 Material itq-55, preparation and use procedure (Machine-translation by Google Translate, not legally
专利摘要:
Itq-55 material, preparation and use procedure. The present invention relates to a microporous crystalline material of zeolitic nature which has, in the calcined state and in the absence of defects in its crystalline network manifested by the presence of silanols, the empirical formula X (m1/nxo2) : y yo2 : g geo2 : (1-g) sio2 In which M is selected from h, at least one N-charged inorganic cation, and a mixture of both, X is at least one chemical element of oxidation state 3, And it is at least one chemical element with oxidation state 4 other than si, X takes a value between 0 and 0.2, both included, And it takes a value between 0 and 0.1, both included, G takes a value between 0 and 0.5, both included, Which has been called itq-55, its procurement procedure and its use. (Machine-translation by Google Translate, not legally binding) 公开号:ES2554648A1 申请号:ES201430935 申请日:2014-06-20 公开日:2015-12-22 发明作者:Avelino Corma Canós；Fernando Rey García；Susana Valencia Valencia；Ángel CANTIN SANZ；Miguel Palomino Roca 申请人:Consejo Superior de Investigaciones Cientificas CSIC；Universidad Politecnica de Valencia； IPC主号:
专利说明:
ITQ-55 MATERIAL, PREPARATION AND USE PROCEDURE Technical Field The present invention belongs to the technical field of microporous crystalline materials of a zeolitic nature, useful as adsorbents, catalysts or catalyst components, for transformation processes and in particular for the adsorption and separation of organic and inorganic compounds in the gas or liquid phase. Background Zeolites are microporous crystalline materials formed by a network of TO4 tetrahedra that share all their vertices giving rise to a three-dimensional structure that contains channels and / or cavities of molecular dimensions. They are of variable composition, and T generally represents atoms with a formal oxidation state +3 or +4, such as Si, Ge, Ti, Al, B, Ga, ... When any of the T atoms has an oxidation state less than +4, the crystalline network formed has negative charges that are compensated by the presence in the channels or cavities of organic or inorganic cations. In said channels and cavities organic molecules and H2O can also be accommodated, so, in general, the chemical composition of the zeolites can be represented by the following empirical formula: x (M1 / nXO2): y YO2: z R: w H2O where M is one or more organic or inorganic charge cations + n; X is one or more trivalent elements; And it is one or several 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, yw can be varied by post-synthesis treatments, the chemical composition of a zeolite (as synthesized or after calcination) has a range characteristic of each zeolite and its method of obtaining. The crystalline structure of each zeolite, with a specific system of channels and cavities, gives rise to a characteristic X-ray diffraction pattern, which allows them to be differentiated from each other. 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 give rise to stable organic cations in the reaction medium. The mobilization of the precursor species during the synthesis of zeolites can be carried out in the presence of hydroxyl groups and basic medium, which can be introduced as hydroxide of the same ADE, such as tetrapropylammonium hydroxide in the case of the zeolite ZSM-5. Fluoride ions can also act as mobilizing agents in zeolite synthesis, for example in EP-A-337479 the use of HF in H2O at low pH as a silica mobilizing agent for the synthesis of zeolite ZSM-5 is described. Description of the Invention The present invention relates to a new microporous crystalline material of a zeolitic nature, identified as "ITQ-55 zeolite", to its preparation process and its use. This material, both in its calcined and synthesized form without calcining, has an X-ray diffraction pattern that is different from other known zeolitic materials and, therefore, is characteristic of this material. The present invention relates first to a microporous crystalline material of a zeolitic nature that has, in the calcined state and in the absence of defects in its crystalline network manifested by the presence of silanoles, the empirical formula x (M1 / nXO2): y YO2: g GeO2: (1-g) SiO2 in which M is selected from H +, at least one inorganic cation of charge + n, and a mixture of both, preferably selected from H +, at least one inorganic cation of charge + n selected from alkali metals, alkaline earth metals and combinations thereof, and a mixture of both, X is at least one chemical element of oxidation state +3, preferably selected from Al, Ga, B, Fe, Cr and mixtures thereof. And it is at least one chemical element with oxidation state +4 other than Si, preferably selected from Ti, Sn, Zr, V and mixtures thereof. x takes a value between 0 and 0.2, both included, preferably less than 0.1. and takes a value between 0 and 0.1, both included, preferably less than 0.05. g takes a value between 0 and 0.5, both included, preferably less than 0.33. and because the material, as synthesized, has an X-ray diffraction pattern with at least 2 valores angle values (degrees) and relative intensities (I / I0) shown in Table I, where I0 is the intensity of the most intense peak to which a value of 100 is assigned: Table I2 (degrees) 0.5 Intensity (I / I0) 5.8 d 7.7 d 8.9 d 9.3 mf 9.9 d 10.1 d 13.2 m 13.4 d 14.7 d 15.1 m 15.4 d 15.5 d 17.4 m 17.7 m 19.9 m 20.6 m 21.2 F 21.6 F 22.0 F 23.1 mf 24.4 m 27.0 m where d is a weak relative intensity between 0 and 20%, m is an average relative intensity between 20 and 40%, f is a strong relative intensity between 40 and 60%, and mf is a very strong relative intensity between 60 and 100% . The microporous crystalline material of zeolitic nature according to the invention, after being calcined to remove the organic compounds occluded therein, has an X-ray diffraction pattern with at least 2, angle values (degrees) and relative intensities ( I / I0) indicated in table II: Table II2 (degrees) 0.5 Intensity (I / I0) 6.2 d 7.8 d 8.0 d 9.8 mf 10.0 m 10.3 d 12.3 d 13.4 d 13.7 d 15.0 d 15.2 d 16.8 d 18.1 d 20.1 d 21.3 d 23.5 d 23.9 d 26.8 d where d, m, f and mf have the previous meaning. According to a preferred embodiment of the present invention, the microporous crystalline material of zeolitic nature ITQ-55 has, in the calcined state and in the absence of defects in its crystalline network manifested by the presence of silanoles, the empirical formula x (M1 / nXO2): y YO2: g GeO2: (1-g) SiO2 in which M is selected from H +, at least one inorganic cation of charge + n, preferably alkaline or alkaline earth, alkali metals, alkaline earth metals and combinations thereof, X is at least one chemical element of oxidation state +3, selected from Al, Ga, B, Fe, Cr and mixtures thereof, And it is at least one chemical element with oxidation state +4 other than Si, selected from Ti, Sn, V, Zr and mixtures thereof, x takes a value between 0 and 0.1, both included, and takes a value between 0 and 0.05, both included, g takes a value between 0 and 0.33, both included, and the material, as synthesized, has an X-ray diffraction pattern with at least the 2 angle values (degrees) and relative intensities mentioned above (table I) and said material has a pattern in a calcined state X-ray diffraction with at least 2 angle values (degrees) and relative intensities (I / I0) mentioned above (table II). According to a preferred embodiment of the present invention the microporous crystalline material of zeolitic nature ITQ-55 is a pure silica material, that is to say that in the general formula indicated above "x", "y" and "g" take the value 0. According to another preferred embodiment of the present invention the microporous crystalline material of zeolitic nature ITQ-55 is a material that can have in the general formula indicated above "x" equal to 0, "y" equal to 0 and "g" different from 0 According to another preferred embodiment of the present invention the microporous crystalline material of zeolitic nature ITQ-55 is a material, in whose general formula: X is selected from Al, Ga, B, Fe, Cr, and combinations thereof, and take the value 0, andg takes the value 0. Another preferred embodiment of the present invention is the microporous crystalline material of Zeolitic nature ITQ-55 is a material, it can have in its general formula: Y is selected from Ti, Zr, Sn, and combinations thereof, x takes the value 0, and g takes the value 0. According to another preferred embodiment the microporous crystalline material of zeolitic nature ITQ-55 is a material whose general formula: X is Al, Ga, B, Fe, Cr, and combinations thereof, Y is Ti, Zr, Sn, and combinations thereof and g takes the value 0. In a particular embodiment, the ITQ zeolitic microporous crystalline material 55 is a material whose general formula: X is Al, Ga, B, Fe, Cr, and combinations thereof, and takes the value 0, and g takes a value other than 0 and less than 0.33. Another particular embodiment shows the microporous crystalline material of zeolitic nature ITQ-55 in whose general formula: Y is Ti, Zr, Sn, and combinations thereof, x takes the value 0, and g takes a value other than 0 and less than 0.33. In another particular embodiment, the ITQ zeolitic microporous crystalline material 55 is a material whose general formula: X is Al, Ga, B, Fe, Cr, and combinations thereof, Y is Ti, Zr or Sn, and g takes a value other than 0 and less than 0.33. The X-ray diffraction patterns of the ITQ-55 material were obtained by the powder method using a fixed divergence slit of 1 / 8º and using the K radiation of the Cu. It should be noted that the diffraction data listed for this sample of ITQ-55 zeolite as single or single lines, may be formed by multiple overlaps or overlapping reflections that, under certain conditions, such as differences in crystallographic changes, may appear as resolved or partially resolved lines. Generally, crystallographic changes may include small variations in the parameters of the unit cell and / or changes in the symmetry of the crystal, without a change in structure. Thus, the positions, widths and relative intensities of the peaks depend to some extent on the chemical composition of the material, as well as on the degree of hydration and crystal size. In particular, when the network is composed exclusively of silicon oxide and has been synthesized in the presence of fluoride anions using the quaternary diammonium cation N2, N2, N2, N5, N5, N5,3a, 6a-octamethyl-octahydropentalen-2,5 -diamonium as the structure directing agent, the ITQ-55 zeolite as synthesized presents an X-ray diffraction pattern as shown in Figure 1. This diagram is characterized by angle values 2 (degrees) and relative intensities (I / I0) presented in table III, where d, m, f and mf have the same meaning as in table I. Table III 2 (degrees) 0.5 Intensity (I / I0) 5.78 d 7.68 d 8.91 d 9.31 mf 9.93 d 10.14 d 13.23 m 13.42 d 14.70 d 15.06 m 15.40 d 15.52 d 16.55 d 8 16.84 d 05.05 d 17.40 m 17.73 m 18.02 d 18.60 d 19.93 m 20.56 m 21.17 F 21.47 m 21.56 F 22.01 F 22.51 d 22.88 d 23.14 mf 24.05 d 24.42 m 24.62 d 25.28 d 25.49 d 26.61 d 26.95 m 27.95 d 28.24 d 28.59 d 28.93 d 29.21 d 29.68 d The X-ray diffraction pattern of the previous ITQ-55 sample after being calcined at 800 ° C to remove the internally occluded organic compounds is shown in the figure 2. This diffractogram is characterized by the values of angle 2 (degrees) and relative intensities (I / I0) shown in Table IV, where d, m, f and mf have the same meanings as in Table I. The comparison of the X-ray diffractograms corresponding to the ITQ-55 zeolite as synthesized and in a calcined state They show that the material is thermally stable. Table IV 2 theta (degrees) Intensity 6.18 d 7.80 d 7.98 d 9.82 mf 10.02 m 10.29 d 12.31 d 13.35 d 13.68 d 14.98 d 15.22 d 15.52 d 16.82 d 18.09 d 18.43 d 20.06 d 20.81 d 21.34 d 21.67 d 23.45 d 23.92 d 24.39 d 24.99 d 26.80 d 27.48 d 27.91 d 28.43 d 29.61 d Secondly, the present invention relates to a process for synthesizing the ITQ-55 microporous crystalline material. 5 According to the present invention, the process for synthesizing the crystalline material Microporous, ITQ-55, may comprise a reaction mixture comprising at least: one or more sources of SiO2 one or more sources of organic cation R, at least one source of anions selected from hydroxide anions, anions 10 fluoride and pampering combinations, and water is subjected to heating at a temperature between 80 and 200 ° C, and because the reaction mixture has a composition, in terms of molar ratios, between the intervals 15 R + / SiO2 = 0.01-1.0, OH- / SiO2 = 0-3.0 F- / SiO2 = 0-3.0(F- + OH -) / SiO2 = 0.01-3.0,H2O / SiO2 = 1-50. twenty According to a further particular embodiment of the process, the reaction mixture may further comprise one or more sources of GeO2 and because it has a composition, in terms of molar ratios, between the intervals GeO2 / SiO2 = 0 and 0.5R + / (SiO2 + GeO2) = 0.01-1.0,F - / (SiO2 + GeO2) = 0.0-3.0,OH - / (SiO2 + GeO2) = 0.0-3.0,(F- + OH -) / (SiO2 + GeO2) = 0.01-3.0H2O / (SiO2 + GeO2) = 1-50. According to a further particular embodiment of the process, the anion is preferably fluoride and the reaction mixture has a composition, in terms of molar ratios, between the ranges GeO2 / SiO2 = 0 and 0.5R + / (SiO2 + GeO2) = 0.01-1.0,F - / (SiO2 + GeO2) = 0.01-3.0,H2O / (SiO2 + GeO2) = 1-50. According to another particular particular embodiment of the process, the anion is preferably hydroxide, having a reaction mixture having a composition, in terms of molar ratios, between the intervals GeO2 / SiO2 = 0 and 0.5R + / (SiO2 + GeO2) = 0.01-1.0,OH - / (SiO2 + GeO2) = 0.01-3.0,H2O / (SiO2 + GeO2) = 1-50. According to a further particular embodiment of the process, the reaction mixture may further comprise at least one source of one or more trivalent elements X. In a particular embodiment, the reaction mixture comprises exclusively: one or several sources of SiO2, at least one source of one or more trivalent elements X one or several sources of organic cation R, at least one source of anions selected from hydroxide anions, fluoride anions and pampering combinations, and water, and it has a composition, in terms of molar relationships, between intervals R / SiO2 = 0.01-1.0,X2O3 / SiO2 = 0-0.1, excluding the value 0,OH- / SiO2 = 0-3.0F- / SiO2 = 0-3.0(OH- + F -) / SiO2 = 0.0-3.0, excluding the value 0, andH2O / SiO2 = 1-50. According to this embodiment, if you add at least one source of GeO2 to the reaction mixture, The composition, in terms of molar ratios, will be between the intervals GeO2 / SiO2 = 0 and 0.5, excluding the value 0 R / (SiO2 + GeO2) = 0.01-1.0, X2O3 / (SiO2 + GeO2) = 0-0.1, excluding the value 0, OH - / (SiO2 + GeO2) = 0-3.0 F - / (SiO2 + GeO2) = 0-3.0 (OH- + F -) / (SiO2 + GeO2) = 0.0-3.0, excluding the value 0 , and H2O / (SiO2 + GeO2) = 1-50. According to another particular embodiment, the reaction mixture comprises exclusively: one or several sources of SiO2, at least one source of one or more trivalent elements X one or several sources of organic cation R, one or several sources of hydroxide anions, and water, and has a composition, in terms of molar relationships, comprised between intervals R / SiO2 = 0.01-1.0, X2O3 / SiO2 = 0-0.1, excluding the value 0, OH- / SiO2 = 0-3.0, excluding the value 0, and H2O / SiO2 = 1-50. According to this embodiment, if at least one source of GeO2 is added to the reaction mixture, the composition, in terms of molar ratios, will be between the intervals GeO2 / SiO2 = 0 and 0.5, excluding the value 0 R / (SiO2 + GeO2) = 0.01-1.0,X2O3 / (SiO2 + GeO2) = 0-0.1, excluding the value 0,OH - / (SiO2 + GeO2) = 0-3.0, excluding the value 0, andH2O / (SiO2 + GeO2) = 1-50. According to a particular embodiment, the reaction mixture exclusively comprises: one or several sources of SiO2, at least one source of one or more trivalent elements X one or several sources of organic cation R, one or several sources of fluoride anions, and water, and has a composition, in terms of molar relationships, comprised between intervals R / SiO2 = 0.01-1.0, X2O3 / SiO2 = 0-0.1, excluding the value 0, F- / SiO2 = 0-3.0, excluding the value 0, and H2O / SiO2 = 1-50. According to this embodiment, if you add at least one source of GeO2 to the reaction mixture, The composition, in terms of molar ratios, will be between the intervals GeO2 / SiO2 = 0 and 0.5, excluding the value 0 R / (SiO2 + GeO2) = 0.01-1.0, X2O3 / (SiO2 + GeO2) = 0-0.1, excluding the value 0, F - / (SiO2 + GeO2) = 0-3.0, excluding the value 0, and H2O / (SiO2 + GeO2) = 1-50. According to another preferred embodiment, in the process described above, the reaction mixture may further comprise at least one source of another or other tetravalent elements Y, other than Si and Ge. According to a particular embodiment, the reaction mixture comprises exclusively: one or several sources of SiO2, at least one source of one or more tetravalent elements AND one or several sources of organic cation R, at least one source of anions selected from hydroxide anions, fluoride anions and pampering combinations, and water, and has a composition, in terms of molar relationships, comprised between intervals R / SiO2 = 0.01-1.0, YO2 / SiO2 = 0-0.1, excluding the value 0, OH- / SiO2 = 0-3.0, F- / SiO2 = 0-3.0 (OH- + F -) / SiO2 = 0 -3.0, excluding the value 0, and H2O / SiO2 = 1-50. According to this embodiment, if at least one source of GeO2 is added to the reaction mixture, the composition, in terms of molar ratios, will be between the intervals GeO2 / SiO2 = 0 and 0.5, excluding the value 0 R / (SiO2 + GeO2) = 0.01-1.0,YO2 / (SiO2 + GeO2) = 0-0.1, excluding the value 0,OH - / (SiO2 + GeO2) = 0-3.0,F - / (SiO2 + GeO2) = 0-3.0(OH- + F -) / (SiO2 + GeO2) = 0-3.0, excluding the value 0, andH2O / (SiO2 + GeO2) = 1-50. According to another particular embodiment of the process, the reaction mixture comprises exclusively: one or several sources of SiO2, at least one source of one or more tetravalent elements AND one or several sources of organic cation R, one or several sources of hydroxide anions, and water, and has a composition, in terms of molar relationships, comprised between intervals R / SiO2 = 0.01-1.0, YO2 / SiO2 = 0-0.1, excluding the value 0, OH- / SiO2 = 0-3.0, excluding the value 0, and H2O / SiO2 = 1-50. According to this embodiment, if you add at least one source of GeO2 to the reaction mixture, the composition, in terms of molar relationships will be between the intervals GeO2 / SiO2 = 0 and 0.5, excluding the value 0 R / (SiO2 + GeO2) = 0.01-1.0, YO2 / (SiO2 + GeO2) = 0-0.1, excluding the value 0, OH - / (SiO2 + GeO2) = 0-3.0, excluding the value 0, and H2O / (SiO2 + GeO2) = 1-50. According to another particular embodiment of the process, the reaction mixture comprises exclusively: one or more sources of SiO2, at least one source of one or several tetravalent elements Y one or several sources of organic cation R, one or more sources of fluoride anions, and water, and has a composition, in terms of molar relationships, between intervals R / SiO2 = 0.01-1.0, YO2 / SiO2 = 0-0.1, excluding the value 0, F- / SiO2 = 0-3.0, excluding the value 0, and H2O / SiO2 = 1-50. According to this embodiment, if you add at least one source of GeO2 to the reaction mixture, the composition, in terms of molar relationships will be between the intervals GeO2 / SiO2 = 0 and 0.5, excluding the value 0 R / (SiO2 + GeO2) = 0.01-1.0, YO2 / (SiO2 + GeO2) = 0-0.1, excluding the value 0, F - / (SiO2 + GeO2) = 0-3.0, excluding the value 0, and H2O / (SiO2 + GeO2) = 1-50. According to another particular embodiment of the described process, the reaction mixture may comprise both one or several sources of various trivalent elements X as well as one or several sources of one or several tetravalent elements. According to a particular embodiment, the reaction mixture it comprises exclusively: one or several sources of SiO2, at least one source of one or more trivalent elements X at least one source of one or more tetravalent elements Y one or several sources of organic cation R, at least one source of anions selected from anions hydroxide, fluoride anions and combinations of pampering, and water, and the reaction mixture has a composition, in terms of molar ratios, between the intervals R / SiO2 = 0.01-1.0, X2O3 / SiO2 = 0-0.1, excluding the value 0, YO2 / SiO2 = 0-0.1, excluding the value 0, OH- / SiO2 = 0-3.0 F- / SiO2 = 0-3.0 (OH- + F -) / SiO2 = 0-3.0, excluding the value 0, and H2O / SiO2 = 1-50 According to this embodiment, if at least one source of GeO2 is added to the reaction mixture, the composition, in terms of molar ratios, will be between the intervals GeO2 / SiO2 = 0 and 0.5, excluding the value 0 R / (SiO2 + GeO2) = 0.01-1.0,X2O3 / (SiO2 + GeO2) = 0-0.1, excluding the value 0,YO2 / (SiO2 + GeO2) = 0-0.1, excluding the value 0,OH - / (SiO2 + GeO2) = 0-3.0F - / (SiO2 + GeO2) = 0-3.0(OH- + F -) / (SiO2 + GeO2) = 0-3.0, excluding the value 0, andH2O / (SiO2 + GeO2) = 1-50 According to another particular embodiment, the reaction mixture comprises exclusively: one or several sources of SiO2, at least one source of one or more trivalent elements X at least one source of one or several tetravalent elements Yone or several sources of organic cation R,one or several sources of hydroxide anions, andWater, and has a composition, in terms of molar relationships, comprised between intervals R / SiO2 = 0.01-1.0, X2O3 / SiO2 = 0-0.1, excluding the value 0, YO2 / SiO2 = 0-0.1, excluding the value 0, OH- / SiO2 = 0-3.0, excluding the value 0, and H2O / SiO2 = 1-50. According to this embodiment, if you add at least one source of GeO2 to the reaction mixture, The composition, in terms of molar ratios, will be between the intervals GeO2 / SiO2 = 0 and 0.5, excluding the value 0 R / (SiO2 + GeO2) = 0.01-1.0, X2O3 / (SiO2 + GeO2) = 0-0.1, excluding the value 0, YO2 / (SiO2 + GeO2) = 0-0.1, excluding the value 0, OH - / (SiO2 + GeO2) = 0-3.0, excluding the value 0, and H2O / (SiO2 + GeO2) = 1- fifty. According to another particular embodiment, the reaction mixture comprises exclusively: one or several sources of SiO2, at least one source of one or more trivalent elements X at least one source of one or more tetravalent elements Y one or several sources of organic cation R, a or several sources of fluoride anions, and water, and has a composition, in terms of molar relationships, comprised between intervals R / SiO2 = 0.01-1.0, X2O3 / SiO2 = 0-0.1, excluding the value 0, YO2 / SiO2 = 0-0.1, excluding the value 0, F- / SiO2 = 0-3.0 excluding the value 0, and H2O / SiO2 = 1-50. According to this embodiment, if you add at least one source of GeO2 to the reaction mixture, The composition, in terms of molar ratios, will be between the intervals GeO2 / SiO2 = 0 and 0.5, excluding the value 0 R / (SiO2 + GeO2) = 0.01-1.0, X2O3 / (SiO2 + GeO2) = 0-0.1, excluding the value 0, YO2 / (SiO2 + GeO2) = 0-0.1, excluding the value 0, F - / (SiO2 + GeO2) = 0-3.0 excluding the value 0, and H2O / (SiO2 + GeO2) = 1-50 . According to the procedure described above, the reaction mixture may further comprise a source of inorganic cations M of charge + n, selected from H +, at least one inorganic cation of charge + n selected from alkali metals, alkaline earth metals and combinations thereof , and a mixture of both, According to a preferred embodiment of the described process, the cation R may be N2, N2, N2, N5, N5, N5,3a, 6a-octamethyloctactahydropentalen-2,5-diamonium. In general, it can be said that the reaction mixture can have a composition, in terms of molar ratios, between the intervals GeO2 / SiO2 = 0 and 0.5,R2 + / (SiO2 + GeO2) = 0.01-1.0,Mn + / (SiO2 + GeO2) = 0-1.0OH - / (SiO2 + GeO2) = 0-3.0F - / (SiO2 + GeO2) = 0-3.0(F- + OH -) / (SiO2 + GeO2) = 0-3,X2O3 / (SiO2 + GeO2) = 0-0.1,YO2 / (SiO2 + GeO2) = 0-0.1, andH2O / (SiO2 + GeO2) = 1-50. According to a particular embodiment, the composition of the reaction mixture that results in obtaining the ITQ-55 material can be represented in general by the following formula with the values of the parameters indicated in terms of molar ratios: r R1 / p (OH): s M1 / nOH: t X2O3: u YO2: v F: g GeO2: (1-g) SiO2: w H2O where M is one or several inorganic charge cations + n; preferably alkaline or alkaline earth, X is one or more trivalent elements, preferably Al, B, Ga, Fe, Cr or mixtures thereof; Y is one or several tetravalent elements other than Si, preferably Zr, Ti, Sn, V or mixtures thereof; R is one or more organic cations, p is the cation charge or the average charge of the cations, preferably N2, N2, N2, N5, N5, N5,3a, 6a-octamethylooctahydropentalen-2,5-diamonium; F is one or more sources of fluoride ions, preferably HF, NH4F, or a mixture of both, and the values of g, r, s, t, u, v and w vary in the ranges: g = 0-0.5, preferably 0-0.33 r = ROH / SiO2 = 0.01-1.0, preferably 0.1-1.0 s = M1 / nOH / SiO2 = 0-1.0, preferably 0-0.2 t = X2O3 / SiO2 = 0-0.1, preferably 0-0.05 u = YO2 / SiO2 = 0-0.1, preferably 0-0.05 v = F / SiO2 = 0-3.0, preferably 0-2.0 w = H2O / SiO2 = 1-50, preferably 1-20 The components of the synthesis mixture can come from different sources, and depending on these the crystallization times and conditions may vary. Preferably the heat treatment of the mixture is carried out at a temperature between 110 and 200 ° C. The heat treatment of the reaction mixture can be carried out in static or with stirring of the mixture. Once the crystallization is finished, the solid product is separated by filtration or centrifugation and dried. Subsequent calcination at temperatures above 350 ° C, preferably between 400 and 1300 ° C, and more preferably between 600 and 1000 ° C, causes the decomposition of the organic residues occluded inside the zeolite and the exit thereof, leaving the zeolitic channels free. The source of SiO2 may be, for example, tetraethylorthosilicate, colloidal silica, amorphous silica and a mixture thereof. The fluoride anion can be used as a mobilizing agent for precursor species. The source of fluoride ions is preferably HF, NH4F or a mixture of both. The, or organic cations, represented by R, are added to the reaction mixture 5 preferably in the form of hydroxide, another salt, for example, a halide, and a mixture of hydroxide and another salt, that is, additionally, a source of alkaline, alkaline earth ions or mixture of both (M) can be added, in hydroxide form or salt form. Preferably, the organic cation R is N2, N2, N2, N5, N5, N5,3a, 6a-octamethyl Octahydropentalen-2,5-diamonium, and is preferably added in selected form among hydroxide, another salt and a mixture of hydroxide and another salt, preferably a halide. The organic cation N2, N2, N2, N5, N5, N5,3a, 6a-octamethyl-octahydropentalen-2,5-diamonium is synthesized following the process represented in the following scheme: In this process an aldol condensation reaction is carried out followed by a decarboxylation reaction between dimethyl 1,3-acetonadicarboxylate with 2,3-butanedione to give the corresponding diketone, 3a, 6a-dimethyltetrahydropentalen2.5 (1H, 3H) -Diona. The diketone is transformed into the corresponding diamine by means of a 20 reductive amination reaction in the presence of dimethylamine and using sodium cyanoborohydride as a reducer, giving rise to diamine, N2, N2, N5, N5,3a, 6ahexamethyloctactahydropentalen-2,5-diamine. This diamine is subsequently quaternized with methyl iodide to give the diiodide salt of N2, N2, N2, N5, N5, N5,3a, 6-octamethyl octahydropentalen-2,5-diamonium. 25 The dilakylammonium diode salt can be dissolved in water and exchanged to its hydroxide form using an anion exchange resin in hydroxide form. According to a particular embodiment of the process, an amount of microporous crystalline material, ITQ-55, of the present invention is added to the reaction mixture as a crystallization promoter in an amount between 0.01 and 20% by weight, preferably between 0.05 and 10% by weight with respect to the total of inorganic oxides added. In addition, the material produced by this invention can be pelletized according to known techniques. The present invention also relates to the use of the microporous crystalline material described above and obtained according to the process described above. The material of the present invention can be used as a catalyst or catalyst component in processes of transformation of organic compounds, or as an adsorbent in processes of adsorption and separation of organic compounds. For use in the processes mentioned above it is preferable that ITQ-55 is in its calcined form without organic matter inside. The ITQ-55 material used in these catalytic applications may be in its acid form and / or exchanged with suitable cations, such as H + and / or an inorganic cation of charge + n, selected from alkali metals, alkaline earth metals, lanthanides and combinations of they. The ITQ-55 material used in adsorption / separation processes may be in its purely siliceous form, that is, not containing elements other than silicon and oxygen in its composition. The ITQ-55 material used in adsorption / separation processes may be in the form of silica-germany, that is, not containing elements other than silicon, germanium and oxygen in its composition. The ITQ-55 material is particularly suitable for use as a selective CO2 adsorbent in the presence of hydrocarbons, preferably methane, ethane, ethylene and combinations thereof, in streams containing these gases, either as an adsorbent in powdered or pelletized form or in membrane shape According to a specific embodiment, the ITQ-55 material can be used for the separation of CO2 and methane. According to a specific embodiment, the ITQ-55 material can be used for the separation of CO2 and ethane. According to a specific embodiment, the ITQ-55 material can be used for the separation of CO2 and ethylene. According to another particular embodiment, the ITQ-55 material is particularly suitable for separation in adsorption processes of 1 or 2 carbon hydrocarbons, which contain these gases, either as an adsorbent in powdery or pelletized form or in the form of a membrane. According to a specific embodiment, the ITQ-55 material is used as a selective adsorbent of ethylene in the presence of ethane. According to another specific embodiment, the ITQ-55 material is used as a selective adsorbent of ethylene in the presence of methane. 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. Brief description of the figures Figure 1: represents the most characteristic peaks of the X-ray diffraction pattern of the purely siliceous ITQ-55 material, as synthesized, obtained according to example 2. Figure 2: Represents the most characteristic peaks of the X-ray diffraction pattern of the material of Example 2 in a calcined state. Figure 3: represents the most characteristic peaks of the X-ray diffraction pattern of the ITQ-55 material containing Al and Si in its composition, as synthesized, obtained according to example 4. Figure 4: represents the selectivity of the adsorption of CO2 over that of methane in the ITQ-55 material in its calcined form, obtained according to example 2. The selectivity is expressed as the ratio of the adsorption capacity obtained from the isotherms of pure gases. The present invention is illustrated by the following examples that are not intended to be limiting thereof. EXAMPLES Example 1. Preparation of dihydroxide N2, N2, N2, N5, N5, N5,3a, 6aoctamethyloctactahydropentalen-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 stage without further purification. The resulting solid is suspended in a mixture of 300.0 mL of HCl (1M) and 30.0 mL of glacial acetic acid and then heated at reflux for 24 h. The resulting mixture is cooled first to room temperature and 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, 3a, 6a-dimethyltetrahydropentalen-2.5 (1H, 3H) -dione. This diketone is transformed into the corresponding diamine by the procedure described below. 350.0 mL of a 1.0 M solution of dimethylamine in methanol are cooled in an ice bath and a solution of 5 N HCl in MeOH is dripped on them 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 maintained with continuous stirring for 72 h. 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 obtained is extracted three times with CH2Cl2, drying the set of organic phases over MgSO4. It is concentrated in vacuo to obtain 21.4 g (95%) of the desired diamine, N2, N2, N5, N5,3a, 6-hexamethyloctactahydropentalen-2,5-diamine. Subsequently, the diamine is transformed into the quaternary diamonds dication. To do this, 21.6 g of the diamine obtained above are dissolved in 100.0 mL of MeOH and added slowly, by means of a compensated pressure funnel, 45.0 mL (722.8 mmol) of CH3I 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 is added, continuing stirring until a week is completed. The precipitate obtained is filtered under vacuum by washing with abundant diethyl ether, providing 37.1 g of the desired quaternary ammonium salt in the form of iodide, N2 diiodide, N2, N2, N5, N5, N5,3a, 6a-octamethylctahydropentalen-2 , 5-devil. The filtrate is concentrated in vacuo and the viscous solid obtained is washed with abundant acetone and a new precipitate appears which, after filtration and drying under vacuum, provides 2.0 g more of the ammonium salt (80%). The cation iodide is exchanged for hydroxide using an ion exchange resin according to the following procedure: 20 g (44 mmol) of cation iodide (RI2) is dissolved in water. To the solution obtained is added 89 g of Dowex SBR resin and kept under stirring until the next day. Subsequently, it is filtered, washed with distilled water and a dihydroxide solution of N2, N2, N2, N5, N5, N5,3a, 6-octamethylctahydropentalen-2,5-diamonium (R (OH) 2) is obtained which is titrated with HCl (aq.), Using phenolphthalein as an indicator, obtaining an exchange efficiency greater than 92%. The final solution contains 0.47 equivalents of hydroxide per 1000 g of solution. Example 2. Preparation of zeolite ITQ-55. 6 g of a 40% aqueous solution of colloidal silica (Ludox AS-40) are added over 42.5 g of a dihydroxide solution of N2, N2, N2, N5, N5, N5,3a, 6a-octamethyloctahydropentalen2,5-diamonium (R (OH) 2) containing 0.47 equivalents of hydroxide in 1000 g. The mixture is left evaporating under stirring until complete removal of excess water until reaching the final composition indicated. Finally, a solution of 0.74 g of ammonium fluoride in 2.5 g of water is added. The composition of the gel is: SiO2: 0.25 R (OH) 2: 0.5 NH4F: 5 H2O. The mixture obtained is introduced into an autoclave provided with an internal polytetrafluoroethylene sheath and heated at 150 ° C for 10 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 1 and presents the list of the most characteristic peaks shown in Table III. The calcination at 800 ° C in air for 3 hours allows to eliminate the occluded organic species. The X-ray diffraction pattern of the calcined ITQ-55 zeolite is shown in Figure 2 and shows the most characteristic peaks that appear in Table IV and indicates that the material is stable during this process. Example 3. Preparation of ITQ-55 zeolite. 8 g of tetraethylorthosilicate (TEOS) are added over 40.8 g of a dihydroxide solution of N2, N2, N2, N5, N5, N5,3a, 6a-octamethyloctactahydropentalen-2,5-diamonium (R (OH) 2) containing 0.47 equivalents of hydroxide in 1000 g. 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, 0.77 g of a solution of hydrofluoric acid (50% HF by weight) is added. The gel composition is: SiO2: 0.25 R (OH) 2: 0.5 HF: 5 H2O. The mixture obtained is introduced into an autoclave provided with an internal polytetrafluoroethylene sheath and heated at 150 ° C for 10 days in an oven equipped with a rotation system. The solid obtained by filtering, washing with distilled water and drying at 100 ° C is ITQ-55. Example 4. Preparation of zeolite ITQ-55. 6 g of a 40% aqueous solution of colloidal silica (Ludox AS-40) are added over 42.5 g of a dihydroxide solution of N2, N2, N2, N5, N5, N5,3a, 6a-octamethyloctahydropentalen2,5-diamonium (R (OH) 2) containing 0.47 equivalents of hydroxide in 1000 g. Then 0.14 g of aluminum hydroxide (57% Al2O3) is added and the mixture is left under stirring until complete excess water is removed until the final composition indicated is reached. Finally, a solution of 0.74 g of ammonium fluoride in 2.5 g of water is added. The composition of the gel is: SiO2: 0.02 Al2O3: 0.25 R (OH) 2: 0.5 NH4F: 5 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 has the X-ray diffractogram shown in Figure 3 and indicates that it is ITQ-55 zeolite. Example 5. Preparation of ITQ-55 zeolite. 0.087 g of Ti (IV) tetraethoxide (TEOTi) are added over 8 g of tetraethylorthosilicate (TEOS). Next, 40.8 g of a dihydroxide solution of N2, N2, N2, N5, N5, N5,3a, 6a-octamethylctahydropentalen-2,5-diamonium (R (OH) 2) containing 0.47 equivalents of hydroxide in 1000 are added g. The mixture is left evaporating under stirring until complete elimination of ethanol from the hydrolysis of TEOS and TEOTi plus the amount of water necessary until the final composition indicated is reached. Finally, 0.77 g of a solution of hydrofluoric acid (50% HF by weight) is added. The composition of the gel is: SiO2: 0.01 TiO2: 0.25 R (OH) 2: 0.5 HF: 5 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 is ITQ-55. Example 6. Preparation of ITQ-55 zeolite. 6 g of a 40% aqueous solution of colloidal silica (Ludox AS-40) are added over 42.5 g of a dihydroxide solution of N2, N2, N2, N5, N5, N5,3a, 6a-octamethyloctahydropentalen2,5-diamonium (R (OH) 2) containing 0.47 equivalents of hydroxide in 1000 g. Then 0.1 g of H3BO3 are added and the mixture is left evaporating under stirring until complete removal of excess water until reaching the final composition indicated. Finally, a solution of 0.74 g of ammonium fluoride in 2.5 g of water is added. The composition of the gel is: SiO2: 0.02 B2O3: 0.25 R (OH) 2: 0.5 NH4F: 5 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 is ITQ-55 zeolite. Example 7. Preparation of zeolite ITQ-55. 8 g of tetraethylorthosilicate (TEOS) are added over 36.6 g of a dihydroxide solution of N2, N2, N2, N5, N5, N5,3a, 6a-octamethylctahydropentalen-2,5-diamonium (R (OH) 2) containing 0.53 equivalents of hydroxide in 1000 g. Then 0.0476 g of H3BO3 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. The composition of the gel is: SiO2: 0.01 B2O3: 0.25 R (OH) 2: 10 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 is ITQ-55. Example 8. Preparation of zeolite ITQ-55. 8 g of tetraethylorthosilicate (TEOS) are added over 36.3 g of a dihydroxide solution of N2, N2, N2, N5, N5, N5,3a, 6a-octamethyl octahydropentalene-2,5-diamonium (R (OH) 2) containing 0.532 equivalents of hydroxide in 1000 g. Then 0.805 g of 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. The composition of the gel is: SiO2: 0.2 GeO2: 0.25 R (OH) 2: 10 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 is ITQ-55. Example 9. Adsorption of CO2 at 30 ° C in the ITQ-55 material of example 2. The measurement of the CO2 adsorption capacity of the ITQ-55 material, prepared according to example 2, at 30 ° C and 9 bar corresponds to 2.96 mmol / g. Likewise, the value obtained after performing 20 adsorption / desorption cycles is 2.95 mmol / g, which demonstrates that the ITQ-55 material retains its adsorption capacity after a high number of cycles. Example 10. Adsorption of CO2 at 60 ° C in the ITQ-55 material of example 2. The measurement of the CO2 adsorption capacity of the ITQ-55 material, prepared according to example 2, at 60 ° C and 9 bar corresponds to 2.35 mmol / g. Example 11. Adsorption of methane at 60 ° C in the ITQ-55 material of example 2. The measurement of the methane adsorption capacity of the ITQ-55 material, prepared according to example 2, at 60 ° C and 9 bar corresponds to 0.22 mmol / g, after balancing for 24 hours at this temperature and pressure. Example 12. Adsorption of methane at 30 ° C in the ITQ-55 material of example 2. The measurement of the methane adsorption capacity of the ITQ-55 material, prepared according to example 2, at 30 ° C and 9 bar corresponds to 0.18 mmol / g after equilibrating for 24 hours at this temperature and pressure. The lower adsorption capacity under these conditions compared to that observed in example 5 indicates the low diffusion capacity of methane through the pores of the ITQ-55 zeolite. Example 13. Determination of the selectivity in the separation of CO2 and methane in the ITQ-55 material of example 2. The selectivity in separation of methane and CO2 has been estimated through the ratio of the adsorption values of the pure CO2 and methane isotherms at identical pressure and temperature. It is considered that the selectivity in the separation process will be all the better the higher the ratio between these values. The variation of this ratio with the gas pressure at different temperatures is shown in Figure 4. Example 14. Adsorption of ethane at 30 ° C in the ITQ-55 material of example 2. The measurement of the ethane adsorption capacity of the ITQ-55 material, prepared according to example 2, at 30 ° C and 9 bar corresponds to 0.14 mmol / g after balancing for 24 hours at This temperature and pressure. Example 15. Adsorption of ethene at 30 ° C in the ITQ-55 material of example 2. The measurement of the ethereum adsorption capacity of the ITQ-55 material, prepared according to example 2, at 30 ° C and 9 bar corresponds to 0.75 mmol / g after equilibrating for 24 hours at this temperature and pressure.
权利要求:
Claims (69) [1] 1. A microporous crystalline material of zeolitic nature characterized in that it has, in the calcined state and in the absence of defects in its crystalline network manifested by the presence of silanoles, the empirical formula x (M1 / nXO2): y YO2: g GeO2: (1-g) SiO2 in which M is selected from H +, at least one inorganic cation of charge + n, and a mixture of both, X is at least one chemical element of oxidation state +3, Y is at least one chemical element with oxidation state +4 other than Si, x takes a value between 0 and 0.2, both included, and takes a value between 0 and 0.1, both included, g takes a value between 0 and 0.5, both included, and because the material, as synthesized, has an X-ray diffraction pattern with at least 2 angle values (degrees) and relative intensities (I / I0): 2 (degrees) 0.5 Intensity (I / I0) [5] 5.8 d [7] 7.7 d [8] 8.9 d [9] 9.3 mf [9] 9.9 d [10] 10.1 d [13] 13.2 m [13] 13.4 d [14] 14.7 d [15] 15.1 m [15] 15.4 d [15] 15.5 d [17] 17.4 m [17] 17.7 m [19] 19.9 m [20] 20.6 m [21] 21.2 F [21] 21.6 F [22] 22.0 F [23] 23.1 mf [24] 24.4 m [27] 27.0 m where I0 is the intensity of the most intense peak to which a value of 100 is assignedd is a weak relative intensity between 0 and 20%,m is an average relative intensity between 20 and 40%,f is a strong relative intensity between 40 and 60%, andmf is a very strong relative intensity between 60 and 100%. [2] 2. A microporous crystalline material of zeolitic nature according to claim 1, characterized in that, in a calcined state, it has an X-ray diffraction pattern with at least 2 angle values (degrees) and relative intensities (I / I0 ): 2 (degrees) 0.5 Intensity (I / I0) [6] 6.2 d [7] 7.8 d [8] 8.0 d [9] 9.8 mf [10] 10.0 m [10] 10.3 d [12] 12.3 d [13] 13.4 d [13] 13.7 d [15] 15.0 d [15] 15.2 d [16] 16.8 d [18] 18.1 d [20] 20.1 d [21] 21.3 d [23] 23.5 d [23] 23.9 d [26] 26.8 d where d is a weak relative intensity between 0 and 20%, m is an average relative intensity between 20 and 40%, f is a strong relative intensity between 40 and 60%, and mf is a very strong relative intensity between 60 and 100%. [3] 3. A microporous crystalline material of zeolitic nature according to claim 1, characterized in that X is selected from Al, Ga, B, Fe, Cr and mixtures thereof. [4] Four. A microporous crystalline material of zeolitic nature according to claim 1, characterized in that Y is selected from Zr, Ti, Sn, V and mixtures thereof. [5] 5. A microporous crystalline material of zeolitic nature according to claim 1, characterized in that M is selected from H +, at least one inorganic cation of charge + n selected from alkali metals, alkaline earth metals and combinations thereof, and a mixture of both, [6] 6. A microporous crystalline material of a zeolitic nature according to claim 1, characterized in that "x" is 0, "y" is 0, and "g" is 0. [7] 7. A microporous crystalline material of a zeolitic nature according to claim 1, characterized in that "x" is 0, "y" is 0 and "g" is different from 0. [8] 8. A microporous crystalline material of zeolitic nature according to claim 1, characterized in that: X is Al, Ga, B, Fe, Cr, and combinations thereof, and takes the value 0, and g takes the value 0. [9] 9. A microporous crystalline material of zeolitic nature according to claim 1, characterized in that: Y is Ti, Zr, Sn, and combinations thereof, x takes the value 0, yg takes the value 0. [10] 10. A microporous crystalline material of zeolitic nature according to claim 1, characterized in that: X is Al, Ga, B, Fe, Cr, and combinations thereof, Y is Ti, Zr, Sn, and combinations thereof and g takes the value 0. [11] eleven. A microporous crystalline material of a zeolitic nature according to claim 1 or 2, characterized in that: X is Al, Ga, B, Fe, Cr, and combinations thereof, and takes the value 0, and g takes a value other than 0 and less than 0.33. [12] 12. A microporous crystalline material of zeolitic nature according to claim 1, characterized in that: Y is Ti, Zr, Sn, and combinations thereof, x takes the value 0, and g takes a value other than 0 and less than 0.33. [13] 13. A microporous crystalline material of a zeolitic nature according to claim 1 or 2, characterized in that: X is Al, Ga, B, Fe, Cr, and combinations thereof, Y is Ti, Zr or Sn, and g takes a value other than 0 and less than 0.33. [14] 14. A method for synthesizing the microporous crystalline material described in claims 1 to 13 characterized in that a reaction mixture comprising at least: one or more sources of SiO2 one or several sources of organic cation R, at least one source of anions selected from hydroxide anions, anions fluoride and pampering combinations, and water is subjected to heating at a temperature between 80 and 200 ° C, and because the reaction mixture has a composition, in terms of molar ratios, between the intervals R + / SiO2 = 0.01-1.0,OH- / SiO2 = 0-3.0F- / SiO2 = 0-3.0(F- + OH -) / SiO2 = 0.01-3.0,H2O / SiO2 = 1-50. [15] fifteen. A method according to claim 14, characterized in that a reaction mixture further comprises one or more sources of GeO2 and has a composition, in terms of molar ratios, between the intervals GeO2 / SiO2 = 0 and 0.5R + / (SiO2 + GeO2) = 0.01-1.0,F - / (SiO2 + GeO2) = 0.0-3.0,OH - / (SiO2 + GeO2) = 0.0-3.0,(F- + OH -) / (SiO2 + GeO2) = 0.01-3.0H2O / (SiO2 + GeO2) = 1-50. [16] 16. A process according to claims 14 and 15, characterized in that the anion is fluoride and because it has a composition, in terms of molar ratios, between the intervals GeO2 / SiO2 = 0 and 0.5R + / (SiO2 + GeO2) = 0.01-1.0,F - / (SiO2 + GeO2) = 0.01-3.0,H2O / (SiO2 + GeO2) = 1-50. [17] 17. A process according to claims 14 and 15, characterized in that the anion is hydroxide and because it has a composition, in terms of molar ratios, between the intervals GeO2 / SiO2 = 0 and 0.5R + / (SiO2 + GeO2) = 0.01-1.0,OH - / (SiO2 + GeO2) = 0.01-3.0, H2O / (SiO2 + GeO2) = 1-50. [18] 18. A method according to one of claims 14 to 17, characterized in that the reaction mixture further comprises at least one source of one or more trivalent elements X. [19] 19. A process according to claims 14 to 18, characterized in that the reaction mixture further comprises at least one source of another or other tetravalent elements Y, other than Si and Ge. [20] twenty. A process according to claims 14 to 19, characterized in that the source of organic cation R is N2, N2, N2, N5, N5, N5,3a, 6a-octamethyloctactahydropentalen-2,5-diamonium. [21] twenty-one. A process according to claim 20, characterized in that the organic cation R is added in selected form among hydroxide, another salt and a mixture of hydroxide and another salt. [22] 22 A process according to one of claims 14 to 21, characterized in that an amount of the microporous crystalline material is added to the reaction mixture as a crystallization promoter, in an amount comprised between 0.01 and 20% by weight with respect to the total of inorganic oxides added. [23] 2. 3. Use of the microporous crystalline material described in claims 1 to 13 and prepared according to the process described in claims 14 to 22 as a catalyst or catalyst component in processes of transformation of organic compounds. [24] 24. Use of the microporous crystalline material described in claims 1 to 13 and prepared according to the process described in claims 14 to 22 in separation processes of organic compounds. [25] 25. Use of the microporous crystalline material described in claims 1 to 13 and prepared according to the process described in claims 14 to 22 as adsorbent in adsorption processes of organic compounds. [26] 26. Use of the microporous crystalline material according to claim 25 as a selective adsorbent of CO2 in the presence of hydrocarbons. [27] 27. Use of the microporous crystalline material according to claim 26 characterized in that 5 hydrocarbons are selected from methane, ethane, ethylene and combinations thereof. Use of the microporous crystalline material according to claim 25 as adsorbent in adsorption processes of 1 or 2 carbon hydrocarbons. 10 [29] 29. Use of the microporous crystalline material according to claim 28 as a selective adsorbent of ethylene in the presence of ethane. [30] 30. Use of the microporous crystalline material according to claim 28 as a selective adsorbent of ethylene in the presence of methane. 0 5 101520253035 2 (degrees) FIG. one Accounts 10000 0 0 5 101520253035 2 (degrees) FIG. 2 0 5 101520253035 2 (degrees) FIG. 3 0123456789 P (bar) FIG. 4
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同族专利:
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