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    • 专利摘要:
    Itq-62 material, its obtaining procedure and its use. In the present invention, a microporous crystalline material is presented, its method of obtaining and using it, having a composition: Xx2o3: yyo2: zzo2 Wherein x is a trivalent element such as al, b, fe, in, ga, cr, or mixtures thereof, where (and z)/x can take values between 9 and infinity; y corresponds to a tetravalent element such as ti, sn, zr, v or mixtures thereof, where z/y can take values between 10 and infinity; z corresponds to a tetravalent element selected from si and ge or mixtures thereof. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2650083A1
    申请号:ES201630820
    申请日:2016-06-16
    公开日:2018-01-16
    发明作者:Avelino Corma Canós；Fernando Rey García；Susana Valencia Valencia；Ángel Cantín Sanz；José Luis Jordá Moret；Pablo Javier BERECIARTUA PÉREZ；Raquel Simancas Coloma；Lindiane BIESEKI
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；Universidad Politecnica de Valencia；
    IPC主号:
    专利说明:

    5 Technical Field
    The present invention belongs to the technical field of microporous crystalline materials of zeolitic nature, useful as adsorbents, catalysts or catalyst components, for different processes. Background
    Zeolites are porous crystalline aluminosilicates that have found important applications as catalysts, adsorbents and ion exchangers. These zeolitic materials have well-defined structures that form channels and cavities in their interior of uniform size and shape that allow the adsorption of certain molecules, while preventing the passage into the glass of other molecules of size too large to diffuse through the pores This characteristic gives these materials molecular sieve properties. These molecular sieves may include, in addition to Si, other elements of group IIIA of the periodic system, all of them tetrahedrally coordinated. The negative charge generated by the tetrahedrally coordinated group IIIA elements in network positions is compensated by the presence in the cation crystal, such as alkaline or alkaline earth cations. These cations can be totally or partially exchanged for other types of cations using techniques
    25 ion exchange, thus being able to vary the properties of a given silicate by selecting the desired cations.
    Many zeolites have been synthesized in the presence of an organic molecule that acts as a structure directing agent. Organic molecules that act as structure directing agents (ADE) generally contain nitrogen in their composition, and can result in stable organic cations in the reaction medium.
    From a point of view of their possible applications, zeolites containing channel systems with different pore openings are especially desirable since they provide 35 selectivities in catalytic processes that cannot be obtained with materials with


    channels with identical openings in all of them. That is why, an important scientific activity has been developed in this regard. Description of the invention
    The present invention relates, on the one hand, to a microporous crystalline material, which may possess the following chemical composition in its calcined form: x X2O3: and YO2: z ZO2 where:
    10 X is a trivalent element selected from Al, B, Fe, In, Ga, Cr, and combinations thereof, preferably Al, B and combinations thereof; Y is a tetravalent element selected from Ti, Sn, Zr, V and combinations thereof, preferably Ti, Sn and combinations thereof; Z is a tetravalent element selected from Si, Ge and combinations thereof,
    15 preferably Si; the value of (y + z) / x is between 9 and infinity, preferably between 20 and infinity; the value of z / y is between 10 and infinity, preferably between 15 and infinity; and because the elements X, Y and Z are located in crystalline positions such as those described in table 1. In addition, said material may present a diffraction diagram such as
    20 described in table 3.
    From the given values it follows that the ITQ-62 crystalline material can be obtained in the absence of added trivalent elements.
    According to a preferred embodiment, the microporous crystalline material described in the present invention has been designated ITQ-62. The structure of this material has a microporous network consisting of two channel systems with openings formed by 8 and 12 TO4 tetrahedra in the same direction, which intersect with two other channel systems in the perpendicular plane, the material being accessible to molecules of interest in catalysis, in
    30 different processes, such as adsorption or separation processes. In addition, it presents smaller structural units with a cube shape, which are not accessible since they only have windows formed by four tetrahedra.
    The structure of the ITQ-62 zeolite can be described by its unit cell, which is the smallest structural unit 35 that contains all the structural elements of this material and whose projections along the crystallographic axes are shown in Figures 1 to 3 .


    Table 1 shows the list of atomic positions of all atoms in tetrahedral coordination in a unit cell. All these atoms are connected to each other through bridge oxygen that bind contiguous tetrahedral atoms two to two. In total, each unit cell contains 48 atoms in tetrahedral coordination, called T1, T2, T3, T4 up to
    5 T48, other than oxygen.
    According to a preferred embodiment, the described material possesses tetrahedral coordination atoms bonded through bridge oxygen atoms that connect adjacent tetrahedral coordination atoms, containing 48 atoms in tetrahedral coordination in
    10 its unit cell, called T1, T2, T3, T4 through T48, which are located in the crystallographic positions with Cartesian atomic coordinates x, y and z shown in Table 1.
    Table 1
    Atomic coordinates for)already)z (Å)
    T1 2.67.11.5
    T2 13.115.71.5
    T3 18.610.21.5
    T4 8.01.51.5
    T5 18.67.11.5
    T6 8.015.71.5
    T7 2.610.21.5
    T8 13.11.51.5
    T9 4.91.51.5
    T10 15.510.21.5
    T11 16.215.71.5
    T12 5.67.11.5
    T13 16.21.51.5
    T14 5.610.21.5
    T15 4.915.71.5
    T16 15.57.11.5
    T17 1.55.33.8
    T18 12.113.93.8
    T19 19.612.03.8


    T20 9.03.43.8
    T21 1.512.03.8
    T22 12.13.43.8
    T23 19.65.33.8
    T24 9.013.93.8
    T25 4.03.43.8
    T26 14.612.13.8
    T27 17.113.83.8
    T28 6.65.23.8
    T29 4.013.83.8
    T30 14.65.23.8
    T31 17.13.43.8
    T32 6.612.13.8
    T33 2.610.26.0
    T34 13.11.56.0
    T35 18.67.16.0
    T36 8.015.76.0
    T37 18.610.26.0
    T38 8.01.56.0
    T39 2.67.16.0
    T40 13.115.76.0
    T41 4.915.76.0
    T42 15.57.16.0
    T43 16.21.56.0
    T44 5.610.26.0
    T45 16.215.76.0
    T46 5.67.16.0
    T47 4.91.56.0
    T48 15.510.26.0
    Each of the T atoms in Table 1 is surrounded by four oxygen atoms as first neighbors and four other T atoms as second neighbors, so that the T atoms are connected two by two through bridge 5 oxygen forming bonds TOT The presence of cations or the different nature of T atoms


    they can modify the values presented in Table 1, so each crystallographic coordinate can be modified up to 1 Å of the value given in Table 1.
    The ITQ-62 zeolite has in its uncalcrated form an X-ray diffraction diagram whose 5 most important diffraction peaks are given in table 2, and in table 3 for its calcined form.
    Table 2
    2Ta Relative Intensity
    6.5 mf
    8.3 mf
    10.1 d
    11.5 md
    13.1 d
    13.5 md
    14.3 md
    15.4 F
    15.7 md
    17.5 md
    17.8 md
    19.6 md
    20.2 d
    21.6 m
    22.0 md
    22.9 md
    23.4 d
    24.3 md
    24.8 md
    25.2 md
    25.5 m
    26.0 md
     a (r 0.5)


    Table 3
    2Ta Relative Intensity
    6.6 mf
    8.4 F
    10.2 md
    11.7 md
    13.2 md
    14.4 md
    15.5 d
    15.9 md
    17.9 md
    19.9 md
    20.6 md
    21.6 d
    22.2 md
    23.1 md
    23.4 md
    23.7 md
    24.4 md
    24.9 md
    25.2 md
    25.6 md
    26.1 md
     a (r 0.5)
    These X-ray diffractograms were obtained with a Panalytical X'Pert Pro diffractometer
    5 equipped with a fixed divergence slit using the radiation KĮ of copper. The relative intensity of the lines is calculated as the percentage with respect to the most intense peak, and is considered very strong (mf) = 80-100, strong (f) = 60-80, average (m) = 40-60, weak ( d} = 20-40, and very weak (md) = 0-20 It should be borne in mind that the diffraction data listed for these samples as single or single lines, may consist of multiple
    10 overlaps or overlapping reflections that, under certain conditions, such as differences in chemical composition, may appear as resolved or partially resolved lines. Generally, changes in chemical composition can


    cause variations in the parameters of the unit cell and / or changes in the symmetry of the crystal, without a change in the structure. These modifications, which also include changes in relative intensities may also be due to differences in the type and amount of compensation cations, network composition, crystal size and shape of
    5 the same, preferential orientation or type of thermal or hydrothermal treatments suffered.
    According to a particular embodiment of the present invention, the value of x can be equal to zero, so it can have a chemical composition:
    10 and YO2: z ZO2 According to another particular embodiment, the value of y is equal to zero, so it can have a chemical composition:
    x X2O3: z ZO2 where the value of z / x can be between 9 and infinity, and more preferably 15 between 20 and infinity.
    According to another preferred embodiment, the material of the present invention, ITQ-62, may possess a chemical composition in its uncalcined form: n R: x X2O3: and YO2: z ZO2
    where:
    -  R is a structure directing agent, preferably said R contains nitrogen, and more preferably R is selected from a salt of an alkylammonium cation, an alkylammonium polycation, and combinations thereof.
    25-X is a trivalent element selected from Al, B, Fe, In, Ga, Cr and combinations thereof, preferably Al, B and combinations thereof;
    - Y is a tetravalent element selected from Ti, Sn, Zr, V and combinations thereof, preferably between Ti, Sn, and combinations thereof;
    - Z is a tetravalent element selected from Si, Ge and combinations thereof, preferably Si;
    - the value of n / (x + y + z) is between 1 and 0.001;
    According to a preferred embodiment, the directing agent of defined structure as R is an alkylammonium polycation, and more preferably is selected from hydroxide of N2, N2, N2, N5, N5, N5,3a, 6a-octamethyl octahydropentalene-2,5-diamonium, any of its salts and combinations thereof.



    From the values given according to this particular embodiment, it is clear that the ITQ-62 crystalline material can be synthesized in the absence of added trivalent elements. In addition, the n / z ratio may be between 1 and 0.001 in the ITQ-62 material as synthesized. The X-ray diffractogram of the zeolite in its synthesized form according to
    5 This particular embodiment presents the diffraction peaks that are listed in Table 2.
    According to a particular embodiment, x may be 0 and the ITQ-62 material may have a chemical composition: n R: y YO2: z ZO2
    10 where: the value of n / (y + z) can be between 1 and 0.001. According to another particular embodiment, and it can be 0 and the ITQ-62 material can have a chemical composition
    n R: x X2O3: z ZO2
    15 where: the value of z / x is between 9 and infinity, preferably between 20 and infinity, and the value of n / (x + z) is between 1 and 0.001. The present invention also relates to the process for obtaining the microporous crystalline material, ITQ-62, described above.
    According to the present invention, the ITQ-62 material preparation process may comprise at least the following steps:
    a) preparation of a mixture comprising at least H2O, a source of fluoride ions,
    An oxide or other source of the tetravalent material Z, a structure directing agent (R), a source of the trivalent element X, an oxide or other source of the tetravalent material Y, where the synthesis mixture has a molar composition of oxides in the following ranges: (YO2 + ZO2) / X2O3 greater than 2, preferably greater than 5. H2O / (YO2 + ZO2) between 1-50, preferably 2-30.
    30 R / (YO2 + ZO2) between 0.05-3.0, preferably between 0.05-1. F - / (YO2 + ZO2) between 0.01-3.0, preferably between 0.05-1. ZO2 / YO2 greater than 5, preferably between 8-25. SiO2 / GeO2 greater than 1, preferably greater than 5.
    35 b) keep the mixture at a selected temperature between 80 and 200 ° C until the crystals of the material form



    c) recovery of the crystalline material.
    According to a preferred embodiment, Z may be selected from Si, Ge and combinations thereof, preferably Si; X can be selected from Al, B, Fe, In, Ga, Cr and
    5 combinations thereof, preferably Al, B and combinations thereof and Y may be selected from Ti, Sn, Zr, V and combinations thereof, preferably between Ti, Sn and combinations thereof.
    According to another preferred embodiment, the structure directing agent R may be a
    The N-containing compound may preferably be selected from a salt of an alkylammonium cation, an alkylammonium polycation, or combinations thereof. And more preferably it may be an alkylammonium polycation, specifically R may be selected from N2, N2, N2, N5, N5, N5,3a, 6a-octamethyl octahydropentalene-2,5diamonium hydroxide, any of its salts and combinations thereof.
    The crystallization of the material can be carried out under stirring, in autoclaves at a temperature between 80 and 200 ° C, at times sufficient to achieve crystallization, for example between 12 hours and 90 days. At the end of the crystallization stage, the crystals of the material are separated from the mother liquor, and recovered as it has been
    20 indicated above. It should be taken into account that the components of the synthesis mixture can come from different sources, and depending on these, crystallization times and conditions may vary. In order to facilitate synthesis, crystals of the same material can be added
    or of this calcined material as seeds, in amounts of up to 15% by weight with respect to
    25 of the total oxides, to the synthesis mixture. These can be added before or during crystallization.
    According to a particular embodiment, this material could be prepared from a reaction mixture containing H2O, a source of fluoride anions, optionally an oxide or a
    30 source of the trivalent element X, such as Al and / or B, an oxide or a source of the tetravalent element or elements Z, such as Si, a source of Ge, such as GeO2 and an organic structure directing agent ( R) generally an organic cation, which may contain atoms other than C, H and N in its composition. Composite structure directing agents of the alkylammonium type, and more can be used
    Preferably, it is the hydroxide of N2, N2, N2, N5, N5, N5,3a, 6a-octamethylctahydropentalene2,5-diamonium, any of its salts or mixtures thereof.
    10 


    The composition of the reaction mixture has the following composition in terms of molar ratios of oxides:
    Reagents Useful range Preferred range
    5 (YO2 + ZO2) / X2O3 greater than 2 greater than 5H2O / (YO2 + ZO2) 1-50 2-30R / (YO2 + ZO2) 0.05-3.0 0.05-1.0F / (YO2 + ZO2) 0.01-3.0 0.05-1.0ZO2 / YO2 greater than 5 8-25
    10 SiO2 / GeO2 greater than 1 greater than 5
    According to a particular embodiment, the process for preparing the ITQ-62 material may further comprise a step of calcining the crystalline material obtained, calcination that can be carried out under vacuum, in air, nitrogen, hydrogen, argon, helium or any
    15 other gas and combinations thereof and at a temperature between 200 ° C and 1200 ° C, preferably between 200 and 1000 ° C for a time that may be between 2 minutes and 25 hours. The ITQ-62 material after calcination has a pore system free of organic matter, whose X-ray diffractogram shows the peaks listed in Table 3. During this calcination they can remain inside the channels or on the surface
    20 of the organic waste material from the structure director. These residues can be eliminated by a subsequent treatment of washing with water, any alcohol with less than six carbons or mixtures thereof, as well as by aqueous or alcoholic solutions of inorganic salts.
    According to a particular embodiment, said washing process or processes may comprise at least the following step: a) suspension of the material in a solution of a compound selected from an acid, a base, an ammonium salt, a sodium salt, of any metal alkaline, any alkaline earth metal or mixtures thereof. Preferably said solution is an aqueous, alcoholic, organic solution or mixture of both.
    The washing process is carried out at a temperature preferably between 0 ° C and 200 ° C. The diffraction diagram of the resulting material presents the characteristic diffraction peaks of the ITQ-62 material.
    In addition, the calcined ITQ-62 material or the calcined and washed ITQ-62 material may be subjected to one or more post-synthesis processes.
    eleven 


    Such treatments may preferably consist of treating the ITQ-62 with aqueous, alcoholic, organic solutions or mixtures thereof containing trivalent elements X, preferably selected from Al, Ga, B, Cr, Fe In, and mixtures thereof with the in order to incorporate them into the zeolitic network. This post-synthesis treatment can be performed
    5 at alkaline, acidic or neutral pHs at temperatures preferably between 0 and200 ° C for a preferred time between 1 hour to 15 days. The resulting material presents thecharacteristic diffraction peaks of this ITQ-62 material.
    Subsequently, any liquid solids separation technique can be recovered from the washed solid by filtration, centrifugation or 10 and can be subsequently activated by calcination at temperatures above 200 ° C.
    According to a preferred embodiment, the post-synthesis treatment may comprise at least:
    15 a) suspend the material in a solution preferably selected from an aqueous, alcoholic, organic solution and combinations thereof, containing at least one trivalent element X selected from Al, Ga, B, Cr, Fe, In or mixtures thereof ;
    b) recovery of the solid by filtration, centrifugation or any technique of separation of solids from liquids;
    c) activation of the material by calcination at temperatures above 200 ° C. According to a preferred embodiment said treatments are treatment of incorporation of trivalent metals so that they can increase the concentration of some element
    25 trivalent in the composition. On the other hand, the concentration and nature of the trivalent element can be modified with post-synthesis processes.
    According to a particular embodiment, the crystalline material with trivalent metals incorporated by post-synthesis treatments has a molar composition in its anhydrous state that is given by the equation: x X2O3: and YO2: z ZO2
    wherein X is a trivalent element such as Al, B, Fe, In, Ga, Cr or mixtures thereof, Y is a tetravalent element such as Ti, Sn, Zr, V or mixtures thereof, and Z corresponds to a 35 element selected from Si or Ge, or mixtures of them. The value of (y + z) / x is at least 9, and can be between 20 and infinity and the value z / y is at least 10. Of the


    Given values it is clear that ITQ-62 crystalline material can be synthesized in the absence of added trivalent elements. The X-ray diffractogram of the zeolite after post-synthesis treatment to incorporate trivalent elements in its structure presents the characteristic diffraction peaks of the ITQ-62 material. The organic component present in
    5 ITQ-62 material as synthesized can be removed, for example by extraction and / or byheat treatment by heating at a temperature above 200 ° C for a period oftime that can be between 2 minutes and 25 hours.
    Compensation cations in the material in its uncalcined form, or after a
    The heat treatment can be exchanged, if present, for other cations such as metal ions, H + and H + precursors such as NH4 +. Among the cations that can be introduced by ion exchange, those that can have a positive role in the activity of the material as a catalyst are preferred, and cations such as H +, rare earth cations, and metals of the metal are more specifically preferred.
    15 group VIII, as well as group IIA, IIIA, VAT, Va, IB, IIB, IIIB, IVB, VB, VIIB of the periodic table of the elements.
    It is also possible to introduce cations into the ITQ-62 zeolite network through post-synthesis treatments. These treatments consist of suspending the calcined ITQ-62 sample or
    20 calcined and washed in an aqueous, alcoholic, organic solution or mixtures of both containing the trivalent element that it is desired to incorporate at a temperature between 0 and 200 ° C for periods between 1 hour and 15 days.
    In order to prepare catalysts, the crystalline material of the present invention can
    25 combine intimately with hydrogenating-dehydrogenating components such as platinum, palladium, nickel, rhenium, cobalt, tungsten, molybdenum, vanadium, chromium, manganese, iron and combinations thereof. The introduction of these elements can be carried out in the crystallization stage, by exchange (if applicable), and / or by impregnation or by physical mixing. These elements can be introduced in their cationic form and / or from
    30 salts or other compounds that by decomposition generate the metal component or oxide in its appropriate catalytic form.
    The present invention also relates to the use of the material described above according to the present invention and obtained according to the process of the present invention described.
    35 previously in different processes, preferably as a catalyst and as an adsorbent. There are different processes where you can use the material of this
    13 


    invention as a catalyst, for example in hydrocarbon conversion processes, hydrocarbon dewaxing processes, alcohol conversion processes, alcohol conversion processes with less than four carbons in olefins, nitrogen nitrogen pollutant removal processes in gaseous or liquid streams, processes
    5 removal of nitrogen oxides from gaseous streams, elimination processesnitrogen oxides from gaseous streams in the presence of reducing gases where the gasreducer may be selected from ammonia, a hydrocarbon and combinations ofsame.
    Throughout the description and the claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and features of the invention will be derived partly from the description and partly from the practice of the invention. 15 Brief description of the figures
    Figure 1: View of the structure of the ITQ-62 zeolite along the a axis (oxygens omitted for clarity).
    20 Figure 2: View of the structure of the ITQ-62 zeolite along the b-axis (oxygens omitted for clarity).
    Figure 3: View of the structure of the ITQ-62 zeolite along the c axis (oxygens omitted for clarity).
    Figure 4: Rietveld tuning of the X-ray diffraction diagram of a sample of ITQ-62 calcined at 923K, measured using the copper's K alpha radiation. The dots show the experimental diagram. The line along them shows the calculated diagram for the proposed structure. The difference between the two is shown below. The lines
    30 verticals below the diagrams indicate the positions of the Bragg reflections.
    Figure 5: X-ray diffraction diagram of an example ITQ-62 material sample
    without calcining
    35 Figure 6: X-ray diffraction diagram of a sample sample of calcined ITQ-62 material.
    14 


    Figure 7: Schematic representation of the synthesis of the cation N2, N2, N2, N5, N5, N5,3a, 6-octamethyl octahydropentalene-2,5-diamonium.
    The present invention is illustrated by the following examples that are not intended to be limiting thereof.
    EXAMPLES Example 1. Preparation of the hydroxy structure directing agent of 10 N2, N2, N2, N5, N5, N5,3a, 6a-octamethyl octahydropentalene-2,5-diamonium.
    On a freshly prepared and strongly stirred solution of 5.6 g NaHCO3 in 360.0 mL of H2O (pH = 8) 48.2 mL (526.3 mmol) of dimethyl 1,3-acetonadicarboxylate are added followed by 23.0 mL (263.2 mmol) of 2.3 -butanodiona. The mixture remains with continuous stirring for 72 h. After this period the abundant precipitate obtained is filtered under vacuum and cooled in an ice bath, acidifying to pH = 5 with HCl (5%). The resulting crude is extracted three times with CHCl3, washing the organic phase set with brine and drying them over MgSO4. The mixture is filtered through a pleat filter and the filtrate obtained is concentrated in vacuo using it in the next step without major
    20 purification.
    The resulting solid is suspended in a mixture of 300.0 mL HCl (1M) and 30.0 mL of glacial acetic acid and then heated at reflux for 24 h (from an initial brown green to orange color). The resulting mixture is first cooled to room temperature and
    25 then in an ice bath, then extracted five times with CH2Cl2; drying the set of organic phases on MgSO4. The crude obtained is filtered through a pleat filter and concentrated in vacuo to obtain 32.7 g (75%) of the desired diketone. This diketone is transformed into the corresponding diamine, by a reductive amination reaction described below.
    350.0 mL of a 2.0 M solution of dimethylamine in MeOH is diluted with 200.0 mL of MeOH. The solution is cooled in an ice bath and a solution of 5N HCl in MeOH dripped onto it until pH = 7-8 is achieved. Then 16.7 g (100.7 mmol) of the previously prepared diketone dissolved in the minimum possible amount of MeOH are added,
    Followed by 10.2 g (161.2 mmol) of NaBH3CN. The temperature is allowed to rise to room temperature and is left with continuous stirring for 72 h.
    fifteen 


    The possible excess of NaBH3CN is neutralized by adding 5 N HCl in MeOH until pH = 2 is reached, displacing the HCN formed with a stream of N2 to a saturated solution in KOH. The mixture is partially concentrated in vacuo and the resulting crude is basified with a solution of KOH (25%) until pH = 12 is reached and saturated with NaCl. The crude oil obtained
    5 is extracted three times with CH2Cl2, drying the set of organic phases over MgSO4 ,. Beconcentrate in vacuo to obtain 21.4 g (95%) of the desired diamine.
    In a third step, the diamine is transformed into the corresponding diamonium by a quaternization reaction of tertiary amines with methyl iodide, as described below.
    21.6 of the previously desired diamine are dissolved in 100.0 mL of MeOH and slowly added thereto through a 45.0 mL (722.8 mmol) CH3I pressure funnel diluted in 40.0 mL of MeOH. Almost immediately a yellowish precipitate appears. The mixture remains with continuous stirring for 72 hours and then 45.0 ml (722.8 mmol) of CH3I are added, then continuing with continuous stirring until one week is completed. The precipitate obtained is filtered under vacuum by washing with abundant diethyl ether to provide 37.1 g of the desired quaternary ammonium salt. The filtrate is concentrated in vacuo and the viscous solid obtained is washed with abundant acetone, appearing a new
    20 precipitate which after filtering and drying under vacuum provides 2.0 g more of the ammonium salt (80%).
    Finally, this solid, after dissolving it in methanol, is converted into the corresponding hydroxide using an anion exchange resin in excess of 3: 1 molar resin, under stirring, for 12 hours.
    Example 2. Preparation of zeolite ITQ-62
    19.01 g of a solution of the structure directing agent described in the example are added
    30 4 (R (OH) 2) containing 0.27 equivalents of hydroxide in 1000 g. 3.46 g of tetraethylorthosilicate (TEOS) and 0.34 g of germanium oxide (GeO2) are then added. The mixture is left evaporating under stirring until complete elimination of the ethanol from the hydrolysis of the TEOS plus the amount of water necessary until reaching the final composition indicated. Finally, 0.37 g of ammonium fluoride (NH4F) dissolved in 2 is added
    35 g of H2O. The mixture is left evaporating under stirring to reach the final composition indicated. The composition of the gel is:
    16 


    SiO2: 0.2 GeO2: 0.3 R (OH) 2: 0.6 NH4F: 8.4 H2O.
    The mixture obtained is introduced into an autoclave provided with an internal polytetrafluoroethylene sheath and heated at 150 ° C for 17 days in an oven equipped with a rotation system.
    The X-ray diffractogram of the solid obtained by filtering, washing with distilled water and drying at 100 ° C is shown in Figure 5 and presents the list of the most characteristic peaks shown in Table 4.
    Table 4
    2T Relative Intensity
    6.5 100
    8.3 87
    10.1 19
    11.5 3
    13.1 22
    13.5 9
    14.3 3
    15.4 77
    15.7 5
    17.5 eleven
    17.8 16
    19.6 17
    20.2 32
    21.6 62
    22.0 8
    22.9 eleven
    23.4 twenty-one
    24.3 9
    24.8 fifteen
    25.2 eleven
    25.5 49
    26.0 7

    Example 3-Preparation of zeolite ITQ-62 in its calcined form.
    A solid prepared as described in Example 2 is introduced into a tubular oven 5 and calcined in a stream of dry air at 650 ° C for 5 hours to decompose the retained organic matter inside.
    The X-ray diffraction diagram of the calcined ITQ-62 zeolite is shown in Figure 6 and shows the most characteristic peaks shown in Table 5 and indicates that the material is stable during this process.
    Table 5
    2T Relative Intensity
    6.6 100
    8.4 61
    10.2 one
    11.7 4
    13.2 5
    14.4 2
    15.5 twenty-one
    15.9 2
    17.9 one
    19.9 2
    20.6 5
    21.6 18
    22.2 2
    23.1 3
    23.4 5
    23.7 4
    24.4 3
    24.9 4
    25.2 4
    25.6 8
    26.1 3

    Example 4-Preparation of zeolite ITQ-62
    13.33 g of a solution of the structure directing agent described in the example are added
    5 1 (R (OH) 2) containing 0.30 equivalents of hydroxide in 1000 g. 3.46 g of tetraethylorthosilicate (TEOS) and 0.17 g of germanium oxide (GeO2) are then added. The mixture is left evaporating under stirring until complete elimination of the ethanol from the hydrolysis of the TEOS plus the amount of water necessary until reaching the final composition indicated. Finally, 0.33 g of ammonium fluoride (NH4F) dissolved in 2 is added
    10 g of H2O. The mixture is left evaporating under stirring to reach the final composition indicated. The composition of the gel is:
    SiO2: 0.1 GeO2: 0.27 R (OH) 2: 0.55 NH4F: 7.7 H2O.
    The mixture obtained is introduced into an autoclave provided with an internal polytetrafluoroethylene sheath and heated at 150 ° C for 7 days in an oven equipped with a rotation system. The solid obtained by filtering, washing with distilled water and drying at 100 ° C, presents an X-ray diffraction diagram containing the characteristic peaks of the ITQ-62 material.
    Example 5. Preparation of zeolite ITQ-62
    14.93 g of a solution of the structure directing agent described in Example 1 (R (OH) 2) containing 0.27 equivalents of hydroxide in 1000 g are added. Then, 3.44 g of tetraethylorthosilicate (TEOS) and 0.084 g of germanium oxide (GeO2) are added. The mixture is left evaporating under stirring until complete elimination of the ethanol from the hydrolysis of the TEOS plus the amount of water necessary until reaching the final composition indicated. Finally, 0.3 g of ammonium fluoride (NH4F) dissolved in 2 g of H2O is added. The mixture is left evaporating under stirring to reach the final composition indicated. One is added
    0.05 g water suspension of ITQ-62 zeolite prepared as described in example 5. The gel composition is:
    SiO2: 0.05 GeO2: 0.26 R (OH) 2: 0.52 NH4F: 7.3 H2O.
    The mixture obtained is placed in an autoclave provided with an internal polytetrafluoroethylene sheath and heated at 150 ° C for 8 days in an oven equipped with a
    19 


    rotation system The solid obtained by filtering, washing with distilled water and drying at 100 ° C, presents an X-ray diffraction diagram containing the characteristic peaks of the ITQ-62 material. 5 Example 6. Preparation of zeolite ITQ-62
    14.92 g of a solution of the structure directing agent described in Example 1 (R (OH) 2) containing 0.27 equivalents of hydroxide in 1000 g are added. Then, 3.45 g of tetraethylorthosilicate (TEOS) and 0.17 g of germanium oxide (GeO2) are added. Be
    10 leave the mixture evaporating with stirring until complete elimination of the ethanol from the hydrolysis of the TEOS plus the amount of water necessary until reaching the final composition indicated. Finally, 0.33 g of ammonium fluoride (NH4F) dissolved in 2 g of H2O is added. The mixture is left evaporating under stirring to reach the final composition indicated. The composition of the gel is:
    SiO2: 0.1 GeO2: 0.27 R (OH) 2: 0.55 NH4F: 7.7 H2O.
    The mixture obtained is placed in an autoclave provided with an internal polytetrafluoroethylene sheath and heated at 175 ° C for 7 days in an oven equipped with a
    20 rotation system. The solid obtained by filtering, washing with distilled water and drying at 100 ° C, presents an X-ray diffraction diagram containing the characteristic peaks of the ITQ-62 material.
    Example 7. Preparation of zeolite ITQ-62
    33.58 g of a solution of the structure directing agent described in Example 1 (R (OH) 2) containing 0.27 equivalents of hydroxide in 1000 g are added. Then, 6.87 g of tetraethylorthosilicate (TEOS) and 0.17 g of germanium oxide (GeO2) and 0.081g of boric acid (H3BO3) are added. The mixture is left evaporating under stirring until complete.
    The removal of ethanol from the hydrolysis of TEOS plus the amount of water needed until the final composition indicated is reached. Finally, 0.64 g of ammonium fluoride (NH4F) dissolved in 2 g of H2O is added. The mixture is left evaporating under stirring to reach the final composition indicated. The composition of the gel is:
    35 SiO2: 0.05 GeO2: 0.02 B2O3: 0.27 R (OH) 2: 0.55 NH4F: 7.6 H2O.


    The mixture obtained is introduced into an autoclave provided with an internal polytetrafluoroethylene sheath and heated at 150 ° C for 14 days in an oven equipped with a rotation system. The solid obtained by filtering, washing with distilled water and drying at 100 ° C, presents an X-ray diffraction diagram containing the characteristic peaks of the
    5 ITQ-62 material.
    Example 8. Preparation of zeolite ITQ-62
    21.46 g of a solution of the structure directing agent described in the example are added
    10 1 (R (OH) 2) containing 0.23 equivalents of hydroxide in 1000 g. Next, 3.45 g of tetraethylorthosilicate (TEOS) and 0.18 g of germanium oxide (GeO2) and 0.033g of Aluminum Hydroxide (Al (OH) 3) are added. The mixture is left evaporating under stirring until complete elimination of the ethanol from the hydrolysis of the TEOS plus the amount of water necessary until reaching the final composition indicated. Finally, 0.34 is added
    15 g of ammonium fluoride (NH4F) dissolved in 2 g of H2O. The mixture is left evaporating under stirring to reach the final composition indicated. The composition of the gel is:
    SiO2: 0.1 GeO2: 0.012 Al2O3: 0.28 R (OH) 2: 0.56 NH4F: 7.8 H2O.
    The mixture obtained is introduced into an autoclave provided with an internal polytetrafluoroethylene sheath and heated at 150 ° C for 12 days in an oven equipped with a rotation system. The solid obtained by filtering, washing with distilled water and drying at 100 ° C, presents an X-ray diffraction diagram containing the characteristic peaks of the ITQ-62 material.
    Example 9. Preparation of zeolite ITQ-62
    13.33 g of a solution of the structure directing agent described in Example 1 (R (OH) 2) containing 0.3 equivalents of hydroxide in 1000 g are added. Then you
    30 add 3.46 g of tetraethylorthosilicate (TEOS) and 0.17 g of germanium oxide (GeO2). The mixture is left evaporating under stirring until complete elimination of the ethanol from the hydrolysis of the TEOS plus the amount of water necessary until reaching the final composition indicated. Finally, 0.18 g of a solution of hydrofluoric acid (48% HF by weight) is added. The composition of the gel is:


    SiO2: 0.1 GeO2: 0.27 R (OH) 2: 0.55 HF: 7.7 H2O.
    The mixture obtained is placed in an autoclave provided with an internal polytetrafluoroethylene sheath and heated at 150 ° C for 14 days in an oven equipped with a
    5 rotation system. The solid obtained by filtering, washing with distilled water and drying at 100 ° C,presents an X-ray diffraction diagram that contains the characteristic peaks of theITQ-62 material.
    Example 10. Refinement of the structure of an ITQ-62 zeolite according to the 10 Rietveld method.
    The structure of the ITQ-62 zeolite can be satisfactorily refined using the Rietveld method applied to an X-ray diffraction diagram obtained from a sample prepared as described in example 3. The spatial group, the parameters of the
    The refinement and atomic positions in crystallographic coordinates (x / a, y / b and z / c) of the ITQ-62 zeolite are shown in Table 6.
    Table 6
    Space group: C m m m
    20 Unit cell parameters: a = 21.1537 (18) angstroms b = 17.2740 (15) angstroms c = 7.5875 (6) angstroms alpha = beta = gamma = 90º
    25 Atomic positions: Si1 / Ge1 0.12141 (4) 0.41104 (4) 0.20259 (8) Si2 / Ge2 0.23315 (5) 0.08903 (4) 0.20277 (8) Si3 / Ge3 0.07274 (3) 0.30510 (7) 0.50000 Si4 / Ge4 0.19023 (3) 0.19941 (5) 0.50000
    30 O1 0.0779 (8) 0.3512 (9) 0.3160 (16) O2 0.1919 (3) 0.4074 (10) 0.2783 (17) O3 0.1943 (9) 0.1556 (8) 0.3108 (15) O4 0.1149 (6) 0.2267 (9) 0.50000 O5 0.1079 (13) 0.3850 (15) 0.0000
    35 O6 0.2233 (16) 0.1228 (12) 0.0000 O7 0.0999 (12) 0.5000 0.234 (4)
    22 


    O8  0.2082 (11)0.00000.237 (4)
    O9  0.00000.2757 (15)0.50000
    O10 0.25000.250000.50000

    权利要求:
    Claims (26)
    [1]
    1.- A microporous crystalline material, characterized in that it has the following chemical composition in its calcined form:
    5 x X2O3: and YO2: z ZO2where:X is a trivalent element selected from Al, B, Fe, In, Ga, Cr and combinations of thethemselves;And it is a tetravalent element selected from Ti, Sn, Zr, V and combinations of the
    10 themselves; Z is a tetravalent element selected from Si, Ge and combinations thereof; the value of (y + z) / x is between 9 and infinity; the value of z / y is between 10 and infinity; and because the elements X, Y and Z are located in crystalline positions as described in
    15 table 1.
    [2]
    2. A microporous crystalline material according to claim 1, characterized in that it has a diffraction diagram as described in Table 3.
    3. A microporous crystalline material according to claims 1 and 2, characterized in that the value of (y + z) / x is between 20 and infinity; the value of z / y is between 15 and infinity.
    [4]
    4. A microporous crystalline material according to claims 1 to 3, characterized in that 25 X is selected from Al, B and combinations thereof.
    [5]
    5. A microporous crystalline material according to claims 1 to 3, characterized in that Y is selected from Ti, Sn, and combinations thereof.
    6. A microporous crystalline material according to any of claims 1 to 5, characterized in that x is equal to zero and has the following chemical composition: y YO2: z ZO2
    [7]
    7. A microporous crystalline material according to any of claims 1 to 5, characterized in that y is zero and has the following chemical composition: x X2O3: z ZO2

    where the value of z / x is between 9 and infinity.
    [8]
    8. A microporous crystalline material according to one of claims 1 to 7, characterized in that it has a chemical composition in its uncalcined form:
    5 n R: x X2O3: z ZO2: and YO2where:R is a structure managing agent;the value of n / (x + y + z) is between 1 and 0.001;and because it has an x-ray pattern represented in table 2.
    [9]
    9. A microporous crystalline material according to claim 8, characterized in that the structure directing agent R contains N.
    [10]
    10. A microporous crystalline material according to claim 9, characterized in that R 15 is selected from a salt of an alkylammonium cation, an alkylammonium polycation, and combinations thereof.
    [11]
    11. A microporous crystalline material according to claim 10, characterized in that R is an alkylammonium polycation.
    [12]
    12. A microporous crystalline material according to claim 11, characterized in that R is selected from N2, N2, N2, N5, N5, N5,3a, 6a-octamethyl octahydropentalene-2,5diamonium hydroxide, any of its salts or combinations thereof .
    13. A microporous crystalline material according to any of claims 8 to 12, characterized in that x is equal to zero and by the following chemical composition: n R: y YO2: z ZO2 wherein the value of n / (y + z) It is between 1 and 0.001.
    14. A microporous crystalline material according to any of claims 8 to 12, characterized in that y is equal to zero and by the following chemical composition:
    n R: x X2O3: z ZO2 where the value of z / x is between 9 and infinity and the value of n / (x + z) is between 1 and 0.001.

    [15]
    15. A microporous crystalline material according to any of the preceding claims, characterized in that it has tetrahedral coordination atoms linked through bridge oxygen atoms that connect contiguous tetrahedral coordination atoms, containing 48 atoms in tetrahedral coordination in its unit cell, called T1 , T2, T3, T4
    5 to T48, which are located in crystallographic positions with coordinatesAtomic cartesian x, y and z shown in Table 1.
    [16]
    16. Method of preparing the material described according to claims 1 to 15, characterized in that it comprises at least the following steps:
    10 a) preparation of a mixture comprising at least H2O, a source of fluoride ions, an oxide or other source of tetravalent material Z, a structure directing agent (R), a source of trivalent element X, an oxide or Another source of the tetravalent material Y, where the synthesis mixture has a molar composition of oxides in the following ranges:
    15 (YO2 + ZO2) / X2O3 greater than 2 H2O / (YO2 + ZO2) between 1-50 R / (YO2 + ZO2) between 0.05-3.0 F / (YO2 + ZO2) between 0.01-3.0 ZO2 / YO2 greater than 5
    20 SiO2 / GeO2 greater than 1
    b) keep the mixture at a selected temperature between 80 and 200 ° C until the crystals of the material form.
    25 c) recovery of the crystalline material.
    [17]
    17. Method for obtaining a material according to claim 16, characterized in that Z is selected from Si, Ge and combinations thereof, X is selected from Al, B, Fe, In, Ga, Cr and combinations thereof e And is
    30 selected from Ti, Sn, Zr, V and combinations thereof.
    [18]
    18. Method for obtaining a material according to claim 17, characterized in that X is selected from Al, B, and combinations thereof.
    19. Procedure for obtaining a material according to claim 17, characterized in that Y is selected from Ti, Sn, and combinations thereof.
    26 

    [20]
    20. Process for obtaining a material according to claims 16 to 19, characterized in that the structure directing agent R is a compound containing N.
    [21]
    21. Method for obtaining a material according to claim 20, characterized5 because R is selected from a salt of an alkylammonium cation, a polycationalkylammonium or combinations thereof.
    [22]
    22. Process for obtaining a material according to claim 21, characterized in that R is an alkylammonium polycation.
    23. Method for obtaining a material according to claim 22, characterized in that R is selected from N2, N2, N2, N5, N5, N5,3a, 6-octamethyl octahydropentalene-2,5-diamonium hydroxide, any of its salts and combinations thereof.
    24. Method for obtaining a material according to any of claims 16 to 23, characterized in that it also comprises a step calcining the crystalline material obtained.
    20. Method for obtaining a material according to claim 24, characterized in that the calcination is carried out at a temperature between 200 and 1200 ° C.
    [26]
    26.- Procedure for obtaining a material according to any of claims 16 to 25, characterized in that it also comprises one or more post-synthesis processes.
    27. Method for obtaining a material according to claim 26, characterized in that said post-synthesis treatment comprises at least:
    a) suspending the material in a solution containing at least one trivalent element X 30 selected from Al, Ga, B, Cr, Fe, In or mixtures thereof;
    b) recovery of the solid by filtration, centrifugation or any liquid solids separation technique;
    C) activation of the material by calcination at temperatures above 200 ° C.

    [28]
    28.- Method of obtaining a material according to claim 27, characterized in that the solution of step a) is selected from an aqueous, alcoholic, organic solution and combinations thereof.
    5 29.- Use of a material described according to claims 1 to 15 and obtained according to theprocess described in claims 16 to 28 as catalyst.
    [30]
    30. Use of the material described according to claim 29 as a catalyst in hydrocarbon conversion processes.
    [31]
    31.- Use of the material described according to claim 29 as a catalyst in hydrocarbon dewaxing processes.
    [32]
    32.- Use of the material described according to claim 29 as catalyst in processes of conversion of alcohols.
    [33]
    33.- Use of the material described according to claim 29 as a catalyst in processes of conversion of alcohols with less than four carbons into olefins.
    Use of the material described according to claim 29 as a catalyst in processes of elimination of nitrogen contaminants in gaseous or liquid streams,
    [35]
    35.- Use of the material described according to claim 29 as a catalyst in processes of elimination of nitrogen oxides from gaseous streams.
    [36]
    36.- Use of the material described according to claim 29 as catalyst in processes of elimination of nitrogen oxides from gaseous streams in the presence of reducing gases.
    37. Use of the material described according to claim 36 wherein the reducing gas is ammonia.
    [38]
    38.- Use of the material described according to claim 36 wherein the reducing gas is at least one hydrocarbon.
    39. Use of a material described according to any of claims 1 to 15 and obtained according to the process described in claims 16 to 28 as an adsorbent.
    28 

    FIG. 1
    FIG. 2
    FIG. 3

    FIG. 4
    FIG. 5

    FIG. 6
    FIG. 7
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    引用文献:
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    FR2942467B1|2009-02-20|2011-08-12|Inst Francais Du Petrole|PROCESS FOR THE PREPARATION OF A STRUCTURAL TYPE ZEOLITHE ISV|
    EP2739567B1|2011-08-04|2017-01-04|ExxonMobil Chemical Patents Inc.|Emm-23 molecular sieve material, its synthesis and use|EP3640208B1|2017-06-13|2022-01-19|China Petroleum & Chemical Corporation|Molecular sieve scm-14, synthesis method therefor and use thereof|
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