) of NOx.
    Therefore, the present invention relates to a process for the direct synthesis of the material with CHA zeolitic structure in its silicoaluminate form containing copper atoms, comprising at least the following steps:
    (i) Preparation of a mixture containing at least one source of water, a source of copper, a polyamine to form the organometallic complex of Cu, a source of tetravalent element Y, a source of trivalent element X, the cation tetraethylammonium (TEA) as the sole ADEO and a source of alkaline or alkaline earth cations (A), and where the synthesis mixture has the following molar composition:

    YO2: a X2O3: b ADEO: c A: d H2O: e Cu: f Polyamine 30
    where
    a is in the range of 0.001 to 0.2, preferably between 0.005 to 0.1, and more preferably between 0.01 to 0.07.
    b is in the range of 0.01 to 2; preferably between 0.1 to 1, and more preferably between 0.1 to 0.6;
    c is in the range of 0 to 2; preferably between 0.001 to 1, and more preferably between 0.01 to 0.8;
    d is in the range of 1 to 200; preferably between 1 to 50.5 and more preferably between 2 to 20;
    e is in the range of 0.001 to 1; preferably between 0.001 to 0.6, and more preferably between 0.001 to 0.5;
    f is in the range of 0.001 to 1; preferably between 0.001 to 0.6, and more preferably between 0.001 to 0.5. 10
    (ii) Crystallization of the mixture obtained in (i) in a reactor.
    (iii) Recovery of the crystalline material obtained in (ii).
    According to the present invention, Y is a tetravalent element that may be preferably selected from Si, Sn, Ti, Ge and combinations thereof, and more preferably is Si. fifteen
    The Si source used may be selected from silicon oxide, silicon halide, colloidal silica, smoked silica, tetraalkylortosilicate, silicate, silicic acid, a previously synthesized crystalline material, a previously synthesized amorphous material and combinations thereof and, more preferably , is a material selected from a previously synthesized crystalline material, a previously synthesized amorphous material and combinations thereof, and more preferably, a previously synthesized crystalline material.
    According to the present invention, X is a trivalent element that may be preferably selected from Al, B, Fe, In, Ga and combinations thereof, and more preferably is Al.
    The source of Al used can be selected from any aluminum salt, any hydrated aluminum oxide, any aluminum alkoxide, a previously synthesized crystalline material, a previously synthesized amorphous material and combinations thereof, and more preferably, it is a selected material between a previously synthesized crystalline material, a previously synthesized amorphous material and combinations thereof, and more preferably, a previously synthesized crystalline material.
    According to a particular embodiment of the present invention, the crystalline material with the zeolitic structure FAU can be used in (i) as the sole source of Y and X, preferably silicon and aluminum, and which can have a Si / Al ratio preferably greater than 7 .
    Therefore, according to a particular embodiment of the present invention, Y is Si and X is 5 Al whereby the process for the direct synthesis of the material with zeolitic structure CHA in its silicoaluminate form containing copper atoms with high synthesis yields, I would understand at least the following steps:
    (i) Preparation of a mixture containing at least one source of water, a source of copper, a polyamine to form the organometallic complex 10 of Cu, a zeolite with the crystalline structure FAU, such as zeolite Y, as the sole source of silicon and aluminum, the tetraethylammonium cation as the only ADEO and a source of alkaline or alkaline earth cations (A), and where the synthesis mixture has the following molar composition:
     fifteen
    SiO2: a Al2O3: b ADEO: c A: d H2O: e Cu: f Polyamine
    where
    a is in the range of 0.001 to 0.2, preferably between 0.005 to 0.1, and more preferably between 0.01 to 0.07.
    b is in the range of 0.01 to 2; preferably between 0.1 to 20 1, and more preferably between 0.1 to 0.6;
    c is in the range of 0 to 2; preferably between 0.001 to 1, and more preferably between 0.01 to 0.8;
    d is in the range of 1 to 200; preferably between 1 to 50, and more preferably between 2 to 20; 25
    e is in the range of 0.001 to 1; preferably between 0.001 to 0.6, and more preferably between 0.001 to 0.5;
    f is in the range of 0.001 to 1; preferably between 0.001 to 0.6, and more preferably between 0.001 to 0.5.
    (ii) Crystallization of the mixture obtained in (i) in a reactor. 30
    (iii) Recovery of the crystalline material obtained in (ii).
    According to the present invention, any source of Cu can be used in (i). Preferably, the copper source may be selected from nitrate, sulfate, oxalate salts, and combinations thereof, among others.
    According to the present invention, the mixture formed in (i) is free of any phosphorus source. 5
    According to a preferred embodiment of the present invention, the mixture formed in (i) may be free of any source of fluorine.
    According to a preferred embodiment of the present invention, the source of alkaline or alkaline earth cations may be any source of these elements, and may preferably be selected from a source of Na, K, and combinations thereof.
    According to the present invention, any polyamine or mixtures of different polyamines capable of forming a complex with copper atoms can be used in (i), regardless of their form (cyclic, linear, branched ...), and regardless of the nature of the amine (primary, secondary or tertiary). Preferably, said polyamine may be selected from tetraethylene pentamine, triethylenetetramine, 1,4,8,11-tetraazacyclotetradecane, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, and combinations thereof, among other. Preferably the polyamine is tetraethylene pentamine.
    According to the present invention, the crystallization process described in (ii) is preferably carried out in autoclaves, under conditions that can be static or dynamic (for example by stirring the mixture) at a temperature selected between 100 and 200 ° C preferably between 130 and 200 ° C and more preferably between 130 and 175 ° C; and a crystallization time that can be between 6 hours and 50 days preferably between 1 and 20 days, and more preferably between 2 and 15 days. It should be borne in mind that the components of the synthesis mixture can come from different sources, which may vary the crystallization conditions described.
    According to a particular embodiment of the process of the present invention, it is possible to add CHA crystals to the synthesis mixture, which act as seeds 30 favoring the described synthesis, in an amount up to 25% by weight with respect to the total amount of oxides. These crystals can be added before or during the crystallization process.
    According to the process of the present invention, after the crystallization described in (ii), the resulting solid is separated from the mother liquor and recovered. The recovery step (iii) can be carried out by different known separation techniques such as, for example, decantation, filtration, ultrafiltration, centrifugation or any other solid-liquid separation technique, and combinations thereof. 5
    The process of the present invention may further comprise the removal of the organic content contained inside the material by means of an extraction process.
    According to a particular embodiment, the removal of the organic compound contained inside the material can be carried out by means of a heat treatment at 10 temperatures above 25 ° C, preferably between 100 and 1000 ° C and for a period of time, preferably between 2 minutes and 25 hours
    According to a particular embodiment of the present invention, in the process of obtaining the material described above, at least one metal can be introduced by post-synthesis processes such as impregnation, ion exchange or combinations thereof. These metals are preferably selected from precious metals, and more preferably from Pt, Pd and combinations thereof, preferably being located in extra-net positions.
    According to another particular embodiment of the present invention, in the process of obtaining the material described above, any metal oxide containing at least one precious metal, preferably selected from Pt, Pd, and combinations thereof, can also be introduced.
    According to another particular embodiment, the material produced according to the present invention can be pelletized using any known technique.
    According to a preferred embodiment, the material obtained according to the present invention can be calcined. Therefore, the zeolitic material with CHA structure can have the following molar composition after being calcined:
    YO2: or X2O3: p A: r Cu
    where or is in the range of 0.001 to 0.2; preferably between 0.005 to 0.1, and more preferably between 0.01 to 0.07; 30
    where p is in the range of 0 to 2, preferably 0.001 to 1; and more preferably between 0.01 to 0.8;
    where r is between the interval 0.001 to 1; preferably between 0.001 to 0.6, and more preferably between 0.001 to 0.5.
    According to a particular embodiment, Y is Si and X is Al, therefore, the zeolitic material with CHA structure could have the following molar composition after being calcined:
    SiO2: or Al2O3: p A: r Cu
    where or is in the range of 0.001 to 0.2; preferably between 0.005 to 0.1, and more preferably between 0.01 to 0.07;
    where p is in the range of 0 to 2, preferably 0.001 to 1; and more preferably between 0.01 to 0.8; 10
    where r is between the interval 0.001 to 1; preferably between 0.001 to 0.6, and more preferably between 0.001 to 0.5.
    According to a preferred embodiment, the material obtained is Cu-SSZ-13.
    According to a particular embodiment of the present invention, the zeolitic material with CHA structure obtained can also comprise a precious metal 15 preferably selected from Pd, Pt and combinations thereof.
    The present invention also relates to the use of the materials described above and obtained according to the process of the present invention as catalysts for the conversion of feeds formed by organic compounds into products of higher added value, or as a molecular sieve for elimination / separation. of streams (eg gas mixtures) by contacting the feeds with the material obtained.
    According to a preferred embodiment, the material obtained in the present invention can be used as a catalyst in selective catalytic reduction (RCS) reactions of NOx (nitrogen oxide) in a gas stream. In particular, the RCS of 25 NOx will be carried out in the presence of reducing agents, preferably selected from ammonium, urea, hydrocarbons, and combinations thereof. According to this particular embodiment, the selective catalytic reduction (RCS) of NOx (nitrogen oxide) can be carried out using a monolith as a substrate and applying a layer of the zeolitic material obtained according to the present invention so that the gas stream can pass through it carrying out the desired reaction. In the same way, a layer of the zeolitic material obtained according to the
    The present invention can be applied to other substrates, such as a filter through which the gas stream will pass.
    According to another particular embodiment of the present invention, the material synthesized according to the present invention and containing a precious metal, such as Pt or Pd, can be used as a catalyst for the selective oxidation of ammonia to nitrogen. According to this particular embodiment, the selective catalytic oxidation of ammonia to nitrogen can be carried out using a monolith as a substrate and applying a layer of the zeolitic material obtained according to the present invention so that the gas stream can pass through it. carrying out the desired reaction. In the same way, a layer of the zeolitic material obtained according to the present invention can be applied on other substrates such as a filter, among others, through which the gas stream will pass.
    According to another particular embodiment, the material described according to the present invention can be used in the conversion of methane to methanol (Wulfers, et al. Chem. Commun. 2015, 51, 4447). fifteen
    Throughout the description and the claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and features of the invention will be derived partly from the description and partly from the practice of the invention. twenty
    Brief description of the figures
    Figure 1: PXRD patterns of the Cu-silicoaluminatos materials with CHA structure synthesized according to the present invention.
    Figure 2: UV-Vis spectra of the Cu-silicoaluminatos materials with CHA structure synthesized according to the present invention. 25
    EXAMPLES
    Example 1: Direct synthesis of Cu-silicoaluminato with CHA structure
    1122.2 mg of a 20% by weight aqueous solution of copper (II) sulfate (CuSO4, Alfa Aesar, 98%) are mixed with 266.2 mg of tetraethylenepentamine (TEPA, 98%, Sigma Aldrich) for the in-situ preparation ”Of the organometallic copper complex, the resulting mixture being kept under stirring for 2 hours. After this time, 9487.3 mg of an aqueous solution of tetraethylammonium hydroxide (TEAOH, Sigma Aldrich, 35% by weight in water), and 1150.1 mg of a
    20% by weight aqueous solution of sodium hydroxide, the resulting mixture being kept under stirring for 15 minutes. Finally, 3608.5 mg of a zeolite with FAU structure (CBV-720, molar ratio SiO2 / Al2O3 = 21) is introduced into the synthesis mixture and the time required to evaporate the excess water until the concentration of water is maintained is stirred desired gel The final composition of the gel is 5 SiO2: 0.047 Al2O3: 0.022 Cu (TEPA) 2+: 0.4 TEAOH: 0.1 NaOH: 4 H2O. The resulting gel is transferred to an autoclave with a Teflon jacket. Crystallization is carried out at 160 ° C for 7 days under static conditions. The solid product is filtered, washed with plenty of water, dried at 100 ° C and finally calcined in air at 550 ° C for 4 h to remove organic debris. The solid yield achieved is greater than 90% (regardless of organic debris).
    The solid is characterized by powder X-ray diffraction, obtaining the characteristic peaks of the CHA structure (see Figure 1).
    The crystalline material obtained without calcining is characterized by UV-VIS spectroscopy to study the stability of the molecules of the organometallic copper complex 15 after the crystallization of the zeolite. As seen in Figure 2, the UV-VIS spectrum shows a single band centered at ~ 265 nm, which has been assigned to the presence of the intact Cu-TEPA complex inside the zeolithic structure (Franco, et al. 2013/159828, 2012).
    Example 2: Direct synthesis of Cu-silicoaluminate with CHA 20 structure
    380.2 mg of a 20% by weight aqueous solution of copper (II) sulfate (CuSO4, Alfa Aesar, 98%) are mixed with 90.2 mg of tetraethylenepentamine (TEPA, 98%, Sigma Aldrich) for the in-situ preparation "Of the organometallic copper complex, keeping the resulting mixture under stirring for 2 hours. After this time, 1578.0 mg of an aqueous solution of tetraethylammonium hydroxide (TEAOH, Sigma Aldrich, 35% by weight in water), and 230.1 mg of an aqueous solution of sodium hydroxide at 20% by weight are added, maintaining the mixture resulting in stirring for 15 minutes. Finally, 601.3 mg of a zeolite with FAU structure (CBV-720, molar ratio SiO2 / Al2O3 = 21) is introduced into the synthesis mixture and the time required to evaporate the excess of 30 water until the concentration is achieved is stirred of desired gel. The final composition of the gel is SiO2: 0.047 Al2O3: 0.045 Cu (TEPA) 2+: 0.4 TEAOH: 0.1 NaOH: 4 H2O. The resulting gel is transferred to an autoclave with a Teflon jacket. Crystallization is carried out at 160 ° C for 7 days under static conditions. The solid product is filtered, washed with plenty of water, dried at 100 ° C and finally calcined in air at 550 ° C 35
    for 4 h to remove organic debris. The solid yield achieved is greater than 90% (regardless of organic debris).
    The solid is characterized by powder X-ray diffraction, obtaining the characteristic peaks of the CHA structure (see Figure 1). Chemical analyzes of the sample indicate a Si / Al ratio of 10.3 and a copper content of 4.1% by weight. 5
    The crystalline material obtained without calcining is characterized by UV-VIS spectroscopy to study the stability of the molecules of the organometallic copper complex after the crystallization of the zeolite. As seen in Figure 2, the UV-VIS spectrum shows a single band centered at ~ 265 nm, which has been assigned to the presence of the intact Cu-TEPA complex inside the zeolithic structure 10 (Franco, et al . 2013/159828, 2012).
    Example 3: Direct synthesis of Cu-silicoaluminate with CHA structure
    234.0 mg of a 20% by weight aqueous solution of copper (II) sulfate (CuSO4, Alfa Aesar, 98%) are mixed with 53.2 mg of tetraethylenepentamine (TEPA, 98%, Sigma Aldrich) for the in-situ preparation ”Of the organometallic copper complex, the resulting mixture being kept under stirring for 2 hours. After this time, 959.1 mg of an aqueous solution of tetraethylammonium hydroxide hydroxide (TEAOH, Sigma Aldrich, 35% by weight in water), 225.1 mg of a 20% by weight aqueous solution of sodium hydroxide and 562.9 mg of water, keeping the resulting mixture under stirring for 15 minutes. Finally, 365.3 20 mg of a zeolite with FAU structure (CBV-720, molar ratio SiO2 / Al2O3 = 21) is introduced into the synthesis mixture and the time required to evaporate the excess water until the concentration is achieved is stirred of desired gel. The final gel composition is SiO2: 0.047 Al2O3: 0.045 Cu (TEPA) 2+: 0.4 TEAOH: 0.2 NaOH: 13 H2O. The resulting gel is transferred to an autoclave with a Teflon jacket. Crystallization is carried out at 160 ° C for 7 days under static conditions. The solid product is filtered, washed with plenty of water, dried at 100 ° C and finally calcined in air at 550 ° C for 4 h to remove organic debris. The solid yield achieved is greater than 90% (regardless of organic debris). 30
    The solid is characterized by powder X-ray diffraction, obtaining the characteristic peaks of the CHA structure (see Figure 1).
    The crystalline material obtained without calcining is characterized by UV-VIS spectroscopy to study the stability of the molecules of the organometallic copper complex
    after crystallization of the zeolite. As seen in Figure 2, the UV-VIS spectrum shows a single band centered at ~ 265 nm, which has been assigned to the presence of the intact Cu-TEPA complex inside the zeolithic structure (Franco, et al. 2013/159828, 2012).
    Example 4: Catalytic tests for the RCS reaction of NOx 5
    The catalytic activity for the selective catalytic reduction of NOx is studied using a tubular, fixed-bed quartz reactor 1.2 cm in diameter and 20 cm long. In a typical experiment, the catalyst is compacted into particles between 0.25-0.42 mm in size, introduced into the reactor, and the temperature is increased to 550 ° C (see reaction conditions in Table 1); 10 subsequently, that temperature is maintained for one hour under a flow of nitrogen. Once the desired temperature has been reached, the reaction mixture is fed. The NOx RCS is studied using NH3 as a reducer. The NOx present at the outlet of the gases from the reactor is analyzed continuously by means of a chemiluminescent detector (Thermo 62C). The catalytic results are summarized in Table 2.

    Table 1: Reaction conditions of the NOx RCS.
     Total gas flow (ml / min)  300
     Catalyst Load (mg)  40
     NO concentration (ppm)  500
     NH3 concentration (ppm)  530
     O2 concentration (%)  7
     H2O concentration (%)  5
     Temperature range studied (° C)  170-550

    Table 2: Conversion (%) of NOx at different temperatures (200, 250, 300, 350, 20 400, 450, 500 ° C) using the Cu-CHA catalyst synthesized following the methodology described in the present invention.

     Conversion (%) of NOx at different temperatures
     200ºC 250ºC 300ºC 350ºC 400ºC 450ºC 500ºC
     Example 2  89.8 89.4 91.8 91.9 95.2 95.3 74.1
    权利要求:
    Claims (34)
    [1]
    R E I V I N D I C A C I O N E S
    1. Process for the direct synthesis of a material with CHA zeolitic structure in its silicoaluminate form containing copper atoms comprising at least the following steps:
    (i) Preparation of a mixture containing at least one source of water, a source of copper, a polyamine, a source of tetravalent element Y, a source of trivalent element X, the tetraethylammonium cation as the sole ADEO and a source of alkaline or alkaline earth cations (A), and where the synthesis mixture has the following molar composition:
    YO2: a X2O3: b ADEO: c A: d H2O: e Cu: f Polyamine
    where
    a is in the range of 0.001 to 0.2;
    b is in the range of 0.01 to 2;
    c is in the range of 0 to 2; fifteen
    d is in the range of 1 to 200;
    e is in the range of 0.001 to 1;
    f is in the range of 0.001 to 1.
    (ii) Crystallization of the mixture obtained in (i) in a reactor.
    (iii) Recovery of the crystalline material obtained in (ii). twenty
    [2]
    2. Process for the direct synthesis of a material according to claim 1, characterized in that c is in the range of 0.001 to 1.
    [3]
    3. Process for the direct synthesis of a material according to claim 1, characterized in that Y is a tetravalent element selected from Si, Sn, Ti, Ge and combinations thereof. 25
    [4]
    4. Process for the direct synthesis of a material according to claim 3, characterized in that Y is Si and comes from a source selected from silicon oxide, silicon halide, colloidal silica, smoked silica, tetraalkylortosilicate, silicate, silicic acid, a material previously synthesized crystalline, a previously synthesized amorphous material and combinations thereof 30
    [5]
    5. Process for the direct synthesis of a material according to claim 4, characterized in that the source of Y is a previously synthesized crystalline material.
    [6]
    6. Process for the direct synthesis of a material according to claim 1, characterized in that X is selected from Al, B, Fe, In, Ga and combinations thereof. 5
    [7]
    7. Process for the direct synthesis of a material according to claim 6, characterized in that X is Al and comes from a source selected from aluminum salt, any hydrated aluminum oxide, any aluminum alkoxide, a previously synthesized crystalline material, a material previously synthesized amorphous and combinations thereof. 10
    [8]
    8. Process for the direct synthesis of a material according to claim 7, characterized in that the source of X is a previously synthesized crystalline material.
    [9]
    9. Process for the direct synthesis of a material according to the preceding claims, characterized in that a zeolite with FAU structure is the only source of Y and X.
    [10]
    10. Process for the direct synthesis of a material according to claim 1, characterized in that any source of copper can be used in step (i).
    [11]
    11. Process for the direct synthesis of a material according to claim 10, characterized in that the copper source is selected from nitrate, sulfate, oxalate salts, and combinations thereof.
    [12]
    12. Process for the direct synthesis of a material according to claim 1, characterized in that the polyamine of step (i) comprises primary, secondary, tertiary amines, or mixtures thereof.
    [13]
    13. Process for the direct synthesis of a material according to claim 12, characterized in that the polyamine required in step (i) is selected from tetraethylenepentamine, triethylenetetramine, 1,4,8,11-tetraazacyclotetradecane, 1,4,8,11- Tetramethyl-1,4,8,11-tetraazacyclotetradecane, or mixtures thereof.
    [14]
    14. Process for the direct synthesis of a material according to claim 13, characterized in that the polyamine used in step (i) is tetraethylenepentamine.
    [15]
    15. Process for the direct synthesis of a material according to claims 1 to 14, characterized in that the crystallization process described in (ii) is carried out in 30 autoclaves, under static or dynamic conditions.
    [16]
    16. Process for the direct synthesis of a material according to claims 1 to 15, characterized in that the crystallization process described in (ii) is carried out at a temperature between 100 and 200 ° C.
    [17]
    17. Process for the direct synthesis of a material according to claims 1 to 16, characterized in that the crystallization time of the process described in (ii) is between 6 hours and 50 days.
    [18]
    18. Process for the direct synthesis of a material according to claims 1 to 17, characterized in that it further comprises adding CHA crystals as seeds to the synthesis mixture in an amount up to 25% by weight with respect to the total amount of oxides . 10
    [19]
    19. Process for the direct synthesis of a material according to claim 1, characterized in that the recovery step (iii) is carried out with a separation technique selected from decantation, filtration, ultrafiltration, centrifugation and combinations thereof.
    [20]
    20. Process for the direct synthesis of a material according to claims 1 to 19, characterized in that it also comprises the elimination of the organic content contained inside the material by means of an extraction process.
    [21]
    21. Process for the direct synthesis of a material according to claims 1 to 20, characterized in that it further comprises the elimination of the organic content contained inside the material by means of a heat treatment at temperatures between 100 and 1000 ° C, during a period of Time between 2 minutes and 25 hours.
    [22]
    22. Process for the direct synthesis of a material according to claims 1 to 21, characterized in that the material obtained is pelleted.
    [23]
    23. Process for the direct synthesis of a material according to claims 1 to 22, characterized in that it further comprises introducing at least one precious metal.
    [24]
    24. Process for the direct synthesis of a material according to claim 23, characterized in that the precious metal is selected from Pd, Pt and combinations thereof.
    [25]
    25. Zeolitic material with CHA structure obtained according to the process described in claims 1 to 24, characterized by the following molar composition after being calcined:
    YO2: or X2O3: p A: r Cu
    where or is in the range of 0.001 to 0.2;
    where p is between the range of 0 to 2;
    where r is between the interval 0.001 to 1.
    [26]
    26. Zeolitic material with CHA structure obtained according to claim 25, characterized in that Y is Si and X is Al and by the following molar composition:
    SiO2: or Al2O3: p A: r Cu
    where or is in the range of 0.001 to 0.2;
    where p is between the range of 0 to 2;
    where r is between the interval 0.001 to 1.
    [27]
    27. Zeolitic material with CHA structure obtained according to claims 25 and 26, characterized in that the material is Cu-SSZ-13.
    [28]
    28. Zeolitic material with CHA structure obtained according to claims 25 to 27, characterized in that it further comprises a precious metal.
    [29]
    29. Zeolitic material with CHA structure obtained according to claim 28, characterized in that the precious metal is selected from Pd, Pt and 15 combinations thereof.
    [30]
    30. Use of the zeolitic material with CHA structure described in claims 25 to 29, and obtained according to the process described in claims 1 to 24 in processes for the conversion of feeds formed by organic compounds into products of higher added value, or for their elimination / separation of the reactive current 20 by contacting said feed with the described material.
    [31]
    31. Use of the zeolitic material with CHA structure according to claim 30, as a catalyst for the selective catalytic reduction (RCS) of nitrogen oxides (NOx) in a gas stream.
    [32]
    32. Use of the zeolitic material with CHA structure according to claim 31, as a catalyst for the NOx RCS, characterized in that it is carried out in the presence of a reducing agent, selected from ammonia, urea, hydrocarbons, and combinations thereof.
    [33]
    33. Use of the zeolitic material with CHA structure according to claim 30, as a catalyst in the conversion of methane into methanol. 30
    [34]
    34. Use of the zeolitic material with CHA structure according to claims 28 and 29, as a catalyst in the selective oxidation of ammonia to nitrogen.
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    ES201530606A|ES2589059B1|2015-05-05|2015-05-05|DIRECT SYNTHESIS OF Cu-CHA THROUGH THE COMBINATION OF A CU AND TETRAETHYLAMM COMPLEX, AND APPLICATIONS IN CATALYSIS|ES201530606A| ES2589059B1|2015-05-05|2015-05-05|DIRECT SYNTHESIS OF Cu-CHA THROUGH THE COMBINATION OF A CU AND TETRAETHYLAMM COMPLEX, AND APPLICATIONS IN CATALYSIS|
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    PCT/ES2016/070337| WO2016177924A1|2015-05-05|2016-05-03|Direct synthesis of cu-cha by means of combining a cu complex and tetraethylammonium and applications in catalysis|
    US15/569,700| US10676367B2|2015-05-05|2016-05-03|Direct synthesis of Cu-CHA by means of combining a Cu complex and tetraethylammonium and applications in catalysis|
    EP16728352.2A| EP3293149B1|2015-05-05|2016-05-03|Direct synthesis of cu-cha by means of combining a cu complex and tetraethylammonium and applications in catalysis|
    JP2017557354A| JP2018514497A|2015-05-05|2016-05-03|CU-CHA direct synthesis by combination of CU complex and tetramethylammonium and its catalytic use|
    BR112017023663-0A| BR112017023663A2|2015-05-05|2016-05-03|direct synthesis of cu-cha by combining a cu-tetraethylammonium complex and catalysis applications.|
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    ZA2017/07109A| ZA201707109B|2015-05-05|2017-10-19|Direct synthesis of cu-cha by means of combining a cu complex and tetraethylammonium and applications in catalysis|
    HK18109376.5A| HK1249889A1|2015-05-05|2018-07-19|Direct synthesis of cu-cha by means of combining a cu complex and tetraethylammonium and applications in catalysis|
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