Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
  • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
  • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
  • B01J20/16—Alumino-silicates
  • B01J20/18—Synthetic zeolitic molecular sieves
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
  • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
  • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
  • C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced

Definitions

• the present invention relates to a novel crystallized solid, hereinafter referred to as IM-20, having a new crystalline structure and to the process for preparing said solid.
• zeolite NU-87 US-5,178,748
• zeolite MCM-22 US Pat. No. 4,954,325
• gallophosphate cloverite
• zeolites ITQ-12 US-6,471,939
• UQ-13 UQ-13
• CIT-5 US-6,043,179
• ITQ-21 WO-02/092511
• ITQ-22 Corma, A.
• sources of germanium and silicon in the synthesis media can also make it possible to obtain new frameworks of this type, that is to say containing D4R units, both in conventional non-fluorinated basic medium and in fluorinated medium, as in the case of ITQ-17 and ITQ-21 zeolites (Corma et al., Chem., 2001, 16, 1486, Chem., 2003, 9, 1050), or M-12 (JL. Paillaud et al., Science, 2004, 304, 990).
• the present invention relates to a new crystalline solid, called crystallized solid IM-20, having a new crystalline structure.
• Said solid has a chemical composition expressed by the following general formula: mXO 2 : nGeO 2 : PZ 2 O 3 : qR: sF: wH 2 0 wherein R represents one or more organic species, X represents a or more tetravalent element (s) different from germanium, Z represents at least one trivalent element and F is fluorine, m, n, p, q, s and w respectively representing the number of moles of XO 2 , GeO 2 , Z 2 O 3 , R, F and H 2 O and m is between 0.3 and 0.8, n is between 0.2 and 0.7, p is between 0 and 0.1.
• q is 0 to 0.2
• s is 0 to 0.2
• w is 0 to 1.
• the crystallized solid IM-20 according to the invention has, in its crude synthesis form, an X-ray diffraction pattern including at least the lines listed in Table 1.
• the crystallized solid Evl-20 according to the invention has, in its calcined form, an X-ray diffraction pattern including at least the lines listed in Table 2.
• This new crystalline solid EVI-20 has a new crystalline structure.
• the measurement error ⁇ (d hk i) on d hk i is calculated by means of the Bragg relation as a function of the absolute error ⁇ (2 ⁇ ) assigned to the measurement of 2 ⁇ .
• An absolute error ⁇ (2 ⁇ ) equal to ⁇ 0.02 ° is commonly accepted.
• the relative intensity 1 / I 0 assigned to each value of d h w is measured from the height of the corresponding diffraction peak.
• the X-ray diffraction pattern of the crystallized solid IM-20 according to the invention in its raw synthesis form, comprises at least the lines at the values of d hk given in Table 1.
• the X-ray diffraction pattern of the EVI-20 crystalline solid according to the invention in its calcined form, has at least the lines of the hk values i given in table 2. in the column of d hkl, it was reported the average values of interplanar spacings in Angstroms ( ⁇ ). Each of these values shall be assigned the measurement error ⁇ (d hk i) between ⁇ 0,2 and ⁇ 0,003.
• Table 1 Mean values of d h ki and relative intensities measured on an X-ray diffraction pattern of the crystallized solid IM-20 crude synthesis
• Table 2 Mean dhki values and relative intensities measured on an X-ray diffraction pattern of the calcined IM-20 calcined solid
• the relative intensity I / Io is given in relation to a scale of relative intensity where it is assigned a value of 100 to the most intense line of the X-ray diffraction pattern: ff ⁇ 15; ⁇ F ⁇ 30; ⁇ Mf ⁇ 50; 50 ⁇ m ⁇ 65; 65 ⁇ F ⁇ 85;FF> 85.
• the IM-20 crystallized solid according to the invention has a novel basic crystal structure or topology which is characterized by its X-ray diffraction patterns in the synthetic and calcined synthetic forms given in FIG. 1 and FIG. 2 respectively.
• Said solid EVI-20 has a chemical composition defined by the following general formula: mx0 2: nGeO 2: pZ 2 O 3: qR: sF: wH 2 O (I) wherein R represents one or more kind (s) organic ( s), X represents one or more tetravalent element (s) different from the germanium, Z represents at least one trivalent element and F is fluorine.
• m, n, p, q, s and w respectively represent the number of moles of XO 2 , GeO 2 , Z 2 O 3 , R, F and H 2 O and m is between 0.3 and 0.8, n is between 0.2 and 0.7, p is between 0 and 0.1, q is between 0 and 0.2, s is between 0 and 0.2 and w is between 0 and 1.
• the molar ratio m / n of the framework of crystallized solid IM-20 according to the invention is between 1 and 10, preferably between 1 and 5. and most preferably between 1.5 and 2.
• the molar ratio ⁇ (n + m) / p ⁇ is greater than or equal to 10 and is preferably greater than or equal to 20.
• the value of p is between 0 and 0.1, very preferably between 0 and 0.05 and even more preferably between 0.005 and 0.02.
• the value of q is between 0 and 0.2, advantageously between 0.02 and 0.2 and very advantageously between 0.05 and 0.15.
• s is between 0 and 0.2, preferably s is between 0.01 and 0.2 and very preferably s is between 0.02 and 0.1.
• the value taken by w is, according to the invention, between 0 and 1, preferably between 0.3 and 0.5.
• X is preferably selected from silicon, tin and titanium, very preferably X is silicon, and Z is preferably selected from aluminum, boron, iron, indium and gallium. and very preferably Z is aluminum.
• X is silicon: the crystallized solid IM-20 according to the invention is then, when element Z is present, a crystallized metallogermanosilicate having an X-ray diffraction pattern identical to that described in Table 1 when it is in its raw form of synthesis and identical to that described in Table 2 when it is in its calcined form.
• the crystallized solid EM-20 according to the invention is then a crystallized aluminogermanosilicate having an X-ray diffraction pattern identical to that described in Table 1 when it is in its raw form of synthesis and identical to that described in Table 2 when it is in its calcined form.
• the crystallized solid IM-20 according to the invention comprises at least one organic species such as that described below or its decomposition products, or its precursors.
• the organic species (s) R (s) present in the general formula defining the IM-20 solid is (are) at least partly, and preferably wholly, the said organic species (s).
• R is the 1-butyl-3-methylimidazolium cation.
• Said organic species R which acts as a structurant, can be removed by the conventional routes of the state of the art such as heat and / or chemical treatments.
• the crystallized solid IM-20 according to the invention is preferably a zeolitic solid.
• the invention also relates to a process for preparing crystalline solid M-20 in which an aqueous mixture comprising at least one source of at least one germanium oxide, at least one source of at least one oxide XO 2 , is reacted, optionally at least one source of at least one oxide Z 2 O 3 , at least one organic species R and at least one source of fluoride ions, the mixture preferably having the following molar composition: (XO 2 + GeO 2 ) / Z 2 O 3 : at least 5, preferably at least 10, H 2 O / (XO 2 + GeO 2 ): 1 to 50, preferably 5 to 20, R / (XO 2 + GeO 2 ): 0.3 to 3, preferably 0.4 to 1.5,
• XO 2 / GeO 2 0.5 to 10, preferably 1 to 10, and very preferably 1 to 5, F / (XO 2 + GeO 2 ): 0.1 to 2, preferably 0.2 to 1, where X is one or more different tetravalent element (s) of germanium, preferably chosen from silicon, tin and titanium and very preferably X is silicon, Z is one or more trivalent element (s) chosen from the group formed by the following elements: aluminum, iron, boron, indium and gallium, preferably aluminum.
• R is an organic species acting as an organic structuring agent.
• R is the compound 1-butyl-3-methylimidazolium.
• 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 silica source may be any of those commonly used in the synthesis of zeolites, for example powdered solid silica, silicic acid or colloidal silica. or dissolved silica or tetraethoxysilane (TEOS).
• TEOS tetraethoxysilane
• 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.
• Colloidal silicas having different particle sizes, for example of equivalent diameter may be used average between 10 and 15 nm or between 40 and 50 nm, such as those sold under the trademark "LUDOX”.
• the source of germanium may be any compound comprising the germinal element and able to release 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 germanium source may preferably be GeO 2 amorphous germanium oxide.
• 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 source of alumina is preferably sodium aluminate, or an aluminum salt, for example chloride, nitrate, hydroxide or sulfate, a aluminum alkoxide or alumina proper, 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.
• the fluorine may be introduced in the form of alkali metal or ammonium salts, for example NaF, NH 4 F or NH 4 HF 2, or in the form of hydrofluoric acid or in the form of hydrolyzable compounds which can release fluoride anions in the form of water such as silicon fluoride SiF 4 or fluorosilicates ammonium (NH 4 ) 2 SiF 6 or sodium Na 2 SiF 6 .
• an aqueous mixture comprising silica, optionally alumina, a germanium oxide, 1-butyl-3-methylimidazolium and a source of fluoride ions is reacted. .
• the process according to the invention consists in preparing an aqueous reaction mixture called gel containing at least one source of at least one germanium oxide, at least one source of at least one oxide XO 2 , optionally at least one source of at least one oxide Z 2 O 3 , at least one source of fluoride ions, and at least one organic species R.
• the amounts of said reagents are adjusted so as to give this gel a composition enabling it to crystallize crystalline solid IM-20 of general formula mXO 2 : nGeO 2 : pZ 2 O 3 : qR: sF: wH 2 0, where m, n, p, q, s and w meet the criteria defined above.
• the gel is then subjected to hydrothermal treatment until crystallized solid IM-20 is formed.
• the gel is advantageously placed under hydrothermal conditions under an autogenous reaction pressure, optionally by adding gas, for example nitrogen, at a temperature comprised between 12O 0 C and 200 ° C, preferably between 140 ° C and 180 ° C, and even more preferably at a temperature between 150 ° C. and 175 ° C. until the formation of the IM-20 solid crystals according to the invention.
• the time required to obtain the crystallization generally varies between 1 hour and several months, preferably between 10 hours and 20 days, depending on the composition of the reagents in the gel, the stirring and the reaction temperature.
• the reaction is carried out with stirring or without stirring.
• seeds 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 crystalline solid IM-20 at the expense of impurities.
• Such seeds comprise crystalline solids, in particular IM-20 solid crystals.
• the crystalline seeds are generally added in a proportion of between 0.01 and 10% of the weight of the oxides (XO 2 + GeO 2 ), XO 2 preferably being silica, used in the reaction mixture.
• 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.
• the calcination step is advantageously carried out by one or more heating steps at temperatures ranging from 100 to 1000 ° C. for periods ranging from a few hours to several days.
• the crystallized solid in its crude synthesis form first undergoes heating under a neutral gas, for example under a sweep. nitrogen, at a temperature preferably between 100 and 250 ° C for a period advantageously between 2 and 8 hours and calcination under an atmosphere of a neutral gas, for example under a nitrogen atmosphere, at a temperature preferably between 400 and 700 ° C for a period advantageously between 6 and 10 hours.
• the crystallized solid IM-20 obtained is calcined at a temperature between 400 and 700 ° C for a period of between 6 and 10 hours under air flow and then for a period preferably between 6 and 10 hours. and 10 hours under oxygen flow.
• the present invention also relates to the use of said IM-20 solid as an adsorbent.
• said solid M-20 is stripped of the organic species, preferably the 1-butyl-3-methylimidazolium cation, when it is used as an adsorbent.
• the IM-20 crystallized solid according to the invention is 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 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 without 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 4.23 g.
• the dried solid product is first heated under a nitrogen flush at the temperature of 200 ° C. for 4 hours and then calcination under a nitrogen atmosphere at 550 ° C. for 8 hours. Following these first treatments, the solid obtained is calcined at 550 ° C. for 8 hours under an air flow and then for another 8 hours under an oxygen flow.
• the solid obtained was analyzed by X-ray diffraction and identified as consisting of crystallized solid IM-20: the diffractogram carried out on the solid IM-20 is given in FIG.
• Teflon jacket containing the synthesis mixture (pH ⁇ 9) is then introduced into an autoclave, which is placed in an oven at 170 0 C for a period of 14 days without agitation.
• the dried solid product is first heated under a nitrogen sweep at a temperature of 200 ° C for 4 hours and then calcined under a nitrogen atmosphere at 550 ° C for 8 hours. Following these first treatments, the solid obtained is calcined at 550 ° C for 8 hours under air flow and another 8 hours under oxygen flow.
• the solid obtained was analyzed by X-ray diffraction and identified as consisting of crystallized solid IM-20: the diffractogram carried out on the solid IM-20 is given in FIG.
• Example 3 Preparation of an IM-20 Crystalline Solid According to the Invention 6.952 g of 1-butyl-3-methylimidazolium hydroxide (Solvionic) are added to 7.64 ml of distilled water in a 20 ml Teflon container. mL of interior volume. 0.349 g of aluminum hydroxide (63 to 67% by weight of Al 2 O 3 , Fluka) and 1.862 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.
• Solvionic 1-butyl-3-methylimidazolium hydroxide
• the molar composition of the resulting mixture is: 0.6 SiO 2 : 0.4 GeO 2 : 0.05 Al 2 O 3 : 1 l -butyl-3-methylimidazolium: 1 HF : 10 H 2 O (+ 2% by weight of seeds with respect to the oxides SiO 2 and GeO 2 ).
• 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 without 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 2.27 g.
• the dried solid product is first heated under nitrogen flushing at a temperature of 200 ° C. for 4 hours and then calcination under a nitrogen atmosphere at 55 ° C. for 8 hours. Following these first treatments, the solid obtained is calcined at 550 ° C. for 8 hours under an air flow and then for another 8 hours under an oxygen flow.
• the solid obtained was analyzed by X-ray diffraction and identified as consisting of crystallized solid IM-20: the diffractogram carried out on the solid IM-20 is given in FIG.
• the solid used is the calcined solid of Example 1. It is extruded by kneading with boehmite (Pural SB3, Sasol) in a Z-arm kneader and extruding the paste obtained with a piston extruder. . The extrudates are then dried at 120 ° C. for 12 hours in air and calcined at 55 ° C. for 2 hours under an air flow in a muffle furnace.
• the adsorbent thus prepared is composed of 80% by weight of the zeolitic solid IM-20 and 20% by weight of alumina.

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• 2008
  • 2008-12-18 FR FR0807271A patent/FR2940266B1/fr not_active Expired - Fee Related
• 2009
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