FR2982174A1 - MICROPOROUS CRYSTALLIZED SOLO OF TOPOLOGY -CLO, PROCESS FOR PREPARING THE SAME AND USE THEREOF - Google Patents

Abstract

The present invention relates to a microporous crystalline solid of structural type -CLO having a chemical composition defined by the general formula (a) mXO: nYO: pZO: qR: sF: wH O (a) in which R represents at least one selected compound from N, N-dimethylperhydro-dicyclopenta [b, d] pyrrolium and tetramethylammonium hydroxide and halides, provided that R does not represent only the hydroxide and / or at least one TMA halide, X represents at least a tetravalent element different from germanium, Y represents germanium, Z represents at least one trivalent element, F is fluorine, and m, n, p, q, s and w respectively represent the number of moles of XO, YO, ZO, R, F and H O.

Description

TECHNICAL FIELD The present invention relates to a microporous crystalline solid of -CLO topology. The invention also relates to the process for preparing said microporous crystalline solid and to the use thereof as an adsorbent. Microporous solids are solids widely used in the field of catalysis or separation. With regard to catalysis, the molecules to be treated are species of fossil or biological origin, sometimes of large size. Hydrocarbon feedstocks treated by the hydrocracking process or vegetable oils which may undergo a hydrotreating step before being used as a liquid fuel may in particular be mentioned. The size of the species contained in these feedstocks thus requires that the catalyst used be accessible to them. This implies in the case of microporous catalysts that the solid employed has large pore openings. Therefore, the design and preparation of microporous solids having large pore openings greater than 10 A with possibly cavities larger than 15-20 A in diameter are of primary importance. Among the existing structures, the CL-structure cloverite has the second lowest known framework density, ie 11.1 T / 1000 Å atoms, approximately 13 Å pore openings and 30 Å diameter cavities. However, cloverite is a gallophophate and is therefore less thermally stable than a hypothetical analog silicate or aluminosilicate, while the industry is in demand for compounds having interesting properties in acid catalysis, that is to say in reactions occurring at temperatures above 300 ° C and over many catalytic cycles. Much research has been done to try to synthesize silica-based cloverite because it would be more thermally stable than its equivalent in phosphate system. However, these have never been known to the Inventor. Thus, the present invention is to provide a crystallized microporous solid of -CLO topology that is not in the phosphate system. Another object of the invention is to provide a microporous crystalline solid of -CLO-based topology silica.

Another object of the invention is to provide microporous crystalline solids of -CLO topology that can be used as adsorbents. The subject of the invention is therefore a microporous crystalline solid of structural type -CLO having a chemical composition defined by the general formula (a) mXO 2: nYO 2: pZ 2 O 3: qR: sF: wH 2 O (a) in which R represents at least one organic compound chosen from: - N, N-dimethylperhydro-dicyclopenta [b, d] pyrrolium of formula (I): (I) in which A- is chosen from the group comprising hydroxide and halides, and - hydroxide and tetramethylammonium halides (TMA), provided that R does not represent only the hydroxide and / or at least one TMA halide, X represents at least one tetravalent element different from germanium, Y represents germanium, Z represents minus one trivalent element, F is fluorine, and m, n, p, q, s and w represent respectively the number of moles of XO2, YO2, Z203, R, F and H2O, m being between 0.3 and 0; , 8, n being between 0.2 and 0.7, p being between 0 and 0.1, where q is between 0 and 0.2, s being between 0 and 0.2 and w being between 0 and 1. In an advantageous embodiment of the invention, the X / Ge ratio of a solid of formula (a ) is between 0.25 and 10, preferably between 0.25 and 5, and very preferably between 0.25 and 2. In another advantageous embodiment of the invention, the ratio {(n + m ) / p} of a solid of formula (a) is greater than or equal to 10 and preferably greater than or equal to 20.

In another advantageous embodiment of the invention, the number p of a solid of formula (a) is between 0 and 0.05 and preferably between 0 and 0.02. In another advantageous embodiment of the invention, the number q of a solid of formula (a) is between 0.02 and 0.2 and preferably between 0.05 and 0.15.

In another advantageous embodiment of the invention, the number s of a solid of formula (a) is between 0.01 and 0.2 and preferably between 0.02 and 0.1. In another advantageous embodiment of the invention, the number w of a solid of formula (a) is between 0 and 0.5. In another advantageous embodiment of the invention, the at least one element represented by X in a solid of formula (a) is chosen from the group comprising silicon, tin and titanium. Preferably, X is silicon. In yet another advantageous embodiment of the invention, the at least one element represented by Z in a solid of formula (a) is selected from the group consisting of aluminum, boron, iron, indium and gallium. Preferably, Z is aluminum.

In a particularly advantageous embodiment, the elements X and Z of a solid of formula (a) are respectively silicon and aluminum. In the case where a solid of formula (a) according to the invention is in its raw form of synthesis, that is to say directly from the synthesis and prior to any calcination step (s) and / or ion exchange (s) well known to those skilled in the art, the number q of said solid of formula (a) is strictly greater than 0. A crystallized microporous solid of formula (a) according to the invention is preferably a zeolitic solid. The invention also relates to a process for preparing a solid of formula (a), in which q is strictly greater than 0 and less than 0.2 and comprising: a) a step in which an aqueous mixture, called a gel, is reacted; , comprising: - at least one source of at least one oxide Y02, wherein Y represents germanium, - at least one source of at least one oxide X02, where X represents at least one tetravalent element different from germanium, - optionally at at least one source of at least one oxide Z203, where Z represents at least one trivalent element, at least one of N, N-dimethylperhydro-dicyclopenta [b, d] pyrrolium of formula (I) in which A- is chosen from group comprising hydroxide and halides, - optionally at least one source of fluoride ions, the molar composition of said aqueous mixture being as follows: (XO2 + YO2) / Z2O3: at least 3, H2O / (XO2 + YO2): 1 to 100, R / (XO2 + YO2): 0.1 to 3, XO2 / YO2: 0.1 to 20, F / (XO2 + YO2): 0.05 to 2, and b) u a step of hydrothermal treatment of said mixture until the microporous crystalline solid of -CLO topology is formed, said solid having formula formula (a): mXO2: nYO2: pZ203: qR: sF: wH2O (a) in wherein X, Y, Z, R, m, n, p, s and w are as defined above and wherein q is strictly greater than 0 and less than 0.2. The amounts of said reagents are adjusted so as to impart to said mixture a composition allowing its solid crystallization of formula (a-I).

The time required to obtain the crystallization generally varies between 1 hour and several months depending on the composition of the reagents in the gel, the stirring and the reaction temperature. It will advantageously be between one day and one month, more advantageously between 1 and 3 weeks, even more advantageously between 12 and 16 days. The reaction is carried out with stirring or without stirring. All these parameters can be adjusted by those skilled in the art in the light of this knowledge. After said hydrothermal treatment step, the solid phase is filtered and washed; it is then ready for subsequent steps such as drying, dehydration and calcination and / or ion exchange. For these steps, all the conventional methods known to those skilled in the art can be used. Said N, N-dimethylperhydro-dicyclopenta [b, d] pyrrolium organic species of formula (I), which acts as a structurant, can be removed from a microporous crystalline solid of formula (a), in which q is strictly greater at 0 and less than 0.2, by the conventional routes of the state of the art such as heat and / or chemical treatments to obtain a microporous crystalline solid of formula (aI): mXO 2: nYO 2: pZ 2 O 3: sF: wH 2 O ( aI) wherein X, Y, Z, R, m, n, p, s and w are as defined above.

The source of the element X can be any compound comprising the element X and able to release this element in aqueous solution in reactive form. The source of element Y may be any compound comprising element Y and capable of releasing this element in aqueous solution in reactive form. The source of germanium may be a germanium oxide crystallized in the forms called quartz or rutile. It is also possible to use germanium sources such as tetraethoxygermanium or tetraisopropoxygermanium. The source of element Z may be any compound comprising element Z and capable of releasing this element in aqueous solution in reactive form. The fluorine may be introduced in the form of alkali metal or ammonium salts such as, for example, NaF, NH 4 F, NH 4 HF 2 or in the form of hydrofluoric acid or else in the form of hydrolyzable compounds which can release fluoride anions in water, such as fluoride. silicon SiF4 or ammonium fluorosilicates (NH4) 2SiF6 or sodium Na2SiF6. In an advantageous embodiment of the invention, the molar composition of said reaction mixture is the following: (XO 2 + YO 2) / Z 2 O 3: at least 5, H 2 O / (XO 2 + YO 2): 1 to 50, R / (XO 2 + YO2): 0.15 to 3, XO2 / YO2: 0.25 to 10, F1 (XO2 + YO2): 0.1 to 2, preferably: (XO2 + YO2) / Z2O3: at least 5, H2O / (XO2) + YO2): 1 to 50, R / (XO2 + YO2): 0.15 to 1, XO2 / YO2: 0.25 to 10, F / (XO2 + YO2): 0.1 to 1, very preferably: (XO2 + YO2) / Z2O3: at least 10, H2O / (XO2 + YO2): 2 to 10, R / (XO2 + YO2): 0.25 to 1, XO2 / YO2: 0.25 to 10, F / (XO2 + YO2): 0.2 to 1, and even more preferably: (XO2 + YO2) / Z2O3: at least 10, H2O / (XO2 + YO2): 2 to 10, MXO2 + YO2): 0.25 at 1, XO2 / YO2: 0.5 to 1.5, F / (XO2 + YO2): 0.2 to 1. In an advantageous embodiment of the invention, said process is characterized in that the N, N -dimethylperhydro-dicyclopenta [b, ct] pyrrolium of formula (I) is present in combination with an organic species selected from the group consisting of hydroxide and hal tetramethylammonium (TMA), the molar ratio [compound of formula (I)] / [TMA] being greater than or equal to 5 and up to infinity. In an advantageous embodiment of the invention, said method is characterized in that the element X is selected from the group comprising silicon, tin and titanium. Preferably, X is silicon.

The source of silica (SiO 2) can then be any of those commonly used in the synthesis of zeolites, for example powdered solid silica, silicic acid, colloidal silica or dissolved silica or silica. tetraethoxysilane (TEOS). Among the silicas in powder form, it is possible to use precipitated silicas, in particular those obtained by precipitation from an alkali metal silicate solution, such as aerosilic silicas, pyrogenic silicas, for example "CAB-O-SIL" and silica gels. It is possible to use colloidal silicas having different particle sizes, for example having a mean equivalent diameter of between 10 and 15 nm or between 40 and 50 nm, such as those sold under the trademark "LUDOX" ®.

In an advantageous embodiment of the invention, said source of the oxide Y0 2 is a germanium oxide GeO 2, preferably amorphous. In an advantageous embodiment of the invention, said method is characterized in that the element Z is chosen from the group comprising aluminum, boron, iron, indium and gallium. Preferably, Z is aluminum.

The source of alumina (Al 2 O 3) is then sodium aluminate, an aluminum salt, said salt being chosen from the group comprising chloride, nitrate, hydroxide and sulphate, an aluminum alkoxide or alumina itself, preferably in hydrated or hydratable form, such as for example colloidal alumina, pseudoboehmite, gamma alumina or alpha or beta trihydrate. It is also possible to use mixtures of the sources mentioned above. In a particularly advantageous embodiment of the invention, said process is characterized in that the reaction mixture comprises silica, a germanium oxide, N, N-dimethylperhydro-dicyclopenta [b, d] pyrrolium and a d fluoride ions.

In an advantageous embodiment of the invention, said hydrothermal treatment step of the reaction mixture is carried out under an autogenous reaction pressure, optionally by adding gas, for example nitrogen, at a temperature of between 120.degree. 200 ° C, preferably between 140 ° C and 180 ° C, and even more preferably between 140 ° C and 175 ° C.

It may be advantageous to add seeds to the reaction mixture to reduce the time required for crystal formation and / or the total crystallization time. It may also be advantageous to use seeds to promote the formation of a microporous crystalline solid of formula (a) to the detriment of impurities. Such seeds comprise crystalline solids, in particular solid crystals of formula (a) according to the invention. The crystalline seeds are generally added in a proportion of between 0.01 and 10% of the mass of the oxides (XO2 + YO2), XO2 being preferably silica, used in the reaction mixture.

The compounds of formula (a) according to the invention can be used as adsorbents. Preferably, said compounds are freed from the organic species N, N-dimethylperhydro-dicyclopenta [b, d] pyrrolium, when they are used as adsorbents. When used as adsorbents, the compounds of formula (a) according to the invention are generally dispersed in an inorganic matrix phase which contains channels and cavities which allow access of the fluid to be separated to the crystallized solid. These matrices are preferably mineral oxides, for example silicas, aluminas, silica-aluminas or clays. The matrix generally represents between 2 and 25% by weight of the adsorbent thus formed.

The invention is illustrated by means of the following examples. Example 1 Preparation of a First Microporous Crystalline Solid According to the Invention 5.743 g of N, N-dimethylperhydro-dicyclopenta [b, d] pyrrolium hydroxide are added to 3.92 ml of distilled water in a Teflon container of 20 ml internal volume. 3,660 g of germanium oxide (Aldrich) are then added to this solution. The mixture is stirred for 15 minutes with a magnetic stirrer. 1.401 g of Aerosil 200 (precipitated silica, Degussa) are then introduced. The mixture is then stirred for 2 hours at room temperature. 1.278 ml (1.457 g) of aqueous HF solution (40% hydrofluoric acid, Riedel de Haën) are then added. The mixture is then stirred for 15 minutes. After weighing and adjusting the required water content, the molar composition of the resulting mixture is: 0.4 SiO 2: 0.6 GeO 2: 0.5 N, N-dimethylperhydro-dicyclopenta [b, c /] pyrrolium: 0.5 HF: 5H2O. The Teflon jacket containing the synthesis mixture (pH - 9) is then introduced into an autoclave, which is placed in an oven at 170 ° C. for a period of 14 days in the absence of agitation.

After filtration, the product obtained is washed several times with distilled water. It is then dried at 70 ° C for 24 hours. The mass of dry product obtained is about 3.9 g.

The dried solid product was analyzed by X-ray diffraction and identified as a crystalline germanosilicate of -CLO topology having an X-ray diffraction pattern identical to that described in Table 1 when in its raw form of synthesis .

Table 1: Average values of dhkl and relative intensities measured on an X-ray diffraction diffraction pattern of the crystalline germanosilicate solid of -CLO topology of the invention made according to Example 1. dhid 2 theta (°) Ho (%) 26.42 3.34 FF 18.65 4.73 ff 15.24 5.79 f 13.17 6.70 ff 11.78 7.50 ff 10.73 8.24 ff 9.29 9.51 f 8 , 76 10.09 ff 7.92 11.16 ff 7.59 11.65 f 7.29 12.13 ff 7.04 12.57 ff 6.57 13.46 ff 6.37 13.88 ff 6, 20 14,27 ff 5,89 15,04 ff 5,75 15,41 ff 5,61 15,79 ff 5,24 16,91 ff 4,87 18,20 ff 4,64 19,13 ff 4,59 19,31 ff 4,56 19,47 ff 4,37 20,32 f 4,26 20,86 ff 4,15 21,42 ff 4,10 21,68 ff 3,95 22,47 ff 3,75 23 , 72 ff 3.71 23.96 ff 3.63 24.50 ff 3.57 24.91 ff 3.47 25.62 ff 3.42 26.06 ff 3.33 26.75 ff 3.23 27, 60 ff 2.92 30.64 ff 2.84 31.44 ff 2.77 32.35 ff 2.72 32.90 ff 2.61 34.33 ff 2.56 35.01 ff 2.34 38.48 ff where FF = very strong; m = average; f = weak; F strong; mf = weak medium; ff = very weak. The relative intensity Ho is given in relation to a relative intensity scale where it is assigned a value of 100 to the most intense line of the X-ray diffraction pattern: ff <15; 15f <30; 30mf <50; 50m <65; 65F <85; FFA5. EXAMPLE 2 Preparation of a Second Microporous Crystalline Solid According to the Invention 4,785 g of N, N-dimethylperhydro-dicyclopenta [b, d] pyrrolium hydroxide are added to 7.54 ml of distilled water in a Teflon container 20 mL of interior volume. 3.050 g of germanium oxide (Aldrich) is then added to this solution. The mixture is stirred for 15 minutes with a magnetic stirrer. 4.241 ml (4.029 g) of TEOS (tetraethoxysilane, Aldrich) are then introduced. The mixture is then stirred for 48 hours at room temperature in order to evaporate the ethanol formed by the hydrolysis of the TEOS. 1.065 ml (1.214 g) of aqueous HF solution (40% hydrofluoric acid, Riedel de Haën) are then added. The mixture is then stirred for 15 minutes. After weighing and adjusting the required water content, the molar composition of the resulting mixture is: 0.4 SiO 2: 0.6 GeO 2: 0.5 N, N-dimethylperhydro-dicyclopenta [b, c] pyrrolium: 0.5 HF: 10H2O. The Teflon jacket containing the synthesis mixture (pH - 9) is then introduced into an autoclave, which is placed in an oven at 170 ° C. for a period of 14 days in the absence of agitation.

After filtration, the product obtained is washed several times with distilled water. It is then dried at 70 ° C for 24 hours. The mass of dry product obtained is about 3.12 g. The dried solid product was analyzed by X-ray diffraction and identified as a crystalline germanosilicate of -CLO topology having an X-ray diffraction pattern similar to that described in Table 1 when in its raw synthetic form. . Example 3 Preparation of a Third Microporous Crystalline Solid According to the Invention 5.360 g of N, N-dimethylperhydro-dicyclopenta [b, d] pyrrolium hydroxide are added to 3.54 ml of distilled water in a Teflon container 20 mL of interior volume. 0.426 g of aluminum hydroxide (63 to 67% by weight of Al 2 O 3, Fluka) and 1.140 g of germanium oxide (Aldrich) are then added to this solution. The mixture is stirred for 1 hour with the aid of a magnetic stirrer. About 0.080 g of the product of the synthesis described in Example 1 previously ground (ie 2% by weight relative to the oxides SiO 2, GeO 2 and Al 2 O 3) are then introduced as seeds, then the mixture is stirred for 15 minutes. 2,615 g of Aerosil 200 (precipitated silica, Degussa) are then introduced. The mixture is then stirred for 48 hours at room temperature in order to evaporate the ethanol formed by the hydrolysis of the TEOS. 1.192 ml (1.360 g) of aqueous HF solution (40% hydrofluoric acid, Riedel de Haën) are then added and the mixture is stirred for 15 minutes. After weighing and adjusting the required water content, the molar composition of the resulting mixture is: 0.8 SiO 2: 0.2 GeO 2: 0.05 Al 2 O 3: 0.5 N, N-dimethylperhydrodicyclopenta [b, d] pyrrolium: 0 5 HF: 5 H 2 O (+ 2% by weight relative to the oxides). The Teflon jacket containing the synthesis mixture (pH - 9) is then introduced into an autoclave, which is placed in an oven at 170 ° C. for a period of 14 days in the absence of agitation. After filtration, the product obtained is washed several times with distilled water. It is then dried at 70 ° C for 24 hours. The mass of dry product obtained is about 2.2 g. The dried solid product was analyzed by X-ray diffraction and identified as a crystalline aluminogermanosilicate of -CLO topology having an X-ray diffraction pattern similar to that described in Table 1 when in its raw synthetic form. .

Claims (19)

REVENDICATIONS1. Microporous crystalline solid of structural type -CLO having a chemical composition defined by the general formula (a) mXO 2: nYO 2: pZ 2 O 3: qR: sF: wH 2 O (a) in which R represents at least one organic compound chosen from: - N, N-dimethylperhydro-dicyclopenta [b, d] pyrrolium of formula (I): (I) wherein A- is selected from the group consisting of hydroxide and halides, and - hydroxide and tetramethylammonium halides (TMA) provided that R does not represent only hydroxide and / or at least one TMA halide, X represents at least one tetravalent element different from germanium, Y represents germanium, Z represents at least one trivalent element, F is fluorine. , and m, n, p, q, s and w represent respectively the number of moles of XO2, YO2, Z203, R, F and H2O, m being between 0.3 and 0.8, n being between 0, 2 and 0.7, p being between 0 and 0.1, q being between 0 and 0.2, s being between re 0 and 0.2 and w being between 0 and 1. 2. Crystallized solid according to claim 1, wherein the X / Ge ratio is between 0.25 and 10. 3. Crystallized solid according to any one of claims 1 to 2, wherein the ratio {(n + m) / p} is greater than or equal to 10. 4. Crystallized solid according to any one of claims 1 to 3, wherein p is between 0 and 0.05. 5. Crystallized solid according to any one of claims 1 to 4, wherein q is between 0.02 and 0.2. 6. Crystallized solid according to any one of claims 1 to 5, wherein s is between 0.01 and 0.2. The crystalline solid of any one of claims 1 to 6, wherein w is 0 to 0.5. The crystalline solid of any one of claims 1 to 7, wherein X is selected from the group consisting of silicon, tin and titanium. The crystalline solid of any one of claims 1 to 8, wherein Z is selected from the group consisting of aluminum, boron, iron, indium and gallium. 10. Crystallized solid according to any one of claims 1 to 9, wherein X is silicon and Z is aluminum. 11. A process for preparing a solid according to any one of claims 1 to 10, wherein q is strictly greater than 0 and less than 0.2 and comprising: a) a step in which an aqueous mixture is reacted comprising: at least one source of at least one oxide Y02, where Y represents germanium, at least one source of at least one oxide X02, where X represents at least one tetravalent element different from germanium, optionally at least one source of at least one oxide Z203, wherein Z represents at least one trivalent element, at least one of N, N-dimethylperhydro-dicyclopenta [b, d] pyrrolium of formula (I) wherein A- is selected from the group consisting of hydroxide and halides, - optionally at least one source of fluoride ions, the molar composition of said aqueous mixture being the following: (XO 2 + YO 2) / Z 2 O 3: at least 3, H 2 O / (XO 2 + YO 2): 1 to 100, R / (XO2 + YO2): 0.1 to 3, XO2 / YO2: 0.1 to 20, F / (XO2 + YO2): 0.05 to 2, and b) a step of hydrothermally treating said mixture until the crystallized solid of -CLO topology is formed, said solid having the following formula (a): mXO2: nYO2: pZ203: qR: sF: wH2O (a), wherein X, Y, Z, R, m, n, p, s and w are as defined above and wherein q is strictly greater than 0 and less than 0.2. 12. Process according to claim 11, characterized in that the molar composition of the reaction mixture is the following: (XO2 + YO2) / Z2O3: at least 5, H2O / (XO2 + YO2): 1 to 50, R / (XO2 + YO2): 0.15 to 1, XO2 / YO2: 0.25 to 10, F / (XO2 + YO2): 0.1 to 1. 13. The method of claim 11 or 12 characterized in that N, Ndimethylperhydro-dicyclopenta [b, d] pyrrolium of formula (I) is present in combination with an organic species selected from the group consisting of hydroxide and halides of tetramethylammonium (TMA), the molar ratio [I] / [TMA] being greater than or equal to 5 and up to infinity. 14. Method according to any one of claims 11 to 13 characterized in that X is silicon. 15. Method according to any one of claims 11 to 14 characterized in that the source of the oxide Y02 is a germanium oxide Ge02, preferably amorphous. 16. Method according to any one of claims 11 to 15 characterized in that Z is aluminum. 17. Process according to any one of Claims 11 to 16, characterized in that the reaction mixture comprises silica, a germanium oxide, N, N-dimethylperhydro-dicyclopenta [b, d] pyrrolium and a source of fluoride ions. 18. Process according to any one of claims 11 to 17 characterized in that seeds are added to the reaction mixture. 19. Use of the crystalline solid according to any one of claims 1 to 10 as an adsorbent.