• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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  • 优先权
    • 专利摘要:
    Crystalline material of a zeolitic nature IDM-1. The present invention relates to a microporous material of a zeolitic nature, called IDM-1, to its method of obtaining it and to its applications. Said material may be purely siliceous or incorporate different elements, either in lattice or extra lattice positions. The present invention is encompassed in the fields of crystalline silicas, zeolites and catalysts. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2748650A1
    申请号:ES202030156
    申请日:2020-02-24
    公开日:2020-03-17
    发明作者:Alonso Luis Angel Villaescusa
    申请人:Universidad Politecnica de Valencia；
    IPC主号:
    专利说明:

    [0001]
    [0002] Zeolitic crystalline material IDM-1
    [0003]
    [0004] The present invention relates to a microporous material of a zeolitic nature, called IDM-1, to its method of obtaining it and to its applications. Said material may be purely siliceous or incorporate different elements, either in lattice or extra lattice positions. The present invention is encompassed in the fields of crystalline silicas, zeolites and catalysts.
    [0005]
    [0006] BACKGROUND OF THE INVENTION
    [0007]
    [0008] Zeolites are variable composition microporous crystalline materials characterized by a crystalline network of TO4 tetrahedra (where T represents atoms with a formal oxidation state of 3 or 4, such as Si, Ti, Al, Ge, B and Ga, which share all their vertices giving rise to a three-dimensional structure containing channels and / or cavities of molecular dimensions.When some of the T atoms have an oxidation state of less than 4, the crystal lattice formed has negative charges that are compensated by the presence in the channels or organic or inorganic cation cavities These channels and cavities can also house organic molecules and H2O, so, in general, the chemical composition of zeolites can be represented by the following empirical formula: x (M i / nX02) yYÜ2 zR wH20
    [0009] where M is one or more organic or inorganic cations of charge n, X is one or more trivalent elements, Y is one or more tetravalent elements, generally Si, and R is one or more organic substances Although the nature of M, X, Y and R and the values of x, y, z, and w can, in general, be varied by post-synthesis treatments, the chemical composition of a zeolite (as it is synthesized or after its calcination) has a characteristic range of each zeolite and of their method of obtaining.
    [0010]
    [0011] On the other hand, a zeolite is also characterized by its crystalline structure, which defines a system of channels and cavities and gives rise to a specific X-ray diffraction pattern. In this way, zeolites differ from each other by their range of chemical composition. plus its X-ray diffraction pattern. Both characteristics (crystal structure and chemical composition) also determine the physicochemical properties of each zeolite and its applicability in different industrial processes.
    [0012] There are currently some 250 networks accepted by the IZA (International Zeolite Association, iza-online.org), which include both interrupted networks, in which not all the tetrahedra in the structure are connected, as well as materials that contain defects stacking in some crystallographic directions.
    [0013]
    [0014] Thus, the search for new properties through the discovery of new zeolitic structures is an area of technological interest.
    [0015]
    [0016] DESCRIPTION OF THE INVENTION
    [0017]
    [0018] The present invention relates to a microporous crystalline material of a zeolitic nature, called IDM-1, to its method of obtaining it and to its applications.
    [0019]
    [0020] In a first aspect, the present invention relates to a crystalline material characterized in that it is a zeolite
    [0021] • having a general chemical formula SiO (2-X) (OH) 2x, where x is equal to a value of between 0.02 and 0.12; Y
    [0022] * presents an X-ray diffractogram registered with a Bragg-Bentano geometry diffractometer with a fixed divergence slit and using the Kai and Ka2 Cu radiation, and which includes the following values of angles 20 (0), and relative intensities (l / lo) -100, where the relative intensities are represented by e, f, m, j and d, with values of e = 0-100, f = 80-100, m = 20-80, j = 0-80 and d = 0 -twenty:
    [0023]
    [0024]
    [0025]
    [0026]
    [0027]
    [0028] In the present invention, “zeolite or zeolitic material” is understood to mean microporous crystalline materials of variable composition characterized by a crystalline network of TO4 tetrahedra (where T represents atoms with a formal oxidation state of 3 or 4 that share their vertices giving rise to a structure three-dimensional containing channels and / or cavities of molecular dimensions. It is also possible that the material presents an interrupted network in which not all O atoms are connected to Silicon atoms and are part of Si-OH groups (silanols), since They are structural or due to the presence of connectivity defects.The appearance of the latter may vary depending on the synthesis method and its calcination or subsequent treatments and may play a role in its adsorption properties and have not been taken into account in the compositions expressed above.
    [0029]
    [0030] In the present invention, "relative intensity or (l / l) -100" is understood to be the ratio obtained by dividing the intensity obtained for an angle 20 in the x-ray diffraction diagram by the highest intensity obtained in said diagram and the result multiplied by 100, said operation is performed for all the intensities and independently in all the diagrams obtained, in such a way that each intensity of each diagram is in a range of Oa 100.
    [0031]
    [0032] In a preferred embodiment the crystalline material has a micropore volume, measured from the value of the volume of N2 adsorbed at P / P0 (relative pressure) 0.3 and its density in the liquid state, between 0.15 mL / g and 0 , 25 mL / g. The microporosity in crystalline materials provides regular channels and cavities of molecular size and this empty space distribution is different for each zeolite. Thus, they are able to act as molecular sieves and be used in highly selective separation processes. They are also important in catalysis, since these cavities act as microreactors capable of influencing the distribution of products, providing different selectivities depending on the zeolite used.
    [0033]
    [0034] In the present invention, "micropore" is understood as those pores of less than 2 nm in size. And “microporous material” is understood to be those materials that have pores of less than 2nm in size.
    [0035]
    [0036] In another preferred embodiment, the crystalline material has a mesopore volume, measured from the value of the volume of N2 adsorbed to P / P00.3 and its density in the liquid state, between 0.040 mL / g and 0.300 mL / g. Mesopore volume is calculated as the difference between the total adsorbed volume and the micropore volume. These mesopore sizes are suitable since they facilitate the access to the micropores of the reagents and the exit of the products. In addition, they are also suitable for so-called high-speed reactions in which smaller pore sizes such as micropores, due to their small size, are unsuitable for such reactions since the speed at which catalytic processes occur prevents the use of the possible active centers of the material due to steric impediments due to size.
    [0037]
    [0038] In the present invention, "mesopore" is understood as those pores of size between 2 nm and 50 nm. And “mesoporous material” is understood to be those materials that have pores between 2 nm and 50 nm in size.
    [0039]
    [0040] In another preferred embodiment of the crystalline material of the present invention, silicon is isomorphically substituted by an element selected from Al, B, Ga, Fe, Ti, Sn, Zn, V, and any combination thereof
    [0041]
    [0042] In another preferred embodiment of the crystalline material of the present invention the silicon is substituted by Al in a Si / AI ratio of more than 12. More preferably the value of the Si / AI ratio is more than 30. And even more preferably the value The Si / AI ratio is between 30 and 60. In this way the network acquires negative charges that are compensated by mobile and interchangeable cations in extra-lattice positions.
    [0043]
    [0044] In another preferred embodiment the crystalline material of the present invention silicon is substituted by Ti in a Si / Ti ratio of more than 10. More preferably the value of the Si / Ti ratio is more than 30. And even more preferably the value The Si / Ti ratio is between 30 and 60.
    [0045] Another aspect of the invention refers to the process for obtaining the crystalline material characterized in that it comprises the following steps
    [0046] a) adding to an aqueous solution of a dication (p-Phenylenedimethylene) bis (tripropylammonium) salt at least one source of silica; b) adding to the mixture obtained in step (a) a fluorine source F 'selected from hydrofluoric acid and a fluorine salt, more preferably NH4F, up to a pH of between 12 and 5, more preferably between 10 and 6 , and even more preferably between 9 and 7, homogenizing, where the molar ratio of the mixture is SIO2: a TF2: b H2O, where T represents the cation (p-Phenylenedimethylene) bis (tripropylammonium) and = 0.05- 2 and more preferably a = 0.2-1.5, and where b = 2-100, more preferably b = 5-50, and even more preferably b = 7 50, and still more preferably b = 7-17; Y
    [0047] c) the mixture is introduced into a digestion pump and left with or without stirring in an oven at a temperature of between 80 and 200 ° C, preferably between 130 and 180 ° C, for a period of between 1 h and 50 days;
    [0048] d) cooling the mixture and obtaining the solid by filtering or centrifuging, washing with water and drying,
    [0049] e) calcining in the presence of an oxidizing agent the dry product obtained in step (d) at a temperature of between 3000C and 10000C for a time of between 0.5 h and 2 days.
    [0050]
    [0051] Dication (p-Phenylenedimethylene) bis (tripropylammonium) (Figure 1) is the so-called organic structure directing agent. Through its molecular geometry and electronic density distribution, it organizes the silica joining the network, determining, to a large extent, the distribution of the empty space of the crystallized material when it is subsequently removed from the network.
    [0052]
    [0053] In a preferred embodiment of the process, the silicon source of step (a) is selected from among tetraethyl orthosilicate (TEOS), colloidal silica, amorphous silica and any other silica source, such as other alkoxides or soluble glasses.
    [0054]
    [0055] The calcination stage evicts the host agents from the network and provides empty space for the corresponding applications. Before this stage, the composition Of the uncalcined zeolites prepared in fluoride medium (as is the case), it usually contains the organic cations (T) with which it has been prepared occluded in the channels and fluoride anions (F), occluded in the gaps that the zeolites present in their structure. In general, the charges provided by the cation are compensated by fluoride anions and by the isomorphic substitution of elements in the oxidation state 4 by elements in the oxidation state 3
    [0056]
    [0057] In a preferred embodiment of the process, the dication (p-Phenylenedimethylene) bis (tripropylammonium) is found as (p-Phenylenedimethylene) bis (tripropylammonium) hydroxide, and is obtained by anion exchange from the corresponding halide.
    [0058]
    [0059] In another preferred embodiment of the process, alkoxides are used as the silica source, after step (a) and before step (b) and the obtained mixture is left to stand for a time of between 1h and 5 days. In a more preferred embodiment, during this period, agitation is applied, thus favoring both the hydrolysis of the silicon source in the reaction medium and the evaporation of both the ethanol generated in said hydrolysis and a certain amount of water. These amounts are known as the mass lost by evaporation (Am). The amount of water is readjusted to a H20: Si02 ratio of between 2 and 100, preferably between 5 and 50, and more preferably between 7 and 50, and even more preferably between 7 and 17.
    [0060]
    [0061] In another preferred embodiment of the process heating in a digestion pump of step (c) is selected from either a static autoclave or a stirring autoclave.
    [0062]
    [0063] In another preferred embodiment of the process, step (e) is replaced by a step in which the product obtained in step (d) is chemically treated to dislodge the organic compound from the structure.
    [0064]
    [0065] In another preferred embodiment of the process, step (e) is replaced by a step in which the product obtained in step (d) is photochemical treated to dislodge the organic compound from the structure.
    [0066]
    [0067] In another preferred embodiment of the process for obtaining the crystalline material for Obtaining the dicarthion (p-Phenylenedimethylene) bis (tripropylammonium) halide from step (a) comprises adding dropwise and in an ice bath tripropylamine to a solution of 1,4-bis (chloromethyl) benzene, refluxing and stirring for a time of between 3 h and 7 days and remove the solvent to obtain a solid and wash it.
    [0068]
    [0069] In another preferred embodiment of the process for obtaining the crystalline material for obtaining the dication (p-Phenylenedimethylene) bis (tripropylammonium) halide of step (a) it comprises dissolving 1,4-bis (chloromethyl) benzene in an organic solvent selected from between an alcoholic solvent, chloroform, acetontiril and tetrahydrofuran, more preferably ethanol, in an amount of between 1.5% and 2% by weight with respect to the organic solvent and tripropylamine is added drop by drop and in an ice bath, leaving reflux and stir for a time of between 3 h and 7 days and remove the solvent to obtain a solid that is washed with acetone.
    [0070]
    [0071] In another preferred embodiment of the process for obtaining the crystalline material in step (c), in addition, a source of an element selected from Al, B, Ga, Fe, Ti, Sn, Zn, V and any combination of the above is added, in a molar ratio between said element and silicon of between 0.001 and 0.2000, and preferably between 0.001 and 0.100.
    [0072]
    [0073] In a more preferred embodiment the precursor is aluminum and where said precursor is selected from among aluminum isopropoxide, aluminum nitrate or any other salt or aluminum alkoxide, in a molar ratio of between the precursor in its equivalent oxide form, the AI2O3 and SIO2 of between 0.0005 and 0.1000, and preferably between 0.0005 and 0.0500.
    [0074]
    [0075] The isomorphic substitution of Silicon by Aluminum incorporates a negative charge in the network. Thus, the maximum amount of Aluminum depends on the amount of charges provided by the organic cation inside.
    [0076]
    [0077] In a more preferred embodiment the precursor is titanium and where said precursor is selected from among titanium isopropoxide, tetraethyl orthotitanate, or any other titanium compound, in a molar ratio of between the precursor in its equivalent oxide form, TIO2 and the YES2 between 0.0005 and 0.1000, and preferably between 0. 0005 and 0.0500.
    [0078]
    [0079] A third aspect of the present invention relates to the use of the crystalline material previously described as a catalyst. In a more preferred embodiment the crystalline material where Si is replaced by AI is used as an acid catalyst.
    [0080]
    [0081] In a more preferred embodiment, the use of the crystalline material of the present invention is as a redox catalyst. It is achieved in two ways, (1) introducing redox active centers in the network, for example, Titanium and (2) taking advantage of the presence of reticular Aluminum to incorporate cationic species in extrareticular positions associated with that reticular aluminum (Cu, Co, Fe, etc).
    [0082]
    [0083] In a more preferred embodiment, the use of the crystalline material of the present invention is as a basic catalyst.
    [0084]
    [0085] Another aspect of the invention relates to the use of the crystalline material of the present invention for the separation of molecules as a molecular sieve or for diffusion differences through their empty space.
    [0086]
    [0087] Throughout the description and 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 emerge in part from the description and in part from the practice of the invention. The following examples and figures are provided by way of illustration, and are not intended to be limiting of the present invention.
    [0088]
    [0089] BRIEF DESCRIPTION OF THE FIGURES
    [0090]
    [0091] Fig. 1. Cation used as structure directing agent in the synthesis of zeolite IDM-1.
    [0092]
    [0093] Fig. 2. Diffractograms of the IDM-1 materials obtained in the zeolite experiments in examples (from top to bottom) 2, 3 and 4. The reflection at 28.44 corresponds to Si, used as an internal standard.
    [0094] Fig. 3. Adsorption and desorption isotherms of IDM-1 solids calcined at 550 0C prepared in Examples 2 and 3 (above and below, respectively).
    [0095]
    [0096] Fig. 4. SEM images of the IDM-1 zeolites obtained in examples 2, 3 and 4.
    [0097]
    [0098] Fig. 5. Diffractograms of the calcined solids obtained in the experiments of Example 6.
    [0099]
    [0100] EXAMPLES
    [0101]
    [0102] Next, the invention will be illustrated by tests carried out by the inventors, which shows the effectiveness of the product of the invention.
    [0103]
    [0104] Example 1.
    [0105] This example illustrates the preparation of (p-Phenylenedimethylene) bis (tripropylammonium) hydroxide (Figure 1).
    [0106]
    [0107] 5 g of 1,4-bis (chloromethyl) benzene, 300 g of ethanol are added to a 500 ml flask. About 24.5 g of tripropylamine is added to this mixture with stirring, drop by drop and in an ice bath. After 3 days at reflux and with stirring, the mixture is evaporated on the rotary evaporator until obtaining a white solid. After washing the obtained solid with acetone, the final obtained mass of product is 13.1 g. The nuclear magnetic resonance spectrum indicates that the solid obtained is dicathion (p-Phenylenedimethylene) bis (tripropylammonium) chloride.
    [0108]
    [0109] The hydroxide form of the dication is obtained by anion exchange using an exchange resin (Dowex Monosphere 550A hydroxyde form, Sigma-Aldrich)
    [0110]
    [0111] To a solution of 13 g of the previous product in 194.02 g of water, 100 g of resin are added and it is left stirring for 12 hours. After filtering the resin, the solution was titrated with HCI (aq.) Using phenolphthalein as an indicator, finding an exchange efficiency of 82%. This solution can be concentrated in the rotavapor for its use in synthesis of IDM-1, and its final concentration is obtained by means of a new titration.
    [0112] Example 2
    [0113] This example illustrates the preparation of purely siliceous IDM-1, using (p-Phenylenedimethylene) bis (tripropylammonium) hydroxide as the structural directing organic agent.
    [0114]
    [0115] To 7.17 of a solution containing 1.16 mmoles of (p-Phenylenedimethylene) bis (tripropylammonium) hydroxide per gram of solution, obtained in the manner described in Example 1, is added 3.47g of tetraethyl orthosilicate (TEOS ) and stirred, allowing the evaporation of the ethanol produced in the hydrolysis of TEOS together with water.
    [0116]
    [0117] When the loss by evaporation is 5.51 g, 0.35 g of HF (aq.) (48%, Aldrich) are added and homogenized by hand with the spatula. The obtained paste is introduced into an autoclave internally coated with polytetrafluoroethylene and remains at 150 ° C for 10 days. The autoclave is then cooled, the solid produced is filtered off, washed with water and dried at 600C.
    [0118]
    [0119] Finally, the product obtained and characterized is calcined at 550oC for 5 hours, thus obtaining a white solid that indicates that the calcination has dislodged the host agents from the network and has provided empty space for the corresponding applications and is characterized by X-ray diffraction, lower diagram of Figure 2, where presents an X-ray diffractogram registered with a Bruker diffractometer with Bragg-Bentano geometry with a fixed divergence slit and using the Kai and Ka2 radiation of Cu, comprising the following values of angles 20 (0), and relative intensities (l / lo) -100, where the relative intensities are represented by f, m and d, with values of f = 80-100, m = 20-80 and d = 0-20:
    [0120]
    [0121]
    [0122]
    [0123] Example 3
    [0124] This example illustrates the preparation of purely siliceous IDM-1, using the dication of (p-Phenylenedimethylene) bis (tripropylammonium) as the structure-directing organic agent in its (p-Phenylenedimethylene) bis (tripropylammonium) hydroxide form.
    [0125]
    [0126] Follow Example 2 exactly, except the loss by mass evaporation is 5.81 g and that the reaction time in the autoclave is 17 days at 1500C.
    [0127]
    [0128] It is characterized by X-ray diffraction, the intermediate diagram in Figure 2, where it presents an X-ray diffractogram registered with a Bruker diffractometer with a Bragg-Bentano geometry with a fixed divergence slit and using the Kai and Ka2 radiation of Cu comprising the following angle values 20 (0), and relative intensities (l / l) -100, where the relative intensities are represented by f, m and d, with values def = 80-100, m = 20-80 and d = 0-20:
    [0129]
    [0130]
    [0131]
    [0132] Example 4
    [0133] This example illustrates the preparation of purely siliceous IDM-1, using (p-Phenylenedimethylene) bis (tripropylammonium) hydroxide as the structural directing organic agent.
    [0134]
    [0135] Follow Example 2 exactly, except that the loss by evaporation is 6.11 g and the reaction time is 0 days in the autoclave at 1500C.
    [0136]
    [0137] It is characterized by X-ray diffraction, upper diagram of Figure 2, where it presents an X-ray diffractogram recorded with a Bruker-diffractometer with a Bragg-Bentano geometry with a fixed divergence slit and using the Kai and Ka2 radiation of Cu comprising the following angle values 20 (0), and relative intensities (l / l) -100, where the relative intensities are represented by f, m and d, with values def = 80-100, m = 20-80 and d = 0-20:
    [0138]
    [0139]
    [0140]
    [0141]
    [0142] Example 5
    [0143] N2 adsorption isotherms in the calcined samples of examples 2 and 3.
    [0144]
    [0145] The isotherms (Figure 3) show the characteristics of the presence of the microporous space of zeolites at low pressures. However, they also show a hysteresis cycle at relatively high pressures, suggesting the presence of mesoporous space. This mesoporous space is probably related to the presence of sheets of a few dozen nanometers thick of which their particles consist as can be seen in figure 4, where in addition, a single morphology is shown in each image, which supports that the IDM-1 material is not a mixture of particles with different structures. Table 1 summarizes the information obtained from the isotherms.
    [0146]
    [0147] Table 1. Micro and mesopore volumes of the calcined solids obtained in the corresponding examples.
    [0148]
    [0149]
    [0150]
    [0151]
    [0152] Example 6
    [0153] The same procedure is followed as for preparing the IDM-1 zeolite in Example 2 except for the addition of aluminum isopropoxide (AI (0-i-Pr) 3 together with the tetraethyl orthosilicate (TEOS) in the amounts reflected below:
    [0154]
    [0155] Table 2. Relevant amounts in the preparation of the IDM-1 zeolite in the presence of aluminum.
    [0156]
    [0157]
    [0158]
    [0159]
    [0160] They are characterized by X-ray diffraction, diagrams of figure 5 (IDM-1-AI above and IDM-1-AI2 below), where each of the materials presents an X-ray diffractogram registered with a Bruker diffractometer with Bragg-geometry. Bentane with a fixed divergence slit and using the Kai and Kci2 radiation of Cu and comprising the following values of angles 20 (0), and relative intensities (l / l) -100, where the relative intensities are represented by e, f , m, j and d, with values of e = 0-100, f = 80-100, m = 20-80, j = 0-80 and d = 0-20:
    [0161] . IDM-1-AI1
    [0162]
    [0163]
    [0164]
    [0165]
    [0166]
    [0167]
    权利要求:
    Claims (17)
    [1]
    1. A crystalline material characterized by being a zeolite
    • having a general chemical formula SiO (2-X) (OH) 2X, where x is equal to a value of between 0.02 and 0.12; Y
    * presents an X-ray diffractogram registered with a Bragg-Bentano geometry diffractometer with a fixed divergence slit and using the Kai and Ka2 Cu radiation, and which includes the following values of angles 20 (0), and relative intensities (l / lo) -100, where the relative intensities are represented by e, f, m, j and d, with values of e = 0-100, f = 80-100, m = 20-80, j = 0-80 and d = 0 -twenty:

    [2]
    2. Crystalline material according to claim 1, where it has a volume of micropore, measured from the value of the volume of N2 adsorbed at a relative pressure of 0.3 and its density in the liquid state, between 0.15 mL / g and 0 , 25 mL / g.
    [3]
    3. Crystalline material according to any of claims 1 to 2, where it has a mesopore volume measured from the value of the volume of N2 adsorbed at relative pressure 0.3 and its density in the liquid state, between 0.060 mL / g and 0.250 mL / g.
    [4]
    4. Crystalline material according to any of claims 1 to 3, wherein the silicon is isomorphically substituted by an element selected from Al, B, Ga, Fe, Ti, Sn, Zn, V, and any combination thereof.
    [5]
    5. Crystalline material according to claim 4, where the silicon is substituted by Al in a Si / AI ratio of more than 12, more preferably more than 30 and even more preferably the value of the Si / AI ratio is between 30 and 60 .
    [6]
    6. Crystalline material according to any of claim 4, where the silicon is substituted by Ti in a Si / Ti ratio of more than 10, more preferably more than 30 and even more preferably the value of the Si / Ti ratio is between 30 and 60.
    [7]
    7. Procedure for obtaining the crystalline material characterized in that it comprises the following steps
    a) adding to an aqueous solution of dication (p-Phenylenedimethylene) bis (tripropylammonium) halide at least one source of silica; b) adding to the mixture obtained in step (a) a source of fluorine F-selected from hydrofluoric acid and a fluorine salt, more preferably NH4F, up to a pH of between 12 and 5, more preferably between 10 and 6 , and even more preferably between 9 and 7, homogenizing, where the molar ratio of the mixture is YES2: a TF2: b H20, where T represents the cation (p-Phenylenedimethylene) bis (tripropylammonium) and = 0.05- 2 and more preferably a = 0.2-1.5, and where b = 2-100, more preferably b = 5-50, and even more preferably b = 7 50, and still more preferably b = 7-17;
    c) introduce the mixture obtained in (b) into a digestion pump and leave with or without stirring in an oven at a temperature of between 80 and 200 ° C, preferably between 130 and 180 ° C, for a time of between 1 h and 50 days;
    d) cooling the mixture obtained in (c) and obtaining the solid by filtering or centrifuging, washing with water and drying; Y
    e) calcine in the presence of an oxidizing agent the dry product obtained in step (d) at a temperature of between 3000C and 10000C for a time of between 0.5 h and 2 days.
    [8]
    8. Process for obtaining the crystalline material according to claim 7, where the dication (p-Phenylenedimethylene) bis (tripropylammonium) halide is found as (p-Phenylenedimethylene) bis (tripropylammonium) hydroxide, and is obtained by anion exchange to starting from the corresponding halide.
    [9]
    9. Process for obtaining the crystalline material according to any of claims 7 or 8, wherein after step (a) and before step (b) the mixture obtained is left to stand for a time of between 1h and 5 days, preferably for This rest applies agitation, up to an H20: Si02 ratio of between 2 and 100, preferably between 5 and 50, and more preferably between 7 and 50, and even more preferably between 7 and 17, by evaporation of the solvents.
    [10]
    10. Process for obtaining the crystalline material according to any of claims 7 to 9, wherein the heating in a digestion pump of step (c) is selected from among a static autoclave or a stirring autoclave.
    [11]
    11. Process for obtaining the crystalline material according to any of claims 7 to 10, where to obtain the dication (halide-p-Phenylenedimethylene) bis (tripropylammonium) halide of step (a) comprises adding drop by drop and in an ice bath Tripropylamine to a solution of 1,4-bis (chloromethyl) benzene, leaving under reflux and stirring for a time of between 3 h and 7 days and removing the solvent to obtain a solid and washing it.
    [12]
    12. Process for obtaining the crystalline material according to any of claims 7 to 11, wherein in step (b) a precursor of an element selected from Al, B, Ga, Fe, Ti, Sn, Zn, V is also added. and any combination of the above in a molar ratio between said element and silicon of between 0.001 and 0.2000, and preferably between 0.001 and 0.100.
    [13]
    13. Process for obtaining the crystalline material according to claim 12, wherein the precursor is aluminum and where said precursor is selected from between aluminum isopropoxide, aluminum nitrate or any other aluminum salt, in a molar ratio of between the precursor in its equivalent oxide form, AI2O3 and SIO2 of between 0.0005 and 0.1000, and preferably between 0, 0005 and 0.0500.
    [14]
    14. Use of the crystalline material described according to claims 1 to 6 as a catalyst.
    [15]
    15. Use of the crystalline material described according to claim 5, as an acid catalyst.
    [16]
    16. Use of the crystalline material described according to claim 4 or 5, as a redox catalyst.
    [17]
    17. Use of the crystalline material described according to claims 1 to 6 for the separation of molecules as a molecular sieve or for diffusion differences through their empty space.
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    公开号 | 公开日
    WO2021170890A1|2021-09-02|
    ES2748650B2|2020-07-17|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    ES2208087A1|2002-07-01|2004-06-01|Universidad Politecnica De Valencia|Electroluminescent material containing a conjugated polymer or earth metal complexes inside zeolites and porous materials and the preparation method thereof|
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    PCT/ES2021/070106| WO2021170890A1|2020-02-24|2021-02-15|Crystalline zeolite-type material|
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