• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention is an inorganic-organic porous hybrid material comprising a core of zeolite or an amorphous aluminosilicate with an atomic ratio Si/Al between 1 and a value less than 2.5, and a shell of an MOF formed by a ligand bidentate organic linked covalently to the aluminum atoms of said zeolite or amorphous aluminosilicate. Its manufacturing process does not include any other source of metal than the aluminum contributed by the zeolite on which it grows. The crystallized MOF is rigid and therefore has a greater thermal stability, and does not suffer from breathing phenomena. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2682056A1
    申请号:ES201730353
    申请日:2017-03-16
    公开日:2018-09-18
    发明作者:Jorge José PÉREZ CACHO；Fernando CACHO BAILO；Joaquín CORONAS CERESUELA；Carlos Téllez Ariso
    申请人:Industrias Quimicas Del Ebro SA；Industrias Quim Del Ebro S A；Universidad de Zaragoza；
    IPC主号:
    专利说明:

    TECHNICAL SECTOR The present invention describes a hybrid porous material comprising an MOF and an aluminosilicate. It belongs to the development of porous materials intended for adsorption, separation, catalysis, capture and controlled release of substances in the
    10 industrial chemistry sector.
    STATE OF THE TECHNIQUE
    Metal-organic structures (MOFs) are crystalline solids
    formed by metallic clusters joined by organic ligands. These MOFs form
    15 micro-and mesoporous structures of large specific surface area, even greater than 5000 m2 / g, and large capacity for selective adsorption, capture and separation.
    MOFs are the ordered micro-and mesoporous structures technologically subsequent to zeolites. There is a wide variety of metals and organic ligands
    20 available for synthesis and can be functionally raised to show a certain chemical character with structures and pore sizes on demand according to the application. Thanks to this versatility in the design there are in the MOF technique that crystallize imitating the already known topologies of zeolites.
    25 Zeolites are hydrated crystalline porous aluminosilicates with formula M2InO: Ab03: Si02: H20, "M" being a metal that acts as a compensation cation and "n" its valence. They have rigid pore sizes that act as very restrictive molecular sieves. To the detriment of those with little aluminum content, they are the zeolites that have a low Si / Al ratio and L TA and FAU types almost the only ones
    30 manufactured on an industrial scale. They preferably adsorb C02 and H20, and are useful as adjuvants in detergents, ion exchangers, adsorbents, molecular sieves and catalysts in petrochemical processes of catalytic cracking, among others. Its main drawback is that they have a relatively low stability.
    The most common synthetic zeolites are zeolite A (L TA) in potassium form 3A, sodium 4A and calcium 5A according to their compensation cation, and zeolites X and Y (FAU). They are sold in the form of very fine powders with crystal sizes between 0.1 and 30 micrometers. These materials have great interest in the technique due to the size of their
    5 ordered rigid pores, in the same range of 0.3 -1.3 nanometers as the moleculesof smaller gases, which can therefore be selectively separated bymolecular sieving
    The zeolites are inorganic and suffer a contraction of their structure during their dehydration. They also have poor compatibility with organic polymers, which form the continuous phase of mixed matrix membranes.
    EP 0790253 81 was the first patent related to MOFs and registered by O.M.Yaghi together with NALCO Chemical Co. (USA). It covers virtually all metals and
    15 organic ligands capable of giving rise to an MOF. Since then, the BASF company has patented its own portfolio of patents covering the industrial scale production of MOFs.
    Application WO 2010058123 A1 describes hydrothermal synthesis in the absence of
    20 organic MOF solvents based on aluminum and carboxylate-type ligands in any of its forms. It raises the technological advantage of a synthesis of MOF that is more environmentally friendly than the previous ones.
    From it, BASF registered WO 2012042410 A 1, which describes the synthesis
    25 optimized structures formed by aluminum and bidentate carboxylate ligands, including benzenedicarboxylate or terephthalate (BDC or TPA) that resulted in MIL-53 ("Material Institute Lavoisier" -53), marketed under the name Basolite ® A 100. Develops the synthesis of MOFs based on aluminum avoiding the use of nitrates and chlorides.
    Related to the previous patent, Sánchez-Sánchez reported the synthesis of several MOFs at room temperature and exclusively in water, also by adding an organic ligand deprotonated by the presence of a base or directly in the form of salt (M. Sánchez -Sanchez et al. "Synthesis of metal-organic frameworks in water at 35 room temperature: salts as linker sources", Green Chem., 2015, 17, 1500-1509). While
    The resulting products have unreacted ligand-free pores, the source of aluminum does come from nitrates or chlorides.
    Many patents related to MOFs are currently registered
    5 developing other types of synthesis and improvement of procedures, in addition to theirApplications. WO 2011081779 A2, for example, describes the polymer combinationand MOF in membranes that separate CO2 from methane. Thanks to its metal characterOrganic, MOFs have good compatibility with polymers.
    10 However, MOFs lack narrow pores and a rigid structure, attractive qualities for high efficiency separations. It is common for these structures to present phenomena of flexibility or "breathing" in the presence of adsorbates or with variations in pressure and temperature, which give rise to undesirable variations in pore sizes.
    15 In the search for porous materials for use as high efficiency separators, the possibility of achieving a simultaneous combination of MOF and zeolila properties is raised.
    The technique describes hybrid materials that combine MOFs and zeolites by solvothermal synthesis of MOF using the zeolites as heterogeneous growth surfaces, but where both materials do not react and do not share the same structure or composition. In these processes the addition of two reagents, a metallic source and an organic ligand in the reaction is always needed (Y. Liu et al. "Fast
    25 syntheses of MOFs using nanosized zeolite crystal seeds in situ generated from microsized zeolites ", Cryst. Growth Des., 2013, 13, 2697-2702; G. Zhu et al." Synthesis of zeolite @ metal-organic framework core-shell particles as bifunctional catalysts ", RSC Adv., 2014, 4, 30673-30676; DW Lim et al." An unprecedented single platform via cross-linking ofzeolite and MOFs "Chem. Commun., 2016, 52, 6773-6776).
    These hybrid porous solids are based on an adjacent growth of an MOF on a two-stage support: the impregnation with a metallic source of the support material, and the subsequent addition of ligand and crystallization of the MOF in the presence of the support. The support material has a different chemical composition and does not share its
    atoms or their structure with the MOF that grows, nor does it influence the structure that is formed.
    Such material is described in what is considered the closest document
    5 to the present invention, application EP 2341031 A1. This publication describes a two part porous hybrid material comprising an MOF accompanied by a silica, a zeolite or an active carbon. Specifically, it describes a method for obtaining a porous material comprising the chemical bonding of these materials with the MOF (paragraph [0014]). However, said chemical bond is then described only as a function.
    10 of the method of obtaining the hybrid (paragraph [0044]). As noted above, the method requires the provision of an additional metal precursor as an essential condition, which is indicated both in the description and in the particular implementation of the application. The only example of EP 2341031 A1 reacts zinc nitrate in solution with the organic terephthalate ligand in the presence of mesoporous silica. He
    The result is that the two materials that make up the final hybrid product are independent in their arrangement and chemical composition; Zn40 (TPA) J forms the MOF, while the inorganic part is SiOz. There are no strong covalent bonds between the two hybrid components. The union between the two is due to weak physical or chemical necessity of van der Waals forces, and this does not prevent the breathing process
    20 of the MOF.
    As the core is a rigid inorganic material, these structural stresses in the MOF limit the physical stability of the hybrid itself and can break the weak physical-chemical bonds. These variations with temperature give rise to defects, channels or
    25 holes in the matrices that contain them, which decrease their mechanical and separation properties, acting as a bypass or preferential channels for the molecules to be separated ("TSChung et al." Mixed matrix membranes (MMMs) comprising organic polymers with dispersed inorganic fillers tor gas separation ", Prog. Polym. Sei., 32 (2007), 483-507).
    The procedure described in EP 2341031 A1 requires the contribution of the two reagent sources, metal and ligand, in two different stages for the synthesis of the hybrid material. It does not describe or suggest the possibility of a one-stage process with the addition of ligand only and where the metal is supplied by the inorganic material itself.
    Supplemental metal addition has two main consequences: the first isthat the growth of MOF is not limited to the surface of the inorganic material usedas support It will then be necessary to deduct additional costs in the processderived from the elimination of free MOF that has grown in solution, whose efficiency5 separation will affect the purity of the final hybrid material. For the same reason, themethod does not guarantee the total coating of the inorganic support with MOF in acore-shell conformation, so the selective adsorption performance of theHybrid material are not optimal. The second consequence is that the conditionsThe reaction reactions are not compatible with the stability of low Si / Al zeolites.
    In particular, the process causes the dissolution and disappearance of said zeolite in the case of the growth of an MOF in aqueous medium from terephthalate ligand and an aluminum salt, the conditions closest to the method of the present invention.
    The problem of the technique regarding EP 2341031 A 1 can be considered as the
    Obtaining an aluminosilicate-MOF hybrid material with a core-shell structure, whose shell MOF has a rigid structure and the core is a low Si / Al porous aluminosilicate capable of maintaining its selective adsorption technical performance. The solution proposed by the present invention is a hybrid solid whose MOF ligands of the shell are covalently bonded to aluminum atoms.
    20 of said aluminosilicate and are shared at an interface between both parts of the hybrid material.
    DESCRIPTION OF THE INVENTION The present invention is a porous inorganic-organic hybrid material comprising
    A nucleus of zeolite or an amorphous aluminosilicate with an Si / Al atomic ratio between 1 and a value less than 2.5, and a metal-organic structure shell (MOF) formed by a bidentate organic ligand covalently bonded to atoms of aluminum of said zeolite or amorphous aluminosilicate.
    Within the scope of the present invention, "hybrid material" is defined as that formed by two different materials that also have different structures.
    The present application describes the process of manufacturing a hybrid material with no other metal source than the aluminum provided by the zeolite itself on which it grows.
    No metallic or metal salt dispersion is introduced into the reactor where said hybrid material is formed.
    Thanks to the covalent union of the organic ligands with the inorganic core aluminum, the crystallizing MOF is rigid. As it grows on fixed positions of the zeolite core that acts as a substrate, its X-ray diffractogram does not change with adsorption / desorption or with temperature, it does not suffer breathing phenomena. It therefore has a higher thermal stability, 600 oC (Figure 8), compared to the MOF of the technique, for example the 560 oC of the compound made of aluminum and TPA described in EP 2341031 A1.
    Thanks to its core-shell shape, the hybrid material of the invention combines in a hierarchical way the meso-and microporosities of a MOF outside with high compatibility with polymers and chemically functionalizable to modify its surface and adsorption properties in a versatile way, and a zeolite of low Si / Al ratio in the nucleus, with very narrow rigid micropores and very useful in dehydration and gas separation.
    So that in a very preferable aspect, the hybrid material of the invention has a microporosity of 1-2 nanometers and a mesoporosity of 2-10 nanometers in said MOF, in addition to the microporosity of the corresponding type zeolite between 0.1 And 1 nanometer. The combined presence of mesopores and micropores is shown, for example, in the hybrid material obtained in Example 4 (Figure 5).
    The possible organic ligands that form the MOF are known in the art and are defined. for example. in EP 2341031 A1 (par. [0050). in Spanish):
    The precursor organic ligand may include, for example, at least one organic compound selected from the group consisting of terephthalic acid, substituted terephthalic acid, tribenzoic acid, imidazole, substituted imidazole, pyridine, substituted pyridine, pyrazole, substituted pyrazole, tetrazole and substituted tetrazole. In the present specification, the term "substituted" refers to a compound or radical in which a hydrogen atom of the compound or radical is substituted by at least one (eg 1, 2, 3, 4, 5, 6 or more ) substituents independently selected from a halogen group, (eg F, GI, Br, or 1),
    a hydroxyl group, an alkyl group, an alkoxy group, an amino group, or a combination thereof __. "
    US 2012/0296103 A1 provides another valid definition for the ligands of the present invention (par. [0007], in Spanish):
    "The ligand is the organic parle of the hybrid material. These ligands are usually di-or tricarboxylates, and their derivatives, or derivatives of pyridine. Some of the most common organic ligands are shown below: bdc (benzene-1,4-dicarboxylate ), btc (benzene-1,3,5-tricarboxylate), ndc (naphthalene 2,6-dicarboxylate), bpy (4,4'-bipyridine), hfipbb (4,4'-hexafluoroisopropylidenobisbenzoate), cyclam (1,4, 8, 11-tetraazacyclotetradecane) ".
    So another preferable aspect is that the organic ligand that forms the MOF of the invention be terephthalate, amino-terephthalate, diamino-terephthalate, bromoterephthalate, chloroterephthalate, fluoroterephthalate, iodoterephthalate, methyl-terephthalate, dimethyl-terephthalate, dimethyl-terephthalate, dimethyl-terephthalate, dimethyl-terephthalate, dimethyl-terephthalate, dimethyl-terephthalate, dimethyl terephthalate -terephthalate, fumarate, imidazole, pyridine, pyrazole, tetrazol, naphthalene-2,6-diearboxylate (nde), biphenyl-4,4'-diearboxylate (bpde), 4,4'-bipyridine (bpy), 4.4 ' -hexafluoroisopropylidene bisbenzoate (hfipbb) ° 1,4,8, 11-tetraazacyclotetradecane (eyclam).
    Any of these ligands has been reported in the art as suitable for shaping an MOF, so that including them all as possible components of the MOF of the hybrid material of the invention is a valid theoretical extension of the examples provided in this application. .
    Most preferably, said ligand is terephthalate, the deprotonated form of terephthalic acid. In this case, the MOF grows on the surface of the zeolite crystals with a laminar morphology on the flat initial surface of the zeolite (Figure 4b).
    The material of the invention uses aluminum-rich zeolites, of low Si / Al ratio, as the sole source of metal for the growth of the porous aluminum MOF surrounding the crystals of said zeolite, resulting in a hybrid core-shell material. Access to the porosity of the core is determined by the porosity of the outer MOF (Figure 1).
    The original zeolite is a product of hydrophilic character and high adsorption capacity, which may or may not retain its crystallinity in the final hybrid material.
    The Si / Al ratio of said original zeolite is between 1 and less than 2.5. Lower limit
    5 is limited by the Lowenstein rule that does not allow two adjacent aluminum; isthat is, links of the type -AI-O-AI-. The upper limit determines a concentration ofaluminum too low that does not allow anchoring of the organic ligand or formationof MOF. Thus, for the same crystal structure of the FAU type it is not appreciatedMOF growth starting from zeolite Y of Si / Al ratio = 2.5 (Example 5), while
    10 that from zeolite X of the same type FAU but with a Si / Al ratio = 1-1.5, the zeolite / MOF hybrid solid of the invention is obtained (Example 4).
    The existence of strong covalent bonds between the organic ligands and the aluminum atoms of the original zeolite forming part of a rigid structure give rise to a new MOF of unpublished structure.
    The formation of MOF in the process of the invention starts from a zeolite used as a reagent and growth surface at the same time. Since the medium does not contain another source of aluminum apart from the zeolite, the metal-ligand reaction is restricted to the 20 fixed positions of the aluminum atoms in the rigid structure of said zeolite. The structure of the MOF therefore has a crystalline system similar to the zeolite on which it crystallizes, interatomic distances that fit those metallic positions and related properties, such as the absence of flexibility of its pores and a high aspect ratio. The crystalline system is cubic in the materials a
    25 from zeolites type LTA and FAU. At the aluminosilicate-MOF interface, the two materials that make up the hybrid share the aluminum atoms of their structures, which belong to MOF and aluminosilicate simultaneously.
    The cell lengths of the cubic crystal system of the MOF (a, b, c) of the present
    30 invention were calculated with specialized software (FullProf Suite, Institut LaueLangevin). These lengths and the "d" spacings between MOF sheets and between aluminum atoms are related to the aluminum-aluminum distances present in the zeolites.
    The X-ray diffractogram of the MOF armor corresponds to the additional peaks that appear in the diffraction spectrum of the zeolite of the nucleus (Examples 1, 2, and 4), and is the same as that shown by the MOF that is isolated from the hybrid material (Example 7). This diffractogram indicates a preferential growth of the laminar structure in the
    5 planes (1 O O) Y (2 O O) whose peaks correspond in the case of Examples 1 to 4with atomic spacing (d) of 1.09 and 0.55 nm (Tables 1 and 2, Figures 2 and 3). Of thisdistances, at least 1.09 nm corresponds to the atomic spacing between atoms of Al.
    The diffraction spectrum corresponding to the MOF is: 10 2'Theta [') d [n m) Plane
    8.07 1,089 (1 O O)16.18 0.548 (2 O O)
    with an angle variability of 0.1 ° and spacing variability of 0.01 nm. The spacings (d) are calculated by means of the Bragg equation from the angles (2 · Theta) of the diffractogram peaks.
    Only in the samples of Examples 4 and 7 there is also a growth in the plane (2 1 O), showing a MOF growth perpendicular to the previous planes, corresponding to
    2'Theta [') d [n m) Plane
    8.07 1,089(1 O O)
    16.18 0.548(2 O O)
    18.11 0.489(2 1 O)
    20 These differences ((1 OO), (2 OO) and possibly (2 1 O »also indicate a cubic crystalline structure similar to the zeolites on which it grows, types L TA and FAU, which extends to the MOF. cubic crystalline system as other properties associated with the MOF of the invention, distance of atomic spacings,
    25 lack of flexibility, etc. they are also preserved even in those hybrid materials in which the zeolite core has lost its crystallinity (Example 3).
    In cases where the nucleus retains its crystalline structure, the spectrum will also present the peaks corresponding to the zeolite, whose X-ray spectrum for the various types are known in the art and are collected in the Book "Collection of Simulated XRD Powder Patterns for Zeolitesft by MMJ Treacy and JB Higgins The structures of the zeolites, and in particular of the LTA and FAU types, are described by the IZA (International Zeolite Association), Ch. Baerlocher and LB McCusker, Database of Zeolite Structures: http: / /www.iza-structure.org/databases.
    Thus, one more aspect of the present invention is a porous hybrid material that has X-ray diffraction spectra containing the previous peaks, or the interatomic distances that are reported in the MOF.
    In Example 7, the metal-organic structure corresponding to the shell of the hybrid porous solid of the invention is segregated and separated. The segregated material maintains the laminar structure and the previous X-ray diffractogram (Figures 9 and 10 and Table 2), corresponding to the same cubic structure and the same interlaminar and aluminum-aluminum spacing that it acquired during its growth on the zeolite. The isolated metal-organic structure shows a thermal stability around 560 oC, somewhat lower than the 600 oC to which the MOF that remains attached to the zeolite core degrades. This isolated structure of unprecedented properties, with a high aspect ratio, can be used separately as a rigid MOF for various industrial uses.
    Accordingly, another preferable aspect of the present invention is an isolated MOF structure that has a distance between aluminum atoms of 1.09 nm with a variability of 0.1 nm, or that has the corresponding X-ray spectrum to the MOF of the hybrid material.
    In all cases the Al-Al distances are unique and constant in at least two directions of growth. This is new with respect to procedures that use an additional metallic source. The MIL-53, for example, uses terephthalate as a ligand but has an orthorhombic structure with different unit cell lengths in all directions and different aluminum-aluminum distances in each of the axes.
    Figure 12 shows the nuclear magnetic resonance spectra of 29Si and 27Al of a hybrid material according to the invention compared to those of zeolite 4A of
    departure. Changes in Si-Al coordination related to thepresence of the new TPA-aluminum bonds at the MOF-zeolite interface, produced5 by the chemical reaction of the organic ligands with the aluminum atoms of thecharacteristic zeolites of this invention.
    The hierarchical union of the meso-and microporosities of MOF and zeolite results in a CO2-exclusive effect. The MOF of the shell excludes almost all CO2 and prevents its passage into the porosity of the zeolite core (Figure 7 and Table 3). The organic MOF acts as a "gate" for C02 on the narrow and rigid pore inorganic zeolite core, thus reducing the surface diffusion of CO2 throughout the hybrid solid and improving the efficiency of the H2 / C02 separation. So, the material
    hybrid of Example 1 only adsorbs 1.2 mmol · g · 1, 43% of the CO2 that would be expected according to its composition. which is 87% plp of zeolite and 13% plp of MOF (simulated Example 1 isotherm).
    The MOF therefore aclúa of gate avoiding the passage of the CO, to the zeolite of the nucleus. which would preferentially adsorb a large amount thereof (up to 4.0 mmol · g · 1). The
    The drastic reduction in the adsorption of C02 by the hybrid material of the invention with respect to the starting zeolite makes it very useful in separations of environmental impact gases, and in particular for the efficient separation of the H2 / C02 gas mixture into pre-combustion within CO storage and capture strategies.
    The porous hybrid material of the invention synergistically improves the properties of the materials separately. The compatibility of zeolites with polymers is enhanced by coating with a porous MOF based on the metal of the zeolite itself. The organic character of the MOF prevents the formation of empty holes that are not selective when passing
    30 gases used as fillers in mixed membranes (Fig. 11). These gaps are common with the addition of pure zeolite polymers.
    In the process of obtaining a hybrid material according to the invention, an MOF crystallizes in aqueous medium by coating and anchoring a zeolite from the aluminum it contains.
    said zeolite. No additional metal source is needed for the formation of the MOF.
    So another preferable aspect is the procedure for obtaining the material
    Porous hybrid of the invention, which comprises reacting an organic ligandbidentate in the presence of a zeolite in aqueous dispersion at a temperature between 0 °and 80 ° e, preferably between 15 ° and 40 ° e, for 1 to 28 days, preferably between2 and 7 days, in which said aqueous dispersion has a molar ratio Al zeolite Iligand between 1 and 4 to obtain a zeolite core hybrid, or a ratio
    10 molar Al zeolite, linking between 0.50 and a value less than 1 to obtain an amorphous aluminosilicate core, in which said porous aluminosilicate or said zeolite have a Si / Al ratio between 1 and a value less than 2.5 , to obtain an inactive hybrid material and free organic ligand; followed by the separation and activation of said inactive hybrid material.
    The reaction temperature is limited by the minimum to avoid freezing of the water and the maximum delimited by the increase in the solubility of the organic ligand and the total digestion of the zeolite, which would result in a material other than that of the invention.
    The lowest value of the molar ratio of Al / ligand corresponds to the hybrid material with aluminosilicate core where the total zeolite amortization has occurred (Example 3). Values between 1 and 4 give rise to zeolite-MOF hybrid material. The upper limit is determined by a zero MOF formation.
    A very preferable aspect of the invention is that said starting zeolite is an LTA type zeolite, or a FAU type X or Y zeolite.
    This procedure may include a step of washing the inactive hybrid material after separation of the inactive hybrid material, or the addition of solvent
    30 before said separation to achieve the same washing effect. The washing solvent may be any polar organic solvent miscible with water, preferably DMF, DMSO, DMAc, etc.
    Said separation may be a mechanical separation of a solid in a solution, typically by decantation or filtration.
    The process may also include drying the hybrid material obtained at the evaporation temperature of the less volatile solvent used.
    5 Within the scope of the present application, the expression "inactive hybrid material" refers toto the material of the invention presenting the pores of the newly formed MOF covered byligand deposited without reacting, and therefore is inactive or partially inactive in itsfunctionality
    Said activation is preferably by solvothermal dissolution or by thermal decomposition of the free organic ligand.
    Within the scope of the present application, the term "solvothermal solution" refers to a wash typically for 72 h at a temperature between 25 and 150 oC with a solvent that solubilizes the ligand present in the pores.
    Within the scope of the present application, the term "thermal decomposition" refers to the removal of the unreacted ligand on the surface of the hybrid by subjecting the inactive hybrid product to a temperature between 250 ° C and 400 ° C for a period of time.
    20 typically 72 h.
    The zeolite results in deprotonation of the organic ligand on its surface in aqueous medium and at room temperature. Its subsequent binding to the aluminum of the zeolite occurs in a single stage, creating a high organic MOF coating to its
    25 around.
    So the MOF grows in the process of the invention from the addition of only one organic ligand to a dispersion of zeolite in water. This procedure avoids the need for any additional source of aluminum, such as aluminum, alumina or metallic aluminum salts 30, or a strong deprotonator for the crystallization of MOF. The presence of compensation ions such as nitrates, chlorides or sulfates in the medium is also avoided. Zeolite crystals act simultaneously as a reagent by providing the source of aluminum and as a substrate, enhancing heterogeneous nucleation in the growth of MOF. The method of
    Synthesis is carried out in aqueous medium restricting the use of organic solvents to a washing step.
    A dependence on the amount of MOF formed in the hybrid material is found
    5 of the invention with the Al I ligand ratio that the reaction medium has. Beobtain higher proportions of MOF with respect to zeolite with molar ratios AlI ligand lower (Examples 1 and 2, with 13 and 25% plp of MOF, from 4 and 2 molesof aluminum per mole of organic ligand, respectively). However, if saidmolar ratio is less than 1 the nucleus of the zeolite loses its crystallinity and remains
    10 in the hybrid as an amorphous aluminosilicate (Example 3). Al I ligand ratios greater than 4 do not give rise to MOF growth on the zeolite. The concentration of zeolite or ligand in the medium has no decisive influence on the process and remains constant in the Examples (water molar ratio I ligand = 200).
    These reaction conditions that keep a moderately acidic organic ligand insoluble in water at low temperature also maintain the crystallinity of a zeolite rich in aluminum in the reaction medium.
    In the procedures of the art, however, the addition of a base is required.
    20 strong or a source of metallic aluminum of an acidic nature, or of high temperatures, since the organic ligands are poorly soluble in aqueous medium. These conditions are incompatible with the low stability of high aluminum zeolites. The absence of a strong deprotonator or an additional aluminum source is a definite technological advantage of the process of the invention with respect to
    25 the technique.
    Example 9 shows the manufacture of a hybrid with an MOF of aluminum-TPA and zeolite A in aqueous medium using an aluminum source in the form of metal salt following the conditions of procedures described in the art. The zeolite is incompatible with the reaction medium. Hydrolysis of the AP + cation results in acidity that dissolves the Si / AI = 1 ratio material. This shows the incompatibility of zeolite A (type LTA) with crystallization procedures of MOFs that use additional aluminum salt sources. Figure 13 shows the X-ray spectrum of the material obtained, which can be matched with the MOF spectrum of composition 35 AI (BDC) (OH) of the technique. This MOF does present phenomena of structural variation
    with temperature, whose combined use with zeolites would be discouraged in composite polymeric materials.
    Example 8 describes a polymer added with the hybrid material of the invention
    5 as filler material for application in separation membranes. PolymersWith filler material they are known as mixed matrix membranes. In this case, theMOF shell improves compatibility with the polymer by its organic character,avoiding the formation of empty volumes in the final composite polymeric material.In addition, improved adhesion between inorganic core and MOF shell prevents
    10 formation of defects or gaps in the membrane in processes with temperature change caused by the flexibility of the MOF. Consequently, the hybrid material of the invention improves the compatibility of the zeolite with the polymers.
    Another aspect of the invention is to combine the isolated MOF (Example 7) with a polymer such as those described in WO 2011081779 A2, preferably in a proportion of 5 to 50% w / w.
    In the case of the hybrid material of Example 3, where the low aluminum I ligand ratio in the synthesis entails the complete amorphization of the zeolite crystalline nucleus, the hybrid
    The resulting one maintains a high compatibility with polymers thanks to its superficial organic metal character, in addition to being equally suitable for stream dehydration or selective adsorption processes.
    Another preferable aspect of the invention is the use of the hybrid material in a process of
    Dehydration, separation or selective adsorption of gases or liquids. These processes use composite polymeric materials or mixed matrix membranes, so that another very preferable aspect is that the hybrid material of the invention be part of said mixed matrix membrane or composite polymeric material.
    A further preferable aspect is the use of the hybrid material of the invention as a catalyst, in a catalytic process.
    Another preferable aspect is the use of the MOF of the invention as a desiccant, as a catalyst, as a filler in mixed membranes or a composite polymeric material.
    The following Examples describe zeolite / MOF hybrid solids starting from the most important zeolitic phases in the art, which are zeolite A of type LTA (Examples 1 and 2) and zeolites X and Y of type FAU (Example 4 ), with different metal compensation cations.
    BRIEF DESCRIPTION OF THE FIGURESFigure 1 is an explanatory scheme of the porous hybrid material of the invention. (one):Inorganic core of zeolite or inorganic aluminosilicate with aluminum content.(2): an aluminum-based MOF that surrounds the nucleus, the atoms belonging
    10 metallic interfaces to both structures at the same time.
    Figure 2 is a graph of the intensity in arbitrary units versus the diffraction angle 29 in degrees showing the X-ray diffraction spectra (source of Cu Ka1, ' = 0.15406 nm) of the hybrid powdered materials prepared in the Examples
    15 1, 2 and 3 (curves 1, 2 and 3 respectively). The bars show the simulated diffractions of a zeolite type L 1 A for comparison.
    Figure 3 is a graph of the intensity in arbitrary units versus the diffraction angle 29 in degrees showing the X-ray diffraction spectra (source of
    20 Cu Ka1, ' = 0.15406 nm) of the hybrid powder materials prepared in Examples 4 and 5 (curves 4 and 5 respectively). The bars show the simulated diffractions of a FAU type zeolite for comparison.
    Figure 4a is a scanning electron microscopy image of a zeolite in
    25 powder type L commercial sodium standard TA (Z4A, 10OE); Figure 4b is a scanning electron microscopy image of the porous hybrid solid powder prepared according to Example 1.
    Figure 5 shows the pore size distribution (PSD)
    30 of the hybrid material prepared according to Example 4 and commercial zeolite X (ZEOCHEM® 13X, Si / Al ratio = 1-1.5, FAU type), calculated with the differential increase in surface area in nitrogen adsorption at 77 K against the pore diameter. The solid line corresponds to Example 4. The dotted line corresponds to zeolite X.
    Figure 6 is a graph of the variation of the mass versus the temperature of the hybrid materials manufactured under the conditions of Example 6, in the range of 25 to 750 ° C in an air atmosphere. The dotted line corresponds to fumaric acid, the continuous line to the amino-terephthalic and the broken line to the biphenyldicarboxylic.
    Figure 7 is a graph of the amount of carbon dioxide adsorbed in mmollg under isothermal conditions at 25 oC as a function of the relative pressure of carbon dioxide, expressed as the ratio to the vapor pressure at that temperature, of the material hybrid of Example 1, the MOF structure of Example 7 and commercial zeolites 3A (Z3A, IQE) and 4A (Z4A, IQE). The "simulated Example 1" isotherm is obtained as a linear combination of the isotherms of zeolite 3A and the MOF of Example 7 in an 87/13% w / w ratio.
    Figure 8 is a graph of the variation of the mass versus temperature of the hybrid material manufactured under the conditions of Example 1, the MOF of Example 7 and the zeolite KlNa-L TA (Z3A, 10E) in the range of 25 to 750 oC, in air atmosphere. The solid line corresponds to Example 1. The dotted line corresponds to Example 7. The broken line corresponds to Zeolite 3A (Z3A, IQE).
    Figure 9 is a scanning electron microscopy image of the laminar MOF that grows as a shell in the hybrid material of this invention, segregated and separated as described in Example 7.
    Figure 10 is a graph of the intensity in arbitrary units versus the diffraction angle 28 in degrees, showing the X-ray diffraction spectra (source of Cu Ka1, "= 0.15406 nm) of the composite material prepared according to Example 8, to the powder MOF prepared according to Example 7 and that corresponding to the commercial Udel® 3500 polysulfone, for comparison (curves 8, 7 and PSF, respectively).
    Figure 11 is a scanning electron microscopy image of a composite or composite polymeric material formed by the commercial zeolite / MOF hybrid material of the invention and commercial Udel® 3500 polysulfone, in equal proportions of 50% plp, manufactured according to Example 8.
    Figure 12 is a graph of the chemical shift of the 29Si and 27AI isotopes obtained by nuclear magnetic resonance (NMR) of cross polarity and dispersion of
    Magic angle for Zeolita 4A materials (Z4A, 10O) and the hybrid material of theinvention according to Example 2, of which the convolution of the 29Si spectrum is shown.5 The broken line corresponds to zeolite 4A; the continuous line corresponds to the materialhybrid of the invention.
    Figure 13 is a graph of the intensity in arbitrary units versus the diffraction angle 29 in degrees, showing the X-ray diffraction spectra (source of 10 Cu Ka1, A = O, 15406 nm) of the material manufactured according to Example 9 (curve 9).
    EXAMPLES
    With the intention of showing the present invention in an illustrative way, although in
    In no way limiting, the following examples are provided.
    Example 1: Synthesis of LTAlMOF potassium zeolite hybrid material 0.5 g of terephthalic acid (TPA, Sigma Aldrich, 98% purity) was dispersed as an organic ligand in 10 mL of distilled water and stirred for 10 min. Then 2 were added, 1 g of commercial zeolite 3A (Z3A 10O, K / Na-L TA, 38% K, Si / Al ratio = 1)
    20 to the dispersion of organic ligand in water and stirred for seven days at room temperature. The reaction mixture had approximately the following molar composition: 4 Al: 1 TPA: 200 H20. The solid product obtained was filtered and washed with distilled water and dimethylformamide (DMF) and dried at 200 ° C for 24 h. The solid powder product obtained was calcined at 330 oC for 72 h.
    The product obtained shows an MOF shell with 13% w / w by 87% w / w of the zeolite core (Figure 8), due to the high Al / ligand molar ratio of the reaction, with a value of 4. The Table 1 and Figure 2 show the X-ray diffractogram, which preserves the LTA type peaks of the zeolite together with the diffraction peaks of the MOF. By 30 electron microscopy the rough MOF shell is visible on the flat surface of the initial zeolite crystal (Figure 4). The hybrid product adsorbs a much smaller amount of C02 (Figure 7 and Table 3) than expected by its composition, thanks to the effect of the MOF shell. The pore hierarchy (Figure 5) of the hybrid material reduces the adsorption of C02 in the zeolite of the nucleus when coated with an MOF shell
    35 low surface adsorption of this gas.
    Example 2: Synthesis of LT AlMOF sodium zeolite hybrid material 2.4 g of commercial zeolite 4A (Z4A 10, Na-L TA, Si / Al ratio = 1) were dispersed in 25 mL of distilled water and stirred for 10 min. then 1.1 g of TPA
    5 to the dispersion of zeolite in water and stirred for 72 h at 40 ° C. The reaction mixture had approximately the following molar composition: 2 Al: 1 TPA: 200 H20. The solid product obtained was filtered and washed with distilled water and dimethylsulfoxide (DMSQ) and dried at 200 ° C for 24 h.
    The sodium starting zeolite was varied with respect to Example 1 as compensation cation, mixing order, temperature and reaction time. The hybrid solid product obtained had a higher percentage of MOF than Example 1, approximately 25% w / w MOF and 75% w / w zeolite, due to the lower aluminum / ligand molar ratio (2: 1). The X-ray diffraction spectrum is shown in the
    Figure 2. The NMR spectra of the hybrid material of this Example together with those of Zeolite 4A for comparison (Figure 12) show an affectation of part of the silicon and aluminum atoms of the zeolite core due to the creation of ligand bonds organic-aluminum at the zeolite-MOF interface of the hybrid material.
    Example 3: Synthesis of aluminosilicate / MOF hybrid material 0.8 g of commercial zeolite 4A (Z4A 10, Na-L TA, Si / Al ratio = 1) was dispersed in 18 mL of distilled water and stirred for 10 min. they then added 0.9 g of TPA to the dispersion of zeolite in water and stirred for 72 h at 40 ° C. The reaction mixture had approximately the following molar composition: 0.75 Al: 1 TPA: 180 H20.
    The solid product obtained was filtered and washed with distilled water and DMF Y dried at 200 ° C for 24 h. The aluminiolligando molar ratio too low (0.75) results in total amorphousization of the nucleus, which is no longer zeolite but aluminosilicate.
    The MOF of the shell represents approximately 30% w / w in the final solid. The spectre
    X-ray diffraction is shown in Figure 2. Although the nucleus has now lost its crystallinity and remains as an amorphous aluminosilicate, the hybrid material maintains its core-shell conformation and the shell MOF remains anchored to the atoms of inorganic core aluminum and retains the properties described above, dependent on the starting zeolite on which it grows; namely a
    X-ray diffraction spectrum different from other MOFs in the art with this composition, a cubic crystalline system with unique cell lengths and intermetallic spacing around 1.09 and 0.55 nm and laminar morphology.
    Example 4: Synthesis of FAU XlMOF sodium zeolite hybrid material
    5 2.1 9 of zeolite X (ZEOCHEM® 13X, SilAI ratio = 1-1.5) were dispersed in 20 mL ofdistilled water and stirred for 10 min o 0.9 g of TPA was then added to thedispersion of zeolite in water and stirred for 72 h at room temperature. MixThe reaction presented approximately the following molar composition: 2 Al: 1 TPA:200 H20. The solid product obtained was filtered and washed with distilled water and DMF Yse dried
    10 to 200 oC for 24 h. The solid powder product obtained was calcined at 330 oC for 72 h.
    The porous hybrid material of the invention was manufactured, starting in this case from a less dense FAU type zeolite, with a Si / Al ratio of 1-1.5 higher than those in Examples 1 to 3 but maintaining the ratio aluminum / ligand molar of Example 2 in the reaction (2: 1). The zeolite 13X has a FAU structure of low Si / Al ratio. The high concentration of aluminum and Al-Al distances similar to those of the LTA type favor the surface crystallization of the MOF of the invention. The X-ray diffraction peaks of the MOF (in italics and highlighting) are observed in Table 1 and Figure 3.
    20 with those of the FAU type of the zeolite core.
    The X-ray diffraction spectra of the zeolite / MOF hybrid materials obtained in Example 1 (from LTA type zeolite, columns 1 to 3) and Example 4 (from FAU type zeolite, columns 4 to 6) present the peaks of Table 1. Its relative intensity (1/10) is calculated from the peak with the maximum intensity, which receives the value of
    100: strong (F> 85), semi-strong (60 <SF <85), medium (40 <M <60), semi-weak (15 <SD <40), weak (0 <15). Peaks in italics correspond to the diffraction of the MOF shell present in the hybrid solid.
    30 Table 1
    2'Theta [') d [nm)1/1 02'Theta [']d [n m]10
    7.18 1,231F6.181,428F
    8, 07 1,089D 8, 071,089M
    10.16 0.870M10.1 10.873M
    12.45 16.09
    16.18 18.11
    21.65 23.97 26.09 27.09 29.92 30.80 32.52 34.15
    0.710 0.550
    0.548 0.489
    0.41 0 0.371 0.341 0.329 0.298 0.290 0.275 0.262 SDSD
    D
    D
    SD
    M
    D
    M SDDDSD
    11, 86 15.60 16.18 18.11 20.29 23.57 26.95 31.29
    0.745 0.566
    0.548 0.489
    0.435 0.375 0.328 0.282
    M
    SF MSFMSFSF
    M
    • Tolerances of ± 0.1 ° Y ± 0.01 nm.
    • Difractogram obtained with Cu Ka1 radiation source (A = O, 15406 nm).
    5 The hybrid material obtained shows a distribution of pores composed of those of the FAU type zeolite (0.8 nm) and the MOF, with 1.4 nm micropores and mesopores corresponding to the spaces between the sheets of material (Figure 5) . It presents a hierarchical micro-and mesoporosity derived from its core-shell composition.
    Example 5: Synthesis of FAU Y / MOF sodium zeolite hybrid material 1.8 g of zeolite Y (Zeolyst International CBV100, Si / Al ratio = 2.5) were dispersed in 10 mL of distilled water and stirred for 10 min. They then added 0.5 g of TPA to the dispersion of zeolite in water and stirred for seven days at 40 ° C. The reaction mixture had approximately the following molar composition: 2 Al: 1 TPA: 200
    15 H20. The solid product obtained was filtered and washed with distilled water and DMSO and dried at 200 ° C for 24 h.
    With the same aluminum / ligand ratio and starting from a FAU-type zeolite, as in Example 4, and even with higher reaction time and temperature, it was not possible to react the organic ligands with the zeolite aluminum atoms or therefore obtain the porous hybrid solid. This is because the Si / Al ratio of the starting zeolite means too low concentration of aluminum atoms,
    that will be separated by interatomic distances that do not allow the anchoring of organic ligands at the aluminum-aluminum distances described. A Si / Al relationship
    of 2.5 the upper limit of the range for the initial zeolite of the process of the invention can be considered.
    Example 6: Synthesis of LTAlMOF sodium zeolite hybrid materials
    1.0 g of commercial zeolite 4A (Z4A 10O, Na-L TA, Si / Al ratio = 1) was dispersed in 10 mL of distilled water and stirred for 10 min. Then 0.5 g of 2-aminoterephthalic acid was added (CSH7N04, 99% purity, Sigma Aldrich), 0.32 g of fumaric acid (C4H40 4, 99% purity, Sigma Aldrich) and 0.68 g of biphenyl-4,4'dicarboxylic acid (C14H l00 4, 97 % purity, Sigma Aldrich) to the dispersion of zeolite in water, and stirred for 7 days at 40 ° C. The reaction mixture had approximately the following molar composition: 2 Al: 1 ligand: 200 H20. The solid product obtained was filtered and washed with distilled water and dimethylformamide (DMF), and dried at 200 ° C for
    15-24 h.
    Different porous hybrid solid materials were obtained based on the three different bidentate organic ligands: fumarate, 2-aminoterephthalate and biphenyl-4,4'dicarboxylate. The different solubilities of the aqueous phase ligands give rise to
    20 different degrees of growth of the MOF structure. 10% w / w, 19% w / w and 6% w / w MOF, respectively, are calculated in the hybrid materials from the thermal degradation curves shown in Figure 6.
    Example 7: Disaggregation and separation of MOF
    An amount of 2.5 g of hybrid porous material manufactured under the conditions of Examples 1 to 4 was subjected to milling and dispersed in 200 mL of distilled water with the aid of ultrasound. The suspension obtained was allowed to decant for 5 min and the cloudy supernatant was collected, which was dispersed again in the same volume of distilled water. This operation was repeated at least 3 times with the same supernatant
    30 starting. The solid collected was then separated by centrifugation, and washed with more distilled water and DMF. The solid product was dried at 105 oC for 24 h and calcined at 330 oC for 72 h.
    The product purified under these conditions presented only the X-ray diffraction peaks 35 corresponding to the MOF, as shown in Figure 10 and Table 2.
    Figures 4 and 9 of electron microscopy show the morphology of the MOF shell of the invention, laminated and with a high aspect ratio. Once separated, this MOF of characteristics inherent to its growth on zeolite is especially suitable for applications as fillers in polymers due to its improved interaction
    5 organic-organic and its high aspect ratio.
    Table 2 shows the crystallographic properties of the disaggregated MOF structure.
    They correspond to a cubic crystalline system similar to the zeolite on which it has
    grown, with preferential laminar growth and a diffraction pattern of R-X in terms of
    10 to cell lengths and spacing unpublished and different from the MOF of the technique with this composition.
    Table 2
    Unit cell Blueprints2'Theta [0]d [n m]
    to 1,094 nm(1 OO)8.071,089
    b 1,094 nm(2 O O)16.180.548
    e a = ~ = v 1,094 nm 90 °(2 1 O)18.110.489
    Volume 1.3111 nm '
    15 • Tolerances of ± 0.1 ° Y ± 0.01 nm.
    • Difraclogram obtained with Cu Kal radiation source (A = O, 15406 nm).
    Table 3 and Figure 7 show a low CO2 adsorption of the disaggregated MOF (0.61 mmol'g-1), which results in a reduction of the adsorption of C02 in the core material
    Breastplate of the invention. The thermal stability of the disaggregated MOF is shown in Figure 8, somewhat lower than that shown by the MOF forming part of the shell of the hybrid material of the invention when anchored to the rigid zeolite core.
    Table 3 shows the amounts of CO2 absorbed at 25 oC and at a relative pressure
    25 PIPo = 0.016 And the specific surface area calculated by adjusting the isotherms (Figure 7) to the Langmuir isotherm by the various materials manufactured as described in the Examples. The "simulated Example 1" isotherm is obtained as a linear combination of the isotherms of zeolite 3A and the disaggregated MOF in 87/13% w / w ratio.
    Table 3
    zeolite 4A (IQE)zeolite 3A (IQE)Example 7Example 1Simulated Example 1
    VC02, ads Sesp, C02
    at PIPo = 0.016 Langmuir isotherm
    [mmol 'g "] [m2 'g "]
    3.99 3.10 0.61 1.16 2.69 403 343 105 197 312
    Example 8: Composite pOlimer-zeolite / MOF hybrid
    0.2 0.2 g of hybrid powder material obtained according to Example 2 was mixed with 0.2 g of solid commercial polysulfone pellet (PSF, Udel® 3500). This mixture was added to 3.6 g of chloroform (CHCb) and stirred for 24 h at room temperature to obtain complete dissolution of the PSF. At least 3 periods of 15 min of ultrasound dispersion were intercalated. The dispersion was then poured onto a Petri dish
    10 Steriplan® 13 cm in diameter and allowed to dry for 48 hours partially covered. The composite material obtained was treated under vacuum and 120 ° C for 24 h to obtain a flat sheet of compound between 50 and 150 µm thick.
    Figure 10 shows the X-ray diffraction spectrum of the composite material, with
    15 the crystalline peaks of the zeolite / MOF hybrid material (at 50% w / w) on the amorphous polymer bottom. The morphology, aspect ratio and mainly organic character of the MOF shell of the hybrid material of the invention manufactured according to Example 2 improves the adhesion and compatibility of the zeolite core with the polymer in the composite material, as seen in Figure 11, avoiding space formation
    20 non-selective voids in the separation of mixtures.
    Example 9: Hybrid material with additional metallic source in aqueous medium 0.70 g of AI (N03) J'9H20 was dissolved in 4 mL of distilled water as a metal precursor solution. 0.80 g of commercial zeolite 4A (Z4A 10, Na-L TA, was added,
    25 SitAI ratio = 1) to the previous solution to impregnate it with the metal precursor. At this point, zeolite 4A dissolved due to the acidity produced by the hydrolysis of aluminum. The metal precursor solution was dried at 80 ° C. 0.12 g of TPA was then dispersed in 12 mL of distilled water (organic ligand dispersion) then adding the dry product obtained from the metal precursor solution to the organic ligand dispersion. The mixture was reacted at 100 oC for 24 h. The solid product obtained was filtered and washed with distilled water and dimethylformamide (DMF) and dried at 200 ° C for 24 h.
    权利要求:
    Claims (13)
    [1]
    5 one.Inorganic-organic porous hybrid material, characterized in that it comprises a zeolite core with an Si / Al atomic ratio between 1 and a value of less than 2.5, and a metal-organic shell formed by a bidentate organic ligand covalently bonded to the aluminum atoms of said zeolite.
    [2]
    2. A hybrid material according to claim 1, characterized in that said core zeolite is a zeolite A type LTA, or a zeolite X ° Y type FAU.
    10 15 3.A hybrid material according to claim 1 or 2, characterized in that said bidentate organic ligand is selected from the group consisting of terephthalate, amino-terephthalate, diamino-terephthalate, bromoterephthalate, chloroterephthalate, fluoroterephthalate, iodoterephthalate, methyl-terephthalate, dimethyl terephthalate, nitroterephthalate, hydroxy-terephthalate, fumarate, imidazole, pyridine, pyrazole, tetrazol, naphthalene-2,6-dicarboxylate, biphen il-4, 4 '-dica rboxylate, 4,4'-bipyridine, 4,4'hexafluoroisopropylidene bisbenzo , 1,4,8, 11-tetraazacyclotetradecane.
    20 25 4. 5. 6.A hybrid material according to claim 3, characterized in that said organic ligand is terephthalate. A hybrid material according to any one of claims 1 to 4, characterized in that it has a microporosity of 1-2 nanometers and a mesoporosity of 2-10 nanometers in said metal-organic structure, in addition to the microporosity of the zeolite between 0, 1 -1 nanometer. A hybrid material according to any one of claims 1 to 5, characterized in that it has an X-ray diffraction spectrum comprising the peaks corresponding to the metal-organic structure:
    30 2, Theta [") 8.07 16.18Flat (1 O O) (2 O O)
    with an angle variability of ± ú, 1 0, obtained with a radiation source Cu Ka1, A = O, 15406 nm.
    [7]
    7. A hybrid material according to claim 6, characterized in that said X-ray diffraction spectrum comprises the peaks corresponding to the metal-organic structure:
    2'Theta rl Plano 8.07 (1 OO)
    [16]
    16.18 (2 OO) 18.11 (2 1 O)
    with an angle variability of ± 0.1 0, obtained with a radiation source Cu Ka1, A = O, 15406 nm.
    [8]
    8. Isolated metal-organic structure, characterized in that it has distances between 10 aluminum atoms of 1.09 ± 0.01 nm.
    [9]
    9. Method of obtaining an inorganic-organic porous hybrid material that includes a zeolite core and a shell of laminar metal-organic structure, characterized in that it comprises:
    15 react a bidentate organic ligand in the presence of a zeolite in aqueous dispersion at a temperature between 0 ° and 80 ° C for 1 to 28 days, in which said aqueous dispersion has a molar ratio to zeolite I ligand between 1 and 4, Yen that said zeolite has a Si / Al ratio between 1 and a value of less than 2.5, to obtain an inactive hybrid material and free organic ligand;
    20 separating and activating said inactive hybrid material to obtain the porous hybrid material.
    [10]
    10. A method according to claim 9, characterized in that said temperature is between 15 ° and 40 ° C.
    [11 ]
    eleven . A method according to claim 9 or 10, characterized in that said reaction takes place between 2 and 7 days.
    [12]
    12. A method according to any of claims 9 to 11, characterized
    30 because said activation is carried out by solvothermal dissolution or by thermal decomposition of said free organic ligand.
    [13]
    13. Porous inorganic-organic hybrid material, characterized in that it comprises an amorphous aluminosilicate core with an Si / Al atomic ratio between 1 and a value of less than 2.5, and a metal-organic structure shell formed by a ligand
    5 bidentate organic covalently bonded to the aluminum atoms of saidamorphous aluminosilicate.
    [14]
    14. Procedure for obtaining a porous organic-inorganic hybrid material that includes a core of an amorphous aluminosilicate and a shell of metal structure
    10 organic laminar, comprising: reacting a bidentate organic ligand in the presence of a zeolite in aqueous dispersion at a temperature between 0 ° and 80 ° e for 1 to 28 days, wherein said aqueous dispersion has a molar ratio To the zeolite / ligand between 0.5 and a value less than 1, and in which said zeolite has a Si / Al ratio
    15 between 1 and a value of less than 2.5, to obtain an inactive hybrid material and free organic ligand; separating and activating said inactive hybrid material to obtain the hybrid material
    porous.
    Use of the hybrid material of any one of claims 1 to 7 or 13, in a process of dehydration, separation or selective adsorption of gases or liquids.
    [16]
    16. Use according to claim 15, characterized in that said hybrid material is a
    component of a composite polymeric material or a mixed matrix membrane.
    [17]
    17. Use of the hybrid material of any of claims 1 to 7 or 13, in a catalytic process.
    18. Use of the metal-organic structure of claim 8, in a desiccant process
    or in a catalytic process.
    类似技术:
    公开号 | 公开日 | 专利标题
    ES2821475T3|2021-04-26|Hybrid porous organic-inorganic material, method of obtaining and uses
    Rungtaweevoranit et al.2017|Spiers Memorial Lecture: Progress and prospects of reticular chemistry
    Seoane et al.2013|Crystallization in THF: the possibility of one-pot synthesis of mixed matrix membranes containing MOF MIL-68 |
    Nik et al.2012|Functionalized metal organic framework-polyimide mixed matrix membranes for CO2/CH4 separation
    KR20140035354A|2014-03-21|Activated carbon-metal organic framework composite materials with enhanced gas adsorption capacity and process for the preparation thereof
    Naik et al.2016|PDMS membranes containing ZIF-coated mesoporous silica spheres for efficient ethanol recovery via pervaporation
    JP2005528204A|2005-09-22|Molded body containing metal organic framework
    Peralta et al.2012|Synthesis and adsorption properties of ZIF-76 isomorphs
    US8907114B2|2014-12-09|Method for preparing metal-organic framework crystallised and porous aluminium aromatic azocarboxylates
    KR20110019804A|2011-03-02|Method for preparing organic-inorganic hybrid nanoporous material, organic-inorganic hybrid nanoporous materials obtained by said method and use thereof
    US20120003475A1|2012-01-05|Synthesis Methodology to Produce Nano Metal Organic Framework Crystals
    US20150110712A1|2015-04-23|Crystalline molecular sieves and related structure-directing agents, methods and systems
    Chen et al.2011|Two-step synthesis, structure and adsorption property of a dynamic zinc phosphonocarboxylate framework
    Krachuamram et al.2021|Synthesis and characterization of NaX-type zeolites prepared by different silica and alumina sources and their CO2 adsorption properties
    Xue et al.2018|Large uniform copper 1, 3, 5-benzenetricarboxylate metal-organic-framework particles from slurry crystallization and their outstanding CO2 gas adsorption capacity
    JPWO2019202933A1|2020-07-09|GIS type zeolite
    JPH05254826A|1993-10-05|Synthesis of zeolite of mtt type, product obtained and its application in adsorption and catalyst
    Fallah et al.2019|Study of synthesis of mordenite zeolite/MIL-101 | metal–organic framework compounds with various methods as bi-functional adsorbent
    ES2681995B1|2019-06-28|AUTOMOBILE TRUCK FOR RESIN COLLECTION
    ES2718122A1|2019-06-27|AUTONOMOUS SYSTEM OF MARINE SALVAGE |
    KR20210025921A|2021-03-10|Novel aluminum-based metal-organic framework having a 3-dimensinal porous structure comprising 2 or more ligands, and preparation method therefor and uses thereof
    US9884308B2|2018-02-06|Metal-organic frameworks and process of preparing the same
    Lestari et al.2019|Composite material consisting of HKUST-1 and Indonesian activated natural zeolite and its application in CO2 capture
    EP2762228A1|2014-08-06|Ultraporous metal organic framework materials and method for their production
    KR101777831B1|2017-09-13|Reduction of oxides of nitrogen in a gas stream using molecular sieve ssz-28
    同族专利:
    公开号 | 公开日
    EP3595808B1|2020-08-05|
    ES2821475T3|2021-04-26|
    WO2018167078A1|2018-09-20|
    EP3595808A1|2020-01-22|
    ES2682056B1|2019-06-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US5292880A|1992-05-11|1994-03-08|Mobil Oil Corporation|Synthesis of caprolactam using catalysts|
    US5648508A|1995-11-22|1997-07-15|Nalco Chemical Company|Crystalline metal-organic microporous materials|
    FR2938540B1|2008-11-18|2017-08-11|Centre Nat Rech Scient|METHOD FOR THE HYDROTHERMAL PREPARATION OF CRYSTALLIZED POROUS ALUMINUM CARBOXYLATES OF THE "METAL-ORGANIC FRAMEWORK" TYPE|
    FR2951725B1|2009-10-23|2011-10-28|Inst Francais Du Petrole|NOVEL MIL-53-AI-N3 ORGANIC-INORGANIC HYBRID SOLID WITH AZO-FUNCTION AND PROCESS FOR PREPARING THE SAME|
    KR101663184B1|2009-12-15|2016-10-06|삼성전자주식회사|Hybrid porous material and method of preparing same|
    US20110138999A1|2009-12-15|2011-06-16|Uop Llc|Metal organic framework polymer mixed matrix membranes|
    WO2012042410A1|2010-09-30|2012-04-05|Basf Se|Process for preparing porous metal-organic frameworks based on aluminum fumarate|KR102289660B1|2019-06-26|2021-08-17|한국생산기술연구원|Composition for removing odor and method of preparing same|
    CN110280153B|2019-07-03|2021-10-08|郑州大学|Mixed matrix membrane for efficient separation of propylene/propane and preparation method thereof|
    CN110496603A|2019-07-09|2019-11-26|东北大学|A kind of synthetic method of copper-based flexibility MOF material|
    法律状态:
    2018-09-18| BA2A| Patent application published|Ref document number: 2682056 Country of ref document: ES Kind code of ref document: A1 Effective date: 20180918 |
    2019-06-28| FG2A| Definitive protection|Ref document number: 2682056 Country of ref document: ES Kind code of ref document: B1 Effective date: 20190628 |
    优先权:
    申请号 | 申请日 | 专利标题
    ES201730353A|ES2682056B1|2017-03-16|2017-03-16|HYBRID ORGANIC POROUS MATERIAL - INORGANIC, METHOD OF OBTAINING AND USES|ES201730353A| ES2682056B1|2017-03-16|2017-03-16|HYBRID ORGANIC POROUS MATERIAL - INORGANIC, METHOD OF OBTAINING AND USES|
    ES18711307T| ES2821475T3|2017-03-16|2018-03-13|Hybrid porous organic-inorganic material, method of obtaining and uses|
    PCT/EP2018/056267| WO2018167078A1|2017-03-16|2018-03-13|Organic - inorganic porous hybrid material, method for obtaining it and use thereof|
    EP18711307.1A| EP3595808B1|2017-03-16|2018-03-13|Organic - inorganic porous hybrid material, method for obtaining it and use thereof|
    [返回顶部]