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
• • 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
• • 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
  • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
  • C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G17/00—Compounds of germanium
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G17/00—Compounds of germanium
  • C01G17/006—Compounds containing germanium, with or without oxygen or hydrogen, and containing two or more other elements

Definitions

• the present invention relates to a novel crystalline solid, hereinafter referred to as IM-15, having a novel crystalline structure as well as 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
• ITQ-13 US-6,471,941
• CIT-5 US-6,043,179
• ITQ-21 WO-02/092511
• ITQ-22 Corma, A. et al, Nature Materials 2003.
• Another decisive advantage related to the use of media fluorinated reactions is to obtain new silicic framework topologies containing double four-tetrahedron (D4R) rings, as in the case of ITQ-7, ITQ-12 and ITQ-13 zeolites.
• sources of germanium and silicon in the synthesis media may also make it possible to obtain new frameworks of this type, that is to say containing D4R units, both in conventional nonfluorinated basic medium and in fluorinated medium.
• ITQ-17 and ITQ-21 zeolites A. Corma et al., Chem., Commun., 2001, 16, 1486, Chem.Commun., 2003, 9, 1050
• IM-12 J. Paillaud et al., Science, 2004, 304, 990.
• the present invention relates to a new crystalline solid, called crystalline solid IM-15, having a new crystalline structure.
• Said solid has a chemical composition expressed by the following general formula: mXO 2 : nGeO 2 : ⁇ Z 2 O 3 : qR: sF: wH 2 O 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 0.01 and 0.5, n is between 0.5 and 0.99, p is between 0 and 0.5. , q is 0 to 1, s is 0 to 0.5 and w is 0 to 5.
• the crystallized solid IM-15 according to the invention has an X-ray diffraction pattern including at least the lines listed in Table 1. This new crystalline solid IM-15 has a new crystalline structure.
• the relative intensity I / Io assigned to each value of d hk i is measured from the height of the corresponding diffraction peak.
• the X-ray diffraction pattern of the crystallized solid IM-15 according to the invention comprises at least the lines with the values of d hk given in Table 1. In the column of d hk i, the average values of the distances have been indicated. inter-reticular Angstr ⁇ ms ( ⁇ ). Each of these values shall be assigned the measurement error ⁇ (d hk i) between ⁇ 0,2 and ⁇ 0,003.
• the XRD diagram which made it possible to establish Table 1 was made from a crystallized solid IM-15 in its crude synthesis form.
• Table 1 Mean values of dhk i and relative intensities measured on an X-ray diffraction pattern of the IM-15 crystallized solid
• the relative intensity 1 / I 0 is given in relation to a relative intensity scale where a value of 100 is assigned 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 rays X ray diffraction diagram of the crystalline solid IM-15 according to the invention does not include a line of relative strength 1 / I 0 strong (F) and medium low (mf).
• the crystallized solid IM-15 according to the invention has a new basic crystal structure or topology which is characterized by its X-ray diffraction pattern given in FIG. 1.
• FIG. 1 was established from a crystallized solid IM - 15 in its raw form of synthesis.
• Said IM-15 solid has a chemical composition defined by the following general formula: mXO 2 : nGeO 2 : pZ 2 O 3 : qR: sF: wH 2 O (I), where R represents one or more organic species (s) ( 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, 01 and 0.5, n is 0.5 to 0.99, p is 0 to 0.5, q is 0 to 1, s is 0 to 0.5 and w is in the range of 0 to 0.5; 0 and 5.
• the X / Ge ratio of the framework of crystallized solid IM-15 according to the invention is between 0.01 and 1, preferably between 0.05 and 0.25 and very preferably between 0 and 5. , 05 and 0.1.
• the ratio ⁇ (n + m) / p ⁇ is greater than or equal to 5 and is preferably greater than or equal to 7.
• the value of p is between 0 and 0.5, preferably between 0 and 0.4, very preferably between 0 and 0.1 and even more preferably between 0.01 and 0.05.
• the value of q is between 0 and 1, advantageously between 0.05 and 0.7 and very advantageously between 0.1 and 0.3.
• s is between 0 and 0.5, preferably s is between 0 and 0.3 and very preferably s is between 0.05 and 0.2.
• the value taken by w is, according to the invention, between 0 and 5, preferably between 0.2 and 5.
• X is preferably selected from silicon, tin and titanium 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-15 according to the invention is then, when the element Z is present, a crystallized metallogermanosilicate having an X-ray diffraction pattern. identical to that described in Table 1, in particular when it is in its raw form of synthesis.
• the crystallized solid IM-15 according to the invention is then a crystallized aluminogermanosilicate having an X-ray diffraction pattern identical to that described in Table 1, in particularly when it is in its raw form of synthesis.
• the crystallized solid IM-15 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
• said IM-15 solid comprises at least one organic species such as that described below or its decomposition products, or its precursors.
• the organic species (s) R present in the general formula defining the IM-15 solid is (are) at least partly, and preferably entirely, (the so-called species (s) organic (s).
• R is 1,2-diaminoethane.
• 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 crystalline solid IM-15 according to the invention is preferably a zeolitic solid.
• the invention also relates to a process for preparing crystallized solid IM-15 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 and at least one organic species R and optionally at least one source of fluoride ions, the mixture preferably having the following molar composition:
• GeO 2 / X ⁇ 2 0.3 to 100, preferably 1.5 to 20, and very preferably 4 to 10,
• R is an organic species acting as an organic structuring agent.
• R is the nitrogen compound 1, 2-diaminoethane.
• 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).
• 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, fumed silicas, for example ⁇ erosil, and gel gels.
• silica Can be used colloidal silicas having different particle sizes, for example of mean equivalent diameter of between 10 and 15 nm or between 40 and 50 nm, such as those sold under the trade mark "LUDOX"
• the source of the element Z can 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 sulphate, an 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.
• the source of germanium may for example be a GeO 2 germanium oxide.
• 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 else in the form of a hydrolysable compound 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, 1,2-diaminoethane 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 , optionally 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 allowing it to crystallize into crystalline solid IM-15 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 hydrothermally treated until crystalline solid IM-15 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 of between 120 ° C. and 200 ° C., preferably between 140 ° C. and 180 ° C.
• 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.
• the reaction is generally carried out with stirring or without stirring, preferably in the absence of stirring. 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 the IM-15 crystalline solid at the expense of impurities. Such seeds include crystalline solids, especially IM-15 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.
• steps all the conventional methods known to those skilled in the art can be used.
• the present invention also relates to the use of said IM-15 solid as an adsorbent.
• said IM-15 solid is stripped of the organic species, preferably 1,2-diaminoethane, when used as an adsorbent.
• the crystallized solid IM-15 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 ⁇ 10.5) 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 1.95 g.
• the dried solid product was analyzed by X-ray diffraction and identified as consisting of IM-15 solid and amorphous phase.
• the Teflon jacket containing the synthesis mixture (pH ⁇ 12) is then introduced into an autoclave, which is placed in an oven at 170 0 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 2.32 g.
• the dried solid product was analyzed by X-ray diffraction and identified as consisting solely of IM-15 solid.
• the molar composition of the gel obtained is: 0.1 SiO 2 : 0.9 GeO 2 : 0.01 Al 2 O 3 : 0.5 1,2-diaminoethane: 20 H 2 O.
• Teflon jacket containing the synthesis mixture (pH ⁇ 11.5) is then introduced into an autoclave, which is placed in an oven at 170 ° C for a period of 14 days without agitation.
• the dried solid product was analyzed by X-ray diffraction and identified as consisting of IM-15 solid.
• 2.784 ml (2.502 g) of 1,2-diaminoethane (Aldrich) are added to 10.167 ml of distilled water in a Teflon container of 20 ml of interior volume.
• the mixture is stirred for 5 minutes with the aid of a magnetic stirrer and then 4.388 g of germanium oxide (Aldrich) are added.
• the mixture is stirred for 1 hour.
• 6.191 ml (5.782 g) of TEOS (tetraethoxysilane, Fluka) are then introduced.
• the mixture is then stirred for 10 to 12 hours at room temperature in order to evaporate the ethanol formed by the hydrolysis of TEOS.
• 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 5.78 g.
• the dried solid product was analyzed by X-ray diffraction and identified as consisting of IM-15 solid.
• the solid used is the crude synthetic solid of Example 1 and comprising the organic species 1, 2-diaminoethane. This solid first undergoes heating under a purge of nitrogen at a temperature of 200 ° C. for 4 hours and then a calcination still under a nitrogen atmosphere at 55 ° C. for 8 hours. Following these first treatments, the solid obtained is calcined at
• the solid obtained is then put into the form of extruded by kneading with boehmite (Pural SB3, Sasol) in a Z-arm kneader and extrusion of the paste obtained with a piston extruder.
• the extrudates are then dried at 120 ° C. for 12 hours in air and calcined at 550 ° C. for 2 hours under a stream of air in a muffle furnace.
• the adsorbent thus prepared is composed of 80% of the IM-15 zeolite solid and 20% of alumina.

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• 2006
  • 2006-11-07 FR FR0609765A patent/FR2908127B1/fr not_active Expired - Fee Related
• 2007
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