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    • 专利摘要:
    Method of preparation of the aei zeolitic structure in its silicoaluminate form with high yields, and its application in catalysis. The present invention relates to a new process for the synthesis of the zeolite structure aei in its silicoaluminate form based on the use of another zeolite, the zeolite y, as the sole source of silicon and aluminum to obtain high yields of synthesis (greater than 80% ) in the absence of another source of silicon, cations derived from any phosphine and fluoride anions in the synthesis medium. The n, N-dimethyl-3,5-dimethylpiperidinium cation can be used as adeo, the fau crystal structure being transformed into the aei crystal structure in high yields. Also described is the preparation of catalysts based on the crystalline structure aei in its silicoaluminate form, where cu atoms have been introduced and their subsequent application as a catalyst, preferably in the scr of nox. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2586775A1
    申请号:ES201530514
    申请日:2015-04-16
    公开日:2016-10-18
    发明作者:Avelino Corma Canós；Manuel MOLINER MARÍN；Nuria MARTÍN GARCÍA
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；Universidad Politecnica de Valencia；
    IPC主号:
    专利说明:

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    METHOD OF PREPARATION OF THE AEI ZEOLITICAL STRUCTURE IN ITS SILICALUMUMINUM FORM WITH GREAT PERFORMANCES, AND ITS APPLICATION IN
    catalysis
    DESCRIPTION
    Field of Technology
    The present invention describes a new method of preparation of the zeolite structure AEI in its silicoaluminate form based on the use of another zeolite, such as zeolite Y (zeoltic structure FAU), as the only source of silicon and aluminum to obtain high yields of synthesis (greater than 80%) in the absence of another source of additional silicon, of cations derived from any phosphine and of fluoride anions in the medium of synthesis. The present invention also describes the preparation of zeolite AEI in its silicoaluminate form containing Cu species, synthesized by post-synthetic methodologies, and its application as a catalyst for selective catalytic reduction (RCS) of NOx, among others.
    Background
    Zeolites or molecular sieves are described as materials formed by TO4 tetrahedra (T = Si, Al, P, Ge, B, Ti, Sn ...), interconnected with each other by oxygen atoms, creating pores and cavities of size and shape uniform in the molecular range. These zeolltic materials have important applications as catalysts, adsorbents or ion exchangers among others (Martinez et al., Coord. Chem. Rev., 2011, 255, 1558).
    The formation of nitrogen oxides (NOx) during the combustion of fossil fuels has become a serious problem for today's society, because these gases are one of the largest atmospheric pollutants. Recently, it has been described that one of the most efficient procedures to control the emissions of these gases is the selective catalytic reduction (RCS) of NOx using ammonia as a reducing agent (Brandenberger, et al. Catal. Rev. Sci. Eng., 2008 , 50, 492).
    In this sense, in recent years it has been described that different small-pore zeolites in their silicoaluminate form containing copper atoms inside, have a high
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    catalytic activity and high hydrothermal stability for the RCS reaction of NOx (Bull, et al. U.S. Patent 7601662, 2009; Moliner et al. WO2013159825, 2012). Of the different small pore zeolites, the zeolite SSZ-13 (CHA zeolithic structure) containing copper atoms (Cu-SSZ-13), has been widely used in the literature as a catalyst for the RCS reaction of NOx (Bull, et al. US Patent 7601662, 2009). The SSZ-13 zeolite is formed by a three-way system of pores of small size (<4 A) interconnected by large cavities, and also, said crystalline structure has small boxes, known as double-rings of 6 (DA6). In this sense, the great hydrothermal stability of the Cu-SSZ-13 catalyst is due to the coordination of the copper atoms in the DA6 present in the large cavities of the SSZ-13 zeolite (J. Phys. Chem. C., 2010 , 114, 1633).
    Another zeolite with structural properties related to CHA is the SSZ-39 (AEI zeolithic structure), which is a silicoaluminate with large cavities connected through a three-way system of small pores, and also has DA6 in its structure (Wagner, et al. J. Am. Chem. Soc., 2000, 122, 263). Recently, it has been described that the zeolltic structure AEI in its silicoaluminate form containing copper atoms in its interior, is an active and highly stable catalyst from the hydrothermal point of view for the RCS of NOx with ammonia (Moliner et al. WO2013159825, 2012 ), showing even better catalytic behavior than the Cu-SSZ-13 catalyst (Moliner et al. Chem. Commun. 2012, 48, 8264).
    The first method of synthesis described for the preparation of the zeolite structure AEI in its silicoaluminate form uses various cyclic quaternary ammoniums with alkyl substituents as organic structure directing agents (ADEOs) (Zones, et al. U.S. Patent 5958370, 1999). In these preparations, the use of silicon oxide and aluminum oxide as sources of silicon and aluminum, respectively, has been claimed for the preparation of the zeolite structure AEI in its silicoaluminate form (Zones, et al. USPatent 5958370, 1999 ). Unfortunately, materials with an AEI structure in their silicoaluminate form obtained by means of such a synthesis methodology always have very low yields of synthesis (less than 52%), because the final crystalline solids show a Si / Al ratio much lower than the relation Yes / At initial introduced into the gel of synthesis (see Table 1).
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    Table 1: Synthesis conditions and synthesis yields achieved by the synthesis procedure described in the patent "Zones, et al. U.S. Patent 5958370, 1999 ”
     Relationship Yes / To Performance Ratio
     in the Si / Al mixture in the synthesis
     final solid reagent (% weight)
     Example 2  15 7.3 48%
     Example 16  50 25.5 51%
     Example 18  30 8.6 29%
    These very different Si / Al ratios indicate that most of the silicon species introduced into the synthesis remain in solution after the crystallization process, and are not part of the zeolite produced. Therefore, these low synthetic yields avoid the possible commercial application of SSZ-39 silicoaluminate (AEI structure), although the classical quaternary ammoniums with alkyl substituents used as ADEOs could be attractive for the preparation of the SSZ-39 zeolite from an economic point of view, since they could be easily obtained from commercially available pyridine precursors.
    The synthesis of zeolite AEI in its silicoaluminate form, has been synthesized with high
    synthetic yields (greater than 80%) using clinical quaternary ammoniums such as
    ADEOs and fluoride anions in the synthesis medium (Cao et al., US20050197519, 2005).
    Unfortunately, the presence of fluorine in the synthesis medium and / or in the material
    Synthetic lens is not recommended for possible industrial application. The motive is
    the high corrosivity and danger of fluorhydric acid or fluorinated derivatives
    when used as a reactive source, or as a byproduct formed in post-stages
    synthetic (for example in the calcination stage). Ace! well, the development of
    New efficient synthesis methodologies of the AEI crystalline material in its form
    Silicoaluminate in fluoride anion free media. In addition, this synthesis methodology
    based on the use of fluoride anions in the synthesis medium, results in AEI materials with
    Si / Al ratios in final solids greater than 100 (Cao et al., US20050197519, 2005),
    indicating a low incorporation of aluminum in the crystalline network of the AEI structure. This
    low incorporation of aluminum species severely limits the introduction and stabilization of
    cationic species, such as Cu2 + (it is important to indicate that Al3 + species
    in tetrahedral coordination in the crystalline network of the zeolite generate a negative charge, which
    they will be responsible for compensating and stabilizing the cationic species). Therefore, this
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    low amount of aluminum in the network, avoid the preparation of efficient Cu-AEI catalysts for application in the NOx RCS.
    Recently, the preparation of the AEI crystalline structure in its silicoaluminate form with high yields of synthesis (~ 80%) using tetraethyl phosphonium cations as ADEO (Maruo, et al. Chem. Lett., 2014, 43, 302-304; Sonoda, et al. J. Mater. Chem. A, 2015, 3, 857). Unfortunately, this procedure requires the use of phosphine-derived ADEOs, which has some important disadvantages. On the one hand, the organic molecules derived from phosphines show serious problems for the environment and health, inevitably associated with their use. While on the other hand, the complete elimination of the phosphorous species trapped inside the zeoltic cavities is very complicated, especially in small pore zeolites, and their elimination process requires stages of calcination at very high temperatures and hydrogen atmospheres for the complete decomposition / elimination of these species (Sonoda, et al. J. Mater. Chem. A, 2015, 3, 857).
    As previously mentioned, small pore zeolites substituted with a metal inside, especially small pore zeolites containing copper atoms, exhibit excellent catalytic activity for NOx RCS with ammonia or hydrocarbons as reducing agents in presence of oxygen. The conventional preparation of this type of metal-zeolites is obtained by post-synthetic methods of ionic metal exchange (Bull, et al. U.S. Patent 7601662, 2009).
    According to the present invention, a new method of synthesis of the zeolite structure AEI in its silicoaluminate form has been found in the absence of harmful compounds such as those mentioned above and with adequate Si / Al ratios. In addition, it has been discovered that thanks to the use of zeolites with high silica content as the only source of Si and Al in the synthesis of these materials, silicoaluminatos with high silica content are obtained in addition to yields greater than 80%.
    Description of the Invention
    The present invention relates to a new method of synthesis of the zeolite structure AEI in its silicoaluminate form based on the use of another zeolite, the zeolite Y (zeoltic structure FAU), as the only source of silicon and aluminum to obtain high yields of synthesis (greater than 80%) in the absence of another source of additional silicon,
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    of cations derived from any phosphine and fluoride anions in the synthesis medium. In the present invention, the N, N-dimethyl-3,5-dimethylpiperidinium cation can preferably be used as ADEO, where the FAU crystalline structure is transformed into the AEI crystalline structure with high yields.
    The present invention also relates to the preparation of catalysts based on the crystalline structure AEI in its silicoaluminate form, where Cu atoms have been introduced by post-synthetic treatments, for later application as a catalyst, preferably in the NOx RCS.
    Ace! Thus, the present invention relates to a process of synthesis of a crystalline material having the zeolite structure AEI, which can comprise at least the following steps:
    (i) Preparation of a mixture containing, at least, water, a zeolite with the crystalline structure FAU, such as zeolite Y, as the only source of silicon and aluminum, a cyclic ammonium cation with alkyl substituents such as ADEO, and a source of alkaline or alkaline earth cations (A), and where the synthesis mixture can have the following molar composition:
    SiO2: a AbO3: b OSDA: c A: d H2O
    where it is between 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 b is in the range of 0.01 to 2, preferably 0.1 to 1, and more preferably 0.1 to 0.6;
    where c is between the range of 0 to 2; preferably between 0.001 to 1, and more preferably between 0.01 to 0.8;
    where d is in the range of 1 to 200, preferably 1 to 50, and more preferably 2 to 30.
    (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, the crystalline material with the zeolithic structure FAU is used in (i) as the only source of silicon and aluminum. Preferably, the zeolite used has a Si / Al ratio greater than 7.
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    One of the advantages of the present invention is that the reactive mixture prepared in step (i) is preferably free of phosphorus and fluorinated species (including fluoride anions).
    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, the ADEO required in step (i) can be any cyclic ammonium cation, preferably a cyclic quaternary ammonium with some alkyl substituent in its structure. According to a particular embodiment, the ADEO may preferably be selected from N, N-dimethyl-3,5-dimethylpiperidinium (DMDMP), N, N-diethyl-2,6-dimethylpiperidinium (DEDMP), N, N-dimethyl-2, 6-dimethylpiperidinium, N-ethyl-N-methyl-2,6-dimethylpiperidinium and combinations thereof, preferably the ADEO is N, N-dimethyl-
    3,5-dimethylpiperidinium.
    According to a particular embodiment, the process of the present invention may also comprise another ADEO called cooperative ADEO, which could also be present in step (i), being able to be selected from any cyclic quaternary ammonium or any other organic molecule, as per example, any quaternary amine or ammonium. According to a preferred embodiment, the cooperative ADEO is an ammonium cation, preferably it is a cyclic ammonium cation.
    According to another particular embodiment, the cooperative ADEO is an amine.
    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 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 1 and 10 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 AEI crystals to the synthesis mixture, which act as seeds favoring the synthesis
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    described, 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 described, after the crystallization described in (ii), the resulting solid is separated from the mother liquor and recovered. The recovery stage (iii) can be carried out by different known separation techniques such as decantation, filtration, ultrafiltration, centrifugation or any other solid-liquid separation technique and combinations thereof.
    The process of the present invention may also comprise the elimination 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 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 another particular embodiment, the material produced according to the present invention can be pelletized using any known technique.
    In the process described above, any cation present in the material can be exchanged by ion exchange for other cations using conventional techniques. Thus, depending on the X2O3 / YO2 molar ratio of the synthesized material, any cation present in the material can be exchanged, at least in part, by ion exchange. These exchange cations are preferably selected from metals, protons, proton precursors (such as ammonium ions) and mixtures thereof, and more preferably said cation is a metal selected from rare earths, metals of groups IIA, IIIA, VAT, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII and combinations thereof.
    According to a preferred embodiment, the ion exchange cation is copper.
    The present invention also relates to a zeolitic material with AEI structure obtained according to the process described above and which can have the following molar composition:
    SiO2: or Al2O3: p A: q ADEO1: r H2O
    where
    A is an alkaline or alkaline earth cation;
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    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.
    p is in the range of 0 to 2, preferably 0.001 to 1; and more preferably between 0.01 to 0.8.
    q is between the range of 0.01 to 1, preferably between 0.01 to 0.5; and more preferably between 0.01 to 0.3.
    r is in the range of 0 to 2, preferably 0 to 1.5; and more preferably between 0 to 1.
    According to a preferred embodiment, the material obtained according to the present invention can be calcined. Thus, the zeolite material with AEI structure can have the following molar composition after being calcined:
    SiO2: or Al2O3: p A
    where or is between the interval 0.001 and 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.
    The material of the present invention obtained according to the process described above, has the zeolite AEI network structure.
    According to a particular embodiment, the crystalline material obtained is preferably free from the presence of phosphorus and fluorine.
    According to a preferred embodiment, the material obtained according to the present invention can be ionically exchanged with a metal source preferably selected from rare earths, metals of groups IIA, IIIA, VAT, VA, IB, IIB, IIIB, IVB, VB, VIB , VIIB, VIII and combinations thereof, and subsequently heat treated. Thus, the zeolite material with AEI structure can have the following molar composition after introducing the metal (M):
    SiO2: or Al2O3: r M
    where or is between the interval 0.001 and 0.2, preferably between 0.005 to 0.1; and more preferably between 0.01 to 0.07.
    where r is between the interval 0.001 and 1, preferably between 0.001 to 0.6; and more preferably between 0.001 to 0.5.
    Preferably, the ionically exchanged metal (M) is copper.
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    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 the removal / separation of reactive currents (eg gas mixtures) by contacting the feeds with the material obtained.
    According to a preferred embodiment, the material obtained according to the present invention can be used in the production of olefins after contacting it with an oxygenated organic compound under certain reaction conditions. In particular, when feeding methanol, the olefins obtained are mostly ethylene and propylene. Ethylene and propylene can be polymerized to form polymers and co-polymers, such as polyethylene and polypropylene.
    According to another preferred embodiment, the material obtained in the present invention can be used as a catalyst in selective catalytic reduction (RCS) reactions of NOx (nitrogen oxides) in a gas stream. In particular, the NOx RCS will be performed in the presence of reducing agents, such as ammonium, urea and / or hydrocarbons. Materials to which copper atoms have been introduced according to any of the known techniques are especially useful for this use.
    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 characteristics of the invention will be derived partly from the description and partly from the practice of the invention.
    Brief description of the figures
    Figure 1: RX diffraction patterns of the materials obtained in the present invention EXAMPLES
    Non-limiting examples of the present invention will be described below.
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    Example 1: Synthesis of N, N-dimethyl-3,5-dimethylpiperidinium (DMDMP)
    10 g of 3,5-dimethylpiperidine (Sigma-Aldrich,> 96% by weight) are mixed with 19.51 g of potassium bicarbonate (KHCO3, Sigma-Aldrich; 99.7% by weight) and dissolved in 140 ml of methanol. Then 54 ml of methyl iodide (CH3I, Sigma-Aldrich,> 99% by weight) are added, and the resulting mixture is kept under stirring for 5 days at room temperature. After this time, the reaction mixture is filtered to remove potassium bicarbonate. The filtered solution is partially concentrated by rotary evaporator. Once the methanol has partially evaporated, the solution is washed with chloroform several times and magnesium sulfate (MgSO4, Sigma-Aldrich,> 99.5% by weight) is added. Next, the mixture is filtered to remove magnesium sulfate. The ammonium salt is obtained by precipitation with diethylene ether and subsequent filtration. The final yield of N, N-dimethyl-3,5-dimethylpiperidinium iodide is 85%.
    To prepare the hydroxide form of the organic salt above: 10.13 g of the organic salt are dissolved in 75.3 g of water. Next, 37.6 g of an anion exchange resin (Dower SBR) are added, and the resulting mixture is kept under stirring for 24 hours. Finally, the solution is filtered and N, N-dimethyl-3,5-dimethylpiperidinium hydroxide is obtained (with an exchange rate of 94%).
    Example 2: Synthesis of the silicoaluminate form of the zeolite structure AEI using the zeolite with FAU structure as the only source of silicon and aluminum
    21.62 g of a 6.9% by weight aqueous solution of N, N-dimethyl- hydroxide are mixed
    3,5-dimethylpiperidinium with 1.89 g of a 20% by weight aqueous solution of sodium hydroxide (NaOH, Sigma-Aldrich, 98%). The mixture is kept under stirring for homogenization for 10 minutes. Finally, 3.01 g of zeolite with FAU structure (CBV-720, molar ratio SiO2 / Al2O3 = 21) are added and the mixture is kept under stirring until the desired concentration is achieved. The final gel composition is SiO2 / 0.047 Al2O3 / 0.2 DMDMP: 0.2 NaOH: 15 H2O. This gel is transferred to a steel autoclave with a teflon jacket and heated at 135 ° C for 7 days under static conditions. After this time, the product obtained is recovered by filtration, washing with plenty of water, and then dried at 100 ° C. The material is calcined at 550 ° C for 4 hours in an air atmosphere to eliminate the organic matter contained inside. The solid yield obtained is greater than 80%.
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    Through X-ray diffraction, it is observed that the solid obtained presents the characteristic peaks of the AEI structure (see Figure 1). The chemical composition of the sample indicates a Si / Al ratio of 8.2.
    Example 3: Synthesis of the silicoaluminate form of the zeolite structure AEI using the zeolite with FAU structure as the only source of silicon and aluminum
    2.24 g of a 7.4% by weight aqueous solution of N, N-dimethyl- hydroxide are mixed
    3,5-dimethylpiperidinium with 0.173 g of a 20% by weight aqueous solution of sodium hydroxide (NaOH, Sigma-Aldrich, 98%). The mixture is kept under stirring for homogenization for 10 minutes. Finally, 0.193 g of zeolite with FAU structure (CBV-720, molar ratio SiO2 / Al2O3 = 21) are added and the mixture is kept under stirring until the desired concentration is achieved. The final gel composition is SiO2 / 0.047 Al2O3 / 0.4 DMDMP: 0.2 NaOH: 15 H2O. This gel is transferred to a steel autoclave with a teflon jacket and heated at 135 ° C for 7 days under static conditions. After this time, the product obtained is recovered by filtration, washing with plenty of water, and then dried at 100 ° C. The material is calcined at 550 ° C for 4 hours in an air atmosphere to eliminate the organic matter contained inside. The solid yield obtained is practically 90%.
    Through X-ray diffraction, it is observed that the solid obtained presents the characteristic peaks of the AEI structure (see Figure 1). The chemical composition of the sample indicates a Si / Al ratio of 9.0.
    Example 4: Preparation of zeolite AEI in its silicoaluminate form exchanged with Cu
    The sample synthesized and calcined according to the method set forth in Example 2 of the present invention is washed with 150 g of a 0.04 M aqueous solution of sodium nitrate (NaNO3, Fluka, 99% by weight) per gram of zeolite.
    0.053 g of copper acetate [(CH3COO) 2CuH2O, Probus, 99%) are dissolved in 48 ml of water, and 0.48 g of the previously washed zeolite are added. The suspension is kept under stirring for 20 h at room temperature. After this time, the product obtained is recovered by filtration and washed with plenty of water. Finally the
    material is calcined in air at 550 ° C for 4h. The final copper content in the sample is 4.7% by weight.
    Example 5: Thermal treatments in the presence of steam
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    The sample prepared according to Example 4 of the present invention is treated with steam (2.2 ml / min) at 750 ° C for 13 hours. The solid obtained is characterized by X-ray diffraction, observing the characteristic peaks of the AEI zeolithic structure (see Figure 1).
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    Example 6: Catalytic test for the RCS reaction of NOx
    The 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 synthesized according to the present invention is compacted into particles of a size between 0.25-0.42 mm, introduced into the reactor, and the temperature is increased to 550 ° C (see conditions of reaction in Table 2); 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. 20 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 3.
    Table 2: Reaction conditions for NOx RCS.
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     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 tested (° C)  170-550
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    Table 3: Conversion (%) of NOx at different temperatures (200, 250, 300, 350, 400, 450, 500 ° C) using the Cu-AEI catalysts prepared according to Example 4 and 5 of the present invention
     Conversion (%) of NOx at different temperatures
     200 ° C 250 ° C 300 ° C 350 ° C 400 ° C 450 ° C 500 ° C
     Example 4  73.6 94.3 99.6 99.7 98.6 97.5 89.1
     Example 5  55.3 89.0 97.1 97.9 95.0 89.2 78.0
    Example 7: Synthesis using zeolite with FAU structure and sodium silicate as sources of aluminum and silicon, respectively
    1,982 g of a 6.4% by weight aqueous solution of N, N-dimethyl- hydroxide are mixed
    3.5-dimethylpiperidinium with 0.167 g of a 20% by weight aqueous solution of sodium hydroxide (NaOH, Sigma-Aldrich, 98%). The mixture is kept under stirring for homogenization for 10 minutes. Then, 0.084 g of zeolite with FAU structure (CBV-500, SiO2 / Al2O3 molar ratio = 5.2) and 0.69 g of sodium silicate (NaSiO3, Sigma Aldrich, Na2O 10.6% by weight and SiO2 26.5% by weight) are added and added keep the mixture under stirring until the desired concentration is achieved. The final gel composition is SiO2 / 0.047 Al2O3 / 0.2 DMDMP: 0.2 NaOH: 15 H2O. This gel is transferred to a steel autoclave with a teflon jacket and heated at 135 ° C for 7 days under static conditions. After this time, the product obtained is recovered by filtration, washing with plenty of water, and then dried at 100 ° C.
    Through X-ray diffraction, it is observed that the solid obtained presents the characteristic peaks of the AEI structure. The solid yield obtained is less than 40%.
    Example 8: Synthesis using zeolite with FAU and LUDOX structure as sources of aluminum and silicon, respectively
    2.001 g of a 6.4% by weight aqueous solution of N, N-dimethyl- hydroxide are mixed
    3.5- dimethylpiperidinium with 0.164 g of a 20% by weight aqueous solution of hydroxide
    sodium (NaOH, Sigma-Aldrich, 98%). The mixture is kept under stirring for
    homogenization for 10 minutes. Then, 0.080 g of zeolite are added with
    FAU structure (CBV-500, SiO2 / Al2O3 molar ratio = 5.2) and 0.454 g of Ludox (SiO2, Sigma
    Aldrich, 40% by weight) and the mixture is kept under stirring until concentration is achieved
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    desired. The final gel composition is SiO2 / 0.047 AI2O3 / 0.2 DMDMP: 0.2 NaOH: 15 H2O. This gel is transferred to a steel autoclave with a teflon jacket and heated at 135 ° C for 7 days under static conditions. After this time, the product obtained is recovered by filtration, washing with plenty of water, and subsequently, dried at 100 ° C.
    X-ray diffraction shows that the solid obtained is amorphous.
    Example 9: Synthesis using zeolite with FAU and Aerosil structure as sources of aluminum and silicon, respectively
    1,996 g of a 6.4% by weight aqueous solution of N, N-dimethyl- hydroxide are mixed
    3,5-dimethylpiperidinium with 0.158 g of a 20% by weight aqueous solution of sodium hydroxide (NaOH, Sigma-Aldrich, 98%). The mixture is kept under stirring for homogenization for 10 minutes. Then, 0.078 g of zeolite are added with
    FAU structure (CBV-500, molar ratio SiO2 / Al2O3 = 5.2) and 0.181 g of Aerosil and the mixture is kept under stirring until the desired concentration is achieved. The final gel composition is SiO2 / 0.047 Al2O3 / 0.2 DMDMP: 0.2 NaOH: 15 H2O. This gel is transferred to a steel autoclave with a teflon jacket and heated at 135 ° C for 7 days under static conditions. After this time, the product obtained is recovered by filtration, washing with plenty of water, and then dried at 100 ° C.
    X-ray diffraction shows that the solid obtained is amorphous.
    权利要求:
    Claims (26)
    [1]
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    1. Process of synthesis of a crystalline material that has the zeolite structure AEI characterized in that it comprises at least the following steps:
    (i) Preparation of a mixture containing, at least, water, a zeolite with the crystalline structure FAU as the only source of silicon and aluminum, a cyclic ammonium cation with alkyl substituents such as ADEO, and a source of alkaline or alkaline earth cations (A ), and where the synthesis mixture has the following molar composition:
    SiO2: a AfeOs: b OSDA: c A: d H2O where a is in the range of 0.001 to 0.2; where b is in the range of 0.01 to 2; where c is between the range of 0 to 2; where d is between the range of 1 to 200;
    (ii) Crystallization of the mixture obtained in (i) in a reactor.
    (iii) Recovery of the crystalline material obtained in (ii).
    [2]
    2. Process according to claim 1, characterized in that the cyclic ammonium cation used as ADEO is a quaternary ammonium selected from N, N-dimethyl-3,5-dimethylpiperidinium (DMDMP), N, N-diethyl-2,6-dimethylpiperidinium ( DEDMP), N, N-dimethyl-2,6-dimethylpiperidinium, N-ethyl-N-methyl-2,6-dimethylpiperidinium and combinations thereof.
    [3]
    3. Process according to claim 2, characterized in that the ADEO is N, N-dimethyl-3,5-dimethylpiperidinium.
    [4]
    4. Process according to claim 1, characterized in that it further comprises another cooperative ADEO present in step (i), and is any organic molecule.
    [5]
    5. Process according to claim 4, characterized in that the cooperative ADEO is an ammonium cation.
    [6]
    6. Process according to claim 5, characterized in that the cooperative ADEO is a cyclic ammonium cation.
    5
    10
    fifteen
    twenty
    25
    30
    35
    [7]
    7. Process according to claim 4, characterized in that the ADEO cooperative is an amine.
    [8]
    8. Process according to claims 1 to 7, characterized in that the process of
    crystallization described in (ii) is carried out in autoclaves, in static conditions or
    dynamic.
    [9]
    9. Process according to claims 1 to 8, characterized in that the process of
    Crystallization described in (ii) is carried out at a temperature between 100 and 200 ° C.
    [10]
    10. Process according to claims 1 to 9, characterized in that the crystallization time of the process described in (ii) is between 6 hours and 50 days.
    [11]
    11. Process according to claims 1 to 10, characterized in that it further comprises adding AEI crystals as seeds to the synthesis mixture in an amount up to 25% by weight with respect to the total amount of oxides.
    [12]
    12. Process according to claim 11, characterized in that the AEI crystals are added before the crystallization process or during the crystallization process.
    [13]
    13. Process 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.
    [14]
    14. Process according to claims 1 to 13, characterized in that it also comprises the elimination of the organic content contained inside the material by means of an extraction process.
    [15]
    15. Process according to claims 1 to 13, characterized in that it also comprises the elimination of the organic content contained inside the material by means of a heat treatment at temperatures between 100 and 1000 ° C for a period of time between 2 minutes and 25 hours.
    [16]
    16. Process according to claims 1 to 15, characterized in that the material obtained is pelletized.
    5
    10
    fifteen
    twenty
    25
    30
    35
    [17]
    17. Process according to claims 1 to 16, characterized in that any cation present in the material can be exchanged by ion exchange for other cations using conventional techniques.
    [18]
    18. Process according to claim 17, characterized in that the exchange cation is selected from metals, protons, proton precursors and mixtures thereof.
    [19]
    19. Process according to claim 18, characterized in that the exchange cation is a metal selected from rare earths, metals of groups IIA, IIIA, IVA, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII and combinations thereof.
    [20]
    20. Process according to claim 19, characterized in that the metal is copper.
    [21]
    21. Zeolitic material with AEI structure obtained according to the process described in claims 1 to 20, characterized in that it has the following molar composition
    SiO2: or Al2O3: p A: q ADEO1: r H2O
    where
    A is an alkaline or alkaline earth cation; or is in the range of 0.001 to 0.2; p is between the range of 0 to 1; q is between the range of 0.01 to 1; r is in the range of 0 to 2;
    [22]
    22. Zeolitic material with AEI structure according to claim 21, characterized in that it has the following molar composition after being calcined:
    SiO2: or Al2O3: p A
    where or is between the interval 0.001 and 0.2; where p is between the range of 0 to 2.
    [23]
    23. Zeolithic material with AEI structure according to claim 22, characterized in that it has the following molar composition after introducing the metal (M):
    SiO2: or Al2O3: r M
    where or is between the interval 0.001 and 0.2; where r is between the interval 0.001 and 1.
    [24]
    24. Zeolithic material with AEI structure according to claim 23, characterized in that the metal (M) is copper.
    [25]
    25. Use of a zeoltic material with AEI structure described in claims 21 to 24 and 5 obtained according to the process described in claims 1 to 20 in processes for the
    conversion of feeds formed by organic compounds into products of higher added value, or for their elimination / separation of reactive currents by contacting said feed with the described material.
    10 26. Use of a zeolite material with AEI structure according to claim 25, for the
    olefin production after contacting an oxygenated organic compound under certain reaction conditions.
    [27]
    27. Use of a zeolite material with AEI structure according to claim 25 for the selective catalytic reduction (RCS) of NOx (nitrogen oxides) in a gas stream.
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    同族专利:
    公开号 | 公开日
    JP2018517659A|2018-07-05|
    RU2017139760A3|2019-09-05|
    RU2017139760A|2019-05-16|
    BR112017022001A2|2018-07-03|
    US20180093895A1|2018-04-05|
    CA2982224A1|2016-10-20|
    KR20180030771A|2018-03-26|
    ES2586775B1|2017-08-14|
    US10526208B2|2020-01-07|
    EP3283437A1|2018-02-21|
    WO2016166245A1|2016-10-20|
    CN107635920A|2018-01-26|
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    EP16717888.8A| EP3283437A1|2015-04-16|2016-04-14|Method for preparing the silicoaluminate form of the aei zeolite structure with high yields, and its application in catalysis|
    BR112017022001A| BR112017022001A2|2015-04-16|2016-04-14|A method for the preparation of the silicoaluminate form of the high yield ae zeolite structure and its application in catalysis.|
    RU2017139760A| RU2017139760A3|2015-04-16|2016-04-14|
    CN201680022089.9A| CN107635920A|2015-04-16|2016-04-14|The high yield preparation method of aluminosilicate form zeolite structured AEI, and its application in catalysis|
    PCT/EP2016/058275| WO2016166245A1|2015-04-16|2016-04-14|Method for preparing the silicoaluminate form of the aei zeolite structure with high yields, and its application in catalysis|
    CA2982224A| CA2982224A1|2015-04-16|2016-04-14|Method for preparing the silicoaluminate form of the aei zeolite structure with high yields, and its application in catalysis|
    JP2018505532A| JP2018517659A|2015-04-16|2016-04-14|Method for producing high yield silica aluminate-type zeolite structure and its catalytic use|
    KR1020177032273A| KR20180030771A|2015-04-16|2016-04-14|A process for preparing a silicoaluminate form of AEI zeolite structure at high yield, and its application in catalysis|
    US15/566,302| US10526208B2|2015-04-16|2016-04-14|Method for preparing the silicoaluminate form of the AEI zeolite structure with high yields, and its application in catalysis|
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