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
  • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
• • 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
  • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
  • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
• • 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
• • 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
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
  • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram

Definitions

• the present invention relates to a novel crystallized solid, hereinafter referred to as IM-14, 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
• 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.
• the present invention relates to a new crystalline solid, called crystalline solid IM-14, having a new crystalline structure.
• Said solid has a chemical composition expressed by the following general formula: GeO 2 : nY 2 O 3 : pR: qF: wH 2 0 wherein R represents one or more organic species, Y represents at least one element trivalent and F is fluorine, n, p, q and w respectively representing the number of moles of Y 2 O 3 , R, F and H 2 O and n is between 0 and 0.1, p is between 0 and 0.7, q is 0 to 0.7 and w is 0 to 5.
• the crystallized solid IM-14 according to the invention has an X-ray diffraction pattern including at least the lines listed in Table 1.
• This new crystalline solid IM-14 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 hk i is measured from the height of the corresponding diffraction peak.
• the X-ray diffraction pattern of the IM-14 crystallized solid according to the invention comprises at least the dhki lines given in Table 1. In the dhki column, the average values of the inter-reticular distances in FIG. Angstr ⁇ ms ( ⁇ ).
• 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;
• the diffraction pattern of X-ray crystalline solid IM-14 according to the invention does not comprise lines having a relative intensity of 1 / I 0 strong (F) and low (f).
• the crystallized solid IM-14 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 an IM-solid. 14 in its raw form of synthesis.
• Said IM-14 solid has a chemical composition defined by the following general formula: GeO 2 : nY 2 O 3 : pR: qF: wH 2 O (I), where R represents one or more organic species, Y is at least one trivalent element and F is fluorine.
• R represents one or more organic species
• Y is at least one trivalent element
• F is fluorine.
• n, p, q and w represent respectively the number of moles of Y 2 O 3 , R, F and H 2 O and n is between 0 and 0.1, p is 0 to 0.7, q is 0 to 0.7 and w is 0 to 5.
• the Ge / Y ratio in the crystallized solid IM-14 according to the invention is greater than or equal to 5 and is preferably greater than or equal to 7.
• the value of n is between 0 and 0.1, very preferably between 0 and 0.07 and even more preferably between 0.01 and 0.05.
• the value of p is between 0 and 0.7, advantageously between 0.01 and 0.7 and very advantageously between 0.1 and 0.3.
• q is between 0 and 0.7, preferably q is between 0.1 and 0.7 and very preferably q is between 0.1 and 0.2.
• the value taken by w is, according to the invention, between 0 and 5, preferably between 0.2 and 5.
• Y is preferably selected from aluminum, boron, iron, indium and gallium and very preferably Y is aluminum.
• crystallized solid IM-14 according to the invention is a crystallized metallogermanate having an X-ray diffraction pattern identical to that described in Table 1, in particular when it is in its raw form. of synthesis.
• Y is aluminum: the crystallized solid IM-14 according to the invention is then a crystallized aluminogermanate having an X-ray diffraction pattern identical to that described in Table 1, in particular when it is under its raw form of synthesis.
• the crystallized solid IM-14 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-14 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-14 solid is (are) at least in part, and preferably entirely, (the so-called species (s) organic (s).
• R is 1,2-diaminoethane.
• the IM-14 crystallized solid according to the invention is preferably a zeolitic solid.
• the invention also relates to a process for preparing crystallized solid IM-14 in which an aqueous mixture is reacted comprising at least one source of at least one oxide GeO 2 germanium, optionally at least one source of at least one Y 2 O 3 oxide 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 / Y 2 ⁇ D 3 : at least 5, preferably at least 7, H 2 O / GeO 2 : 1 to 70, preferably 2 to 50,
• R / GeO 2 0.1 to 3, preferably 0.25 to 1,
• R is an organic species acting as an organic structuring agent.
• R is the nitrogen compound 1, 2-diaminoethane.
• the source of germanium may for example be a GeO 2 germanium oxide, for example an amorphous germanium oxide.
• 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 alumina is preferably sodium aluminate, or an aluminum salt, for example chloride, nitrate, hydroxide or sulphate, 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 is reacted comprising a germanium oxide, optionally alumina, 1,2-diaminoethane and a source of fluoride ions.
• the process according to the invention consists in preparing an aqueous reaction mixture called gel containing at least one source of at least one GeO 2 oxide, optionally at least one source of at least one Y 2 O 3 oxide, optionally at least one source of fluoride ions, and at least one organic species R.
• the amounts of said reagents are adjusted to conferring on this gel a composition allowing its crystallization in crystalline solid IM-14 of general formula GeO 2 : nY 2 O 3 : pR: qF: wH 2 O, where n, p, q and w meet the criteria defined above.
• the gel is then subjected to hydrothermal treatment until crystalline solid IM-14 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 12 ° C. and 200 ° C., preferably between 140 ° C. and 180 ° C. C, and even more preferably at a temperature which does not exceed 175 ° C until the formation of IM-14 solid crystals according to the invention.
• gas for example nitrogen
• 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.
• 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 crystallized solid IM-14 at the expense of impurities.
• Such seeds comprise crystalline solids, in particular IM-14 solid crystals.
• the crystalline seeds are generally added in a proportion of between 0.01 and 10% of the weight of the GeO 2 oxide 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 present invention also relates to the use of said IM-14 solid as an adsorbent.
• said IM-14 solid is stripped of the organic species, preferably 1,2-diaminoethane, when used as an adsorbent.
• the IM-14 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 ⁇ 11) 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 1.25 g.
• the dried solid product was analyzed by X-ray diffraction and identified as consisting of IM-14 solid.
• the molar composition of the mixture obtained is: GeO 2 : 0.6 1,2-diaminoethane: 0.4 HF: 8H 2 O
• the Teflon jacket containing the synthesis mixture pH ⁇ 10.5 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 7.85 g.
• the dried solid product was analyzed by X-ray diffraction and identified as consisting of IM-14 solid as well as traces of a dense argutite phase.
• 2,784 ml (2.502 g) of 1,2-diaminoethane (Aldrich) are added to 9,129 ml of distilled water in a Teflon container of 20 ml internal volume.
• the mixture is stirred for 5 minutes with the aid of a magnetic stirrer, then 0.108 g of aluminum hydroxide (63 to 67% by weight of Al 2 O 3 , Fluka) and 7.263 g of germanium oxide ( Aldrich) are added.
• the mixture is stirred for 4 hours.
• the subsequent addition of 1.228 ml (1.388 g) of aqueous HF solution (40% hydrofluoric acid, Carlo Erba) results in an increase in the viscosity of the reaction mixture.
• the mixture is then stirred manually using a stainless steel spatula for 5 to 10 minutes. After weighing and adjusting the required water content, the molar composition of the resulting mixture is: GeO 2 : 0.01 Al 2 O 3 : 0.6 1, 2-diaminoethane: 0.4 HF: 8 H 2 O
• 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.
• 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 6.10 g.
• the dried solid product was analyzed by X-ray diffraction and identified as consisting of IM-14 solid as well as traces of a dense argutite phase.
• the solid used is the crude synthetic solid of Example 1 and comprising the organic species
• the adsorbent thus prepared is composed of 80% of the IM-14 zeolite solid and 20% of alumina.

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• Chemical & Material Sciences (AREA)
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• 2006
  • 2006-11-07 FR FR0609764A patent/FR2908126B1/fr not_active Expired - Fee Related
• 2007
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  • 2007-10-01 WO PCT/FR2007/001611 patent/WO2008059121A2/fr not_active Ceased
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