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WO2014122344A1 - Synthèse de la zéolithe itq-51, procédé d'obtention et d'utilisation - Google Patents

Synthèse de la zéolithe itq-51, procédé d'obtention et d'utilisation Download PDF

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Publication number
WO2014122344A1
WO2014122344A1 PCT/ES2014/070063 ES2014070063W WO2014122344A1 WO 2014122344 A1 WO2014122344 A1 WO 2014122344A1 ES 2014070063 W ES2014070063 W ES 2014070063W WO 2014122344 A1 WO2014122344 A1 WO 2014122344A1
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WIPO (PCT)
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value
material according
crystalline material
microporous crystalline
obtaining
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PCT/ES2014/070063
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English (en)
Spanish (es)
Inventor
Avelino CORMA CANÓS
Manuel MOLINER MARÍN
Raquel MARTÍNEZ FRANCO
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Consejo Superior De Investigaciones Científicas (Csic)
Universitat Politécnica De Valéncia
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Publication of WO2014122344A1 publication Critical patent/WO2014122344A1/fr

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    • 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
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
    • 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
    • C01B37/04—Aluminophosphates [APO compounds]
    • 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
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/065—Aluminophosphates containing other elements, e.g. metals, boron the other elements being metals only
    • 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
    • C01B39/54—Phosphates, e.g. APO or SAPO compounds

Definitions

  • This patent refers to the synthesis of a new porous crystalline material, ITQ-51, its method of preparation and its use in the catalytic conversion of organic compounds.
  • the present patent also describes the novel use of "proton sponges" as organic structure directing agents in the synthesis of porous crystalline materials.
  • Zeolites are porous crystalline aluminosilicates that have found important applications as catalysts, adsorbents and ion exchangers. Many of these zeolitic materials have well-defined structures that form channels and cavities in their interior of uniform size and shape that allow the adsorption of certain molecules, while preventing the passage into the glass of other molecules of size too large to diffuse through of the pores. This characteristic gives these materials molecular sieve properties.
  • T Si or Al
  • heteroatoms have been incorporated into their structures, such as Ti, Sn, Ge, B, Fe, among others.
  • AlPOs aluminophosphates
  • SAPOs silicoaluminophosphates
  • MeAIPOs metalloaluminophosphates
  • ALPOs were first described in 1982 by UOP researchers (Wilson, S. T., et al. J. Am Chem. Soc. 1982, 104, 146).
  • the composition of said materials is formed by aluminum and phosphorus atoms in strict alternation in tetrahedral coordination, connected by oxygen atoms.
  • SAPOs are a particular case of AlPOs, where some of the atoms of the crystalline structure are partially substituted by silicon (Chen, J. S. et al. J. Phys.Chem., 1994, 98, 10216). When this happens, SAPOs show excellent cation exchange capacity. Possibly, the most common SAPOs are in their protonated form.
  • the protons associated with the Si atoms in the crystalline network introduce acidity to these materials, allowing their use as commercial catalysts in acid catalytic processes, such as the methanol-a-olefins process (SW Kaiser, US Patent 4,499,327; 1985).
  • MeAIPOs can be incorporated into the crystal structure of the AlPO, thus obtaining MeAIPOs, where Me can be any heteroatom other than silicon, aluminum and phosphorus.
  • MeAIPOs have been described in the literature. A long list of metals, including Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, have been introduced into the crystalline network of different zeotypes. These MeAIPOs are used as catalysts in different acid and redox catalytic processes (Hartmann et al., Res. Chem. Inter., 2002, 28, 625). Especially interesting is its use as redox catalysts, because the isolated metals in tetrahedral coordination in the crystalline network of the MeAIPOs present changes in their oxidation state.
  • zeolites and related zeotypes are synthesized in the presence of an organic molecule that acts as a structure directing agent.
  • Organic molecules that act as organic structure directing agents may contain nitrogen, phosphorus or PN bonds in their composition, and can result in stable organic cations in the reaction medium.
  • ADEOs organic structure directing agents
  • amines and ammonium cations are amines and ammonium cations.
  • "Proton sponges" are bulky aromatic diamines that have amino groups close to each other (Staab, et al. Angew. Chem. Int. Ed. 1988, 27, 865). The distance between these amino groups is between 2,553-2,654 A.
  • the present invention relates to a microporous crystalline material, which has a chemical composition:
  • - M is an element, or mixture of elements, other than Si, Al and P; preferably selected from Co, Zn, Mg, or mixtures thereof;
  • x is between 0 and 1.5, preferably between 0 and 0.8;
  • y is between 0.3 and 1 .6, preferably between
  • the value of z is between 0 and 1.5, preferably between 0 and 0.8;
  • This new porous crystalline material called ITQ-51 both in its calcined and synthesized form without calcining, has a powder X-ray diffraction pattern that is different from other known zeolitic materials and whose most important diffraction lines are given in the Table 1 for the calcined and anhydrous form and in Table 2 for the uncalcined form.
  • 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 the structure. These modifications, which also include changes in relative intensities, may also be due to differences in the type and amount of compensation cations, network composition, crystal size and shape thereof, preferred orientation or the type of thermal or hydrothermal treatments suffered .
  • the ITQ-51 microporous crystalline material can have "z" equal to zero, so it would have the following chemical composition:
  • x is between 0 and 1.5, preferably between 0 and 0.8.
  • y is between 0.3 and 1 .6, preferably between
  • the microporous crystalline material may have "x" equal to zero and may possess a chemical composition:
  • y is between 0.3 and 1 .6, preferably between 0.6 and 1 .3.
  • z is between 0 and 1.5, preferably between 0 and 0.8.
  • the microporous crystalline material may have "x" and "z" equal to zero and may have a chemical composition:
  • y is between 0.3 and 1 .6, preferably between 0.6 and 1 .3.
  • the microporous crystalline material may have a chemical composition:
  • - R is a structure directing agent preferably selected from an amine, a tetraalkylammonium salt, an organic molecule containing P, or an organic molecule containing P-N bonds and combinations thereof.
  • n / (1 + x + y + z) is between 0 and 8, preferably between 0.001 and 3, and more preferably between 0.05 and 2.
  • - M is an element, or mixture of elements, other than Si, Al and P.
  • x is between 0 and 1.5, preferably between 0 and 0.8.
  • y is between 0.3 and 1 .6, preferably between 0.6 and 1 .3.
  • z is between 0 and 1.5, preferably between 0 and 0.8.
  • the structure directing agent, R is a proton sponge, and preferably 1,8-bis (dimethylamine) naphthalene.
  • "z" may be zero and the microporous crystalline material called ITQ-51 may have a chemical composition:
  • n / (1 + x + y) is between 0 and 8, preferably between 0.001 and 3, and more preferably between 0.05 and 2.
  • x is between 0 and 1.5, preferably between 0 and 0.8.
  • y is between 0.3 and 1 .6, preferably between 0.6 and 1 .3.
  • microporous crystalline material may have the following chemical composition:
  • n R At 2 0 3 : and P 2 0 5
  • n / (1 + y) is between 0 and 8, preferably between 0.001 and 3, and more preferably between 0.05 and 2.
  • y is between 0.3 and 1 .6, preferably between 0.6 and 1 .3.
  • microporous crystalline material may have the following chemical composition:
  • n / (1 + and + z) is between 0 and 8, preferably between 0.001 and 3, and more preferably between 0.05 and 2.
  • y is between 0.3 and 1 .6, preferably between 0.6 and 1 .3.
  • the organic component of the ADE can be removed, for example, by extraction or by heat treatment by heating at a temperature above 250 ° C for a period of time between 2 minutes and 25 hours, preferably between 1 hour and 8 hours.
  • the compensation cations in the material in its uncalcined form, or after thermal treatment can be exchanged in the case of being present, by other cations such as metal ions, H + and precursors of H + such as NH4 + .
  • cations that can be introduced by ion exchange those that can have a positive role in the activity of the material as a catalyst are preferred, and more specifically cations such as H + , rare earth cations, and group VIII metals are preferred, as well as from the NA, MIA, IVA, VA, IB, IIB, IIIB, IVB, VB, VIIB group of the periodic table of the elements.
  • the crystalline material described can also be combined intimately with hydrogenating-dehydrogenating components preferably selected from platinum, palladium, nickel, rhenium, cobalt, tungsten, molybdenum, vanadium, chromium, manganese, iron and combinations thereof.
  • hydrogenating-dehydrogenating components preferably selected from platinum, palladium, nickel, rhenium, cobalt, tungsten, molybdenum, vanadium, chromium, manganese, iron and combinations thereof.
  • the introduction of these elements can be carried out in the crystallization stage, by exchange (if applicable), and / or by impregnation or by physical mixing.
  • These elements can be introduced in their cationic form and / or from salts or other compounds that by decomposition generate the metal component or oxide in its appropriate catalytic form.
  • a material preparation procedure may comprise at least the following steps: a) preparation of a mixture containing at least H 2 0; an oxide or other source of aluminum; an oxide or other source of phosphorus; an oxide or a source of silicon; an oxide or a source of one or more metal elements M, where M is at least one heteroatom other than Si, Al and P; a structure managing agent (R); where the synthesis mixture has a molar composition of oxides in the following ranges:
  • M may be selected from Zn, Mg, Co and mixtures thereof.
  • the structure directing agent R is an amine, a tetraalkylammonium salt, an organic molecule containing P, or an organic molecule containing P-N bonds.
  • R may be a "proton sponge", and more preferably it may be 1,8- bis (dimethylamine) naphthalene.
  • the crystallization of ITQ-51 can be carried out in static or stirring, in autoclaves at a temperature between 80 and 200 ° C, at times sufficient to achieve crystallization, for example between 12 hours and 60 days.
  • the ITQ-51 crystals are separated from the mother liquors, and recovered. It should be taken into account that the components of the synthesis mixture can come from different sources, and depending on these, crystallization times and conditions may vary.
  • ITQ-51 crystals can be added as seeds, in amounts of up to 25% by weight with respect to the total oxides, to the synthesis mixture. These can be added before or during the crystallization of ITQ-51.
  • the process of obtaining the crystalline material may further comprise a step of calcining said crystalline material that can be carried out at a temperature selected between 200 and 1000 ° C.
  • the ITQ-51 material described above and obtained according to the obtaining procedure described above can be used for the transformation of organic compounds, preferably to convert feeds formed by organic compounds into products of higher added value.
  • This gel is transferred to a steel autoclave with the Teflon protected inner walls, and heated at 135 ° C for five days. After this time, the resulting solid is recovered by filtration, washing it thoroughly with water, and subsequently drying it at 100 ° C for one hour. By means of X-ray diffraction it is observed that the solid obtained contains the characteristic peaks of ITQ-51, shown in Table 2.
  • the material is calcined at 550 ° C for 3 hours in air flow to remove organic matter.
  • the powder X-ray diffraction pattern of the solid contains the characteristic peaks of the ITQ-51 zeolite shown in Table 1.
  • the composition of the final gel is 0.4 S ⁇ 0 2/1 Al 2 0 3 / 0.9 P 2 0 5/1 1 DMAN / 38 H 2 0.
  • This gel is transferred to a steel autoclave with inner walls protected by Teflon , and heated at 150 ° C for five days. After this time, the resulting solid is recovered by filtration, washing it thoroughly with water, and subsequently drying it at 100 ° C for one hour.
  • X-ray diffraction it is observed that the solid obtained contains the characteristic peaks of ITQ-51, shown in Table 2.
  • the material is calcined at 550 ° C for 3 hours in air flow to remove organic matter.
  • the powder X-ray diffraction pattern of the solid contains the characteristic peaks of the ITQ-51 zeolite shown in Table 1.
  • the composition of the final gel is 1 Al 2 0 3/1 1 P2O5 / Mg 0.2 / 1 0.3 DMAN / 42 H 2 0.
  • This gel is transferred to a steel autoclave with inner walls protected by Teflon, and heated at 135 ° C for five days. After this time, the resulting solid is recovered by filtration, washing it thoroughly with water, and subsequently drying it at 100 ° C for one hour. By means of X-ray diffraction it is observed that the solid obtained contains the characteristic peaks of ITQ-51, shown in Table 2.
  • the material is calcined at 550 ° C for 3 hours in air flow to remove organic matter.
  • the powder X-ray diffraction pattern of the solid contains the characteristic peaks of the ITQ-51 zeolite shown in Table 1.
  • the composition of the final gel is 1 Al 2 0 3/1 2 P 2 0 5 / 0.2 Zn / 0.3 DMAN 1/42 H 2 0.
  • This gel is transferred to a steel autoclave with inner walls protected Teflon and heated at 135 ° C for five days. After this time, the resulting solid is recovered by filtration, washing it thoroughly with water, and subsequently drying it at 100 ° C for one hour. By means of X-ray diffraction it is observed that the solid obtained contains the characteristic peaks of ITQ-51, shown in Table 2.
  • the composition of the final gel is 1 Al 2 0 3/1 1 P2O5 / Co 0.2 / 1 0.3 DMAN / 42 H 2 0.
  • This gel is transferred to a steel autoclave with inner walls protected by Teflon, and heated at 135 ° C for five days. After this time, the resulting solid is recovered by filtration, washing it thoroughly with water, and subsequently drying it at 100 ° C for one hour. By means of X-ray diffraction it is observed that the solid obtained contains the characteristic peaks of ITQ-51, shown in Table 2.
  • the material is calcined at 550 ° C for 3 hours in air flow to remove organic matter.
  • the powder X-ray diffraction pattern of the solid contains the characteristic peaks of the ITQ-51 zeolite shown in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Materials Engineering (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne une matière cristalline appelée ITQ-51 et qui présente une composition molaire dans son état calciné et anhydre qui est donnée par l'équation: x Si02 : AI2O3 : et P205 : z M où: M est un élément, ou mélange d'éléments, différents de Si, Al et P; - la valeur de x est comprise entre 0 et 1,5, de préférence entre 0 et 0,8; - la valeur de y est comprise entre 0,3 et 1,6, de préférence entre 0,6 et 1,3; - la valeur de z est comprise entre 0 et 1,5, de préférence entre 0 et 0,8.
PCT/ES2014/070063 2013-02-06 2014-01-28 Synthèse de la zéolithe itq-51, procédé d'obtention et d'utilisation WO2014122344A1 (fr)

Applications Claiming Priority (2)

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ES201330141A ES2492415B1 (es) 2013-02-06 2013-02-06 Síntesis de la zeolita itq-51, procedimiento de obtención y uso
ESP201330141 2013-02-06

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WO2014122344A1 true WO2014122344A1 (fr) 2014-08-14

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015196023A1 (fr) * 2014-06-20 2015-12-23 Exxonmobil Research And Engineering Company Séparation, stockage et conversion catalytique de fluides à l'aide d'itq-55

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
BU, XIANHUI; ET AL.: "Crystalline microporous and open framework materials.", THE CHEMISTRY OF NANOSTRUCTURED MATERIALS, 2002, pages 1 - 37 *
DAVIS, MARK E.: "Ordered porous materials for emerging applications.", NATURE, vol. 417, no. 6891, 2002, pages 813 - 821 *
FAN, DONG ET AL.: "A novel solvothermal approach to synthesize SAPO molecular sieves using organic amines as the solvent and template.", JOURNAL OF MATERIALS CHEMISTRY, vol. 22, no. 14, 2012, pages 6568 - 6574 *
LLAMAS-SAIZ, A. L.; ET AL.: "J. Proton sponges.", JOURNAL OF MOLECULAR STRUCTURE, vol. 328, 1994, pages 297 - 323 *
MARTÍNEZ-FRANCO, RAQUEL ET AL.: "Synthesis of an extra-large molecular sieve using proton sponges as organic structure-directing agents.", PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES, vol. 110, no. 10, 2013, pages 3749 - 3754 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015196023A1 (fr) * 2014-06-20 2015-12-23 Exxonmobil Research And Engineering Company Séparation, stockage et conversion catalytique de fluides à l'aide d'itq-55
WO2015196043A1 (fr) * 2014-06-20 2015-12-23 Exxonmobil Research And Engineering Company Séparation et stockage de fluides utilisant de l'itq-55
WO2015196049A1 (fr) * 2014-06-20 2015-12-23 Exxonmobil Research And Engineering Company Séparation et stockage de fluides à l'aide du itq-55
WO2015196018A1 (fr) * 2014-06-20 2015-12-23 Higher Council Of Scientific Research (Csic) Matériau itq-55, procédé pour sa préparation et son utilisation
WO2015196026A1 (fr) * 2014-06-20 2015-12-23 Exxonmobil Research And Engineering Company Séparation et stockage de fluides à l'aide du itq-55
KR20170021314A (ko) * 2014-06-20 2017-02-27 엑손모빌 리서치 앤드 엔지니어링 컴퍼니 Itq-55를 사용한 유체 분리 및 저장
US9617164B2 (en) 2014-06-20 2017-04-11 Exxonmobil Research And Engineering Company Separation, storage, and catalytic conversion of fluids using ITQ-55
US9688542B2 (en) 2014-06-20 2017-06-27 Exxonmobil Research And Engineering Company Separation and storage of fluids using ITQ-55
US9695056B2 (en) 2014-06-20 2017-07-04 Exxonmobil Research And Engineering Company Separation and storage of fluids using ITQ-55
US9738539B2 (en) 2014-06-20 2017-08-22 Exxonmobil Research And Engineering Company Separation and storage of fluids using ITQ-55
US9856145B2 (en) 2014-06-20 2018-01-02 Exxonmobil Research And Engineering Company Material ITQ-55, method for preparation and use
RU2682600C2 (ru) * 2014-06-20 2019-03-19 Хайер Каунсил Оф Сайентифик Рисерч (Ксис) Материал ITQ-55, способ получения и применение
KR102360244B1 (ko) 2014-06-20 2022-02-09 엑손모빌 리서치 앤드 엔지니어링 컴퍼니 Itq-55를 사용한 유체 분리 및 저장

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ES2492415A1 (es) 2014-09-08

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