US20080035524A1 - Microporous Amorphous Material, Preparation Method Thereof and Use of Same in the Catalytic Conversion of Organic Compounds - Google Patents

Microporous Amorphous Material, Preparation Method Thereof and Use of Same in the Catalytic Conversion of Organic Compounds Download PDF

Info

Publication number
US20080035524A1
US20080035524A1 US11/547,805 US54780505A US2008035524A1 US 20080035524 A1 US20080035524 A1 US 20080035524A1 US 54780505 A US54780505 A US 54780505A US 2008035524 A1 US2008035524 A1 US 2008035524A1
Authority
US
United States
Prior art keywords
sio
amorphous material
material according
elements
organic compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US11/547,805
Inventor
Avelino Corma Canos
Maria Diaz Cabanas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Consejo Superior de Investigaciones Cientificas CSIC
Universidad Politecnica de Valencia
Original Assignee
Consejo Superior de Investigaciones Cientificas CSIC
Universidad Politecnica de Valencia
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Consejo Superior de Investigaciones Cientificas CSIC, Universidad Politecnica de Valencia filed Critical Consejo Superior de Investigaciones Cientificas CSIC
Assigned to UNIVERSIDAD POLITECNICA DE VALENCIA, CONSEJO SUPERIOR DE INVESTIGACIONES CIENTIFICAS reassignment UNIVERSIDAD POLITECNICA DE VALENCIA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DIAZ CABANAS, MARIA JOSE, CORMA CANOS, AVELINO
Publication of US20080035524A1 publication Critical patent/US20080035524A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and alumina
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B01J35/60—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/033—Using Hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/46—Amorphous silicates, e.g. so-called "amorphous zeolites"
    • 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
    • C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
    • 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
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
    • C07C2/66—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J35/615—
    • B01J35/633—
    • B01J35/643—
    • B01J35/66—

Definitions

  • Zeolites are microporous crystalline materials formed by a crystal lattice of TO 4 tetrahedra which share all their vertices giving rise to a three-dimensional structure containing channels and/or cavities of molecular dimensions. They have variable composition, and T generally represents atoms with formal oxidation state of +3 or +4, such as for example Si, Ge, Ti, Al, B or Ga, among others.
  • each zeolite with a specific system of channels and cavities, gives rise to a characteristic X-ray diffraction pattern. So, the zeolites are differentiated among each other by their range of chemical composition and their X-ray diffraction pattern. Both characteristics (crystal structure and chemical composition) also determine the physico-chemical properties of each zeolite and its possible application in different industrial processes.
  • Amorphous micro- and mesoporous materials have been developed such as silicates, silicoaluminates and silicotitanates, among others, in an attempt to achieve molecular sieve properties, in other words very narrow pore distributions.
  • microporous materials when there existed a narrow distribution of pores, it was found that the materials could not be regarded as completely amorphous.
  • IR infrared
  • the present invention relates to a microporous amorphous material characterised in that it has a chemical composition in the calcined and anhydrous state which can be represented by the following empirical formula: x(M 1/n XO 2 ):y YO 2 :SiO 2 wherein:
  • X is preferably selected from among Al, Ga, B, Fe, Cr and a mixture of same
  • Y is preferably selected from among Ti, Ge, Sn, V and a mixture of same.
  • said microporous amorphous material is characterised in that it has a chemical composition in the calcined and anhydrous state which can be represented by the following empirical formula: x(M 1/n XO 2 ):y YO 2 :SiO 2 wherein:
  • the trivalent element or elements X are preferably selected from among Al, Ga, B, Fe, Cr and a mixture of same
  • Y is preferably selected from among Ti, Ge, Sn, V and a mixture of same
  • the inorganic cations which M can represent can be cited, for example, one or more alkaline, alkaline earth metals or mixtures of same.
  • the microporous amorphous material can have a composition which corresponds to the formula: x(M 1/n XO 2 ):SIO 2 wherein:
  • the microporous amorphous material has a composition in the calcined and anhydrous state which corresponds to the formula: y YO 2 :SiO 2 wherein:
  • the microporous amorphous material has a composition in the calcined and anhydrous state which corresponds to the formula: x(HXO 2 ):SiO 2 wherein:
  • the microporous amorphous material has a composition in the calcined and anhydrous state which corresponds to the formula SiO 2 .
  • microporous non-crystalline material of the present invention which we shall generically call MAS, has a pore distribution that is narrow and uniform in the micropore range.
  • Said microporous non-crystalline material is characterised in that its X-ray diffraction pattern does not display any diffraction peaks and its IR spectrum does not show bands developed in the range between 400 and 600 cm ⁇ 1 , such bands being characteristic of crystalline silicates, such as for example zeolites.
  • the present invention also relates to a method for synthesising a microporous amorphous material defined earlier, comprising at least:
  • reaction mixture comprising at least:
  • the method for synthesising a microporous amorphous material comprises:
  • reaction mixture comprising at least:
  • the method for synthesising a microporous amorphous material comprises:
  • reaction mixture comprising at least:
  • the method for synthesising a microporous amorphous material comprises:
  • reaction mixture comprising at least:
  • the method for synthesising a microporous amorphous material comprises:
  • reaction mixture comprising at least:
  • the reaction mixture has a composition, in terms of molar ratios of oxides, lying between the intervals:
  • the sources of SiO 2 can be mentioned, for example, tetraethylorthosilicate, colloidal silica and amorphous silica.
  • Al can be used; for example, aluminium alcoxides, aluminium oxides or aluminium salts can all be used as sources of aluminium.
  • the organic compound R is preferably in the form of hydroxide.
  • the organic cation in salt form (for example, a halide, preferably chloride, bromide or iodide).
  • the organic compound comprises one or more amine groups.
  • Said organic compound can also comprise one or more ammonium groups.
  • the organic compound is selected from among N(16)-methylsparteinium, 1,4-biscyclohexylpyrrolidiniumbutane hydroxide, 1,8-bisquinuclidiniumoctane hydroxide, 1,4-biscyclohexylpyrrolidiniumbutane hydroxide, hexamethonium hydroxide and tetraethylammonium hydroxide.
  • the heat treatment of the reaction mixture can be carried out statically or with stirring of the mixture.
  • the solid product is separated and dried.
  • the reaction mixture has a composition which accords with the empirical formula: a ROH:b M 1/n F:x X 2 O 3 :y YO 2 :SiO 2 :w H 2 O where X is one or more elements in an oxidation state +3, Y is one or more elements in an oxidation state +4, M is selected from among H + , one or more inorganic cations of charge +n and mixtures of same; and R is one or more organic compounds, and the values a, b, x, y and w are in the ranges:
  • the present invention also refers to a method of use of the microporous amorphous material defined earlier as a catalyst in a conversion process for organic compounds consisting of placing a feed in contact with a quantity of that catalyst.
  • Said process can be a process of catalytic cracking of organic compounds, preferably hydrocarbons.
  • the process is selected from among a hydrocracking process, gentle hydrocracking of hydrocarbons, gentle hydrocracking of functionalised hydrocarbons, gentle hydrocracking of hydrocarbons and functionalised hydrocarbons, hydroisomerisation of olefins, an isomerisation process of light paraffins, deparaffining, isodeparaffining and an alkylation process.
  • said alkylation can be selected from among alkylation of isoparaffins with olefins, alkylation of olefins with isoparaffins, alkylation of aromatics with olefins or alcohols, alkylation of substituted aromatics with olefins or alcohols, alkylation of thiophenic compounds with olefins or alcohols, alkylation of alkylthiophenic compounds with olefins or alcohols and alkylation of alkylbenzothiophenic compounds with olefins or alcohols.
  • said alkylation is the alkylation of benzene with propylene.
  • the microporous amorphous material can act as a catalyst in a process which is an acylation reaction of substituted aromatic compounds using acids, acid chlorides or organic acid anhydrides as acylating agents.
  • the process is a selective oxidation of organic compounds using an oxidising agent selected from among H 2 O 2 , organic peroxides and organic hydroperoxides.
  • the process is selected from among a Meerwein-Pondorf-Verley type oxidation reaction and a Baeyer-Villiger type oxidation reaction.
  • said microporous amorphous material can be used as a catalyst in a process of epoxidation of olefins, oxidation of alkanes, oxidation of alcohols and oxidation of organic compounds containing sulphur and which can produce sulphoxides and sulphones, using organic or inorganic hydroperoxides, such as for example, H 2 O 2 , tertbutylhydroperioxide, cumene hydroperoxide or molecular oxygen as oxidising agents and in ammoximation of ketones, and more specifically of cyclohexanone to cyclohexanone oxime with NH 3 and H 2 O 2 , or NH 3 and O 2 .
  • organic hydroperoxides such as for example, H 2 O 2 , tertbutylhydroperioxide, cumene hydroperoxide or molecular oxygen as oxidising agents and in ammoximation of ketones, and more specifically of cyclohexan
  • the microporous amorphous material of the present invention can be used as a catalyst in a Baeyer-Villiger type oxidation using H 2 O 2 as the oxidising agent.
  • FIG. 1 shows the X-ray diffraction diagram of a sample of the microporous amorphous material of the invention, prepared as per example 1, using N(16)-methylspartenium, and prior to calcining.
  • FIG. 2 shows the IR spectrum of a sample of the microporous amorphous material of the invention, known as MAS-1, prepared as per example 1, using N(16)-methylspartenium, and prior to calcining.
  • FIG. 3 shows the pore distribution of a sample of the microporous amorphous material of the invention, prepared as per example 1, using N(16)-methylspartenium, and calcined.
  • FIG. 4 shows the X-ray diffraction diagram of a sample of the microporous amorphous material of the invention, prepared as per example 2, using N(16)-methylspartenium, and prior to calcining.
  • FIG. 5 shows the X-ray diffraction diagram of a sample of the microporous amorphous material of the invention containing Ti, prepared as per example 3, using N(16)-methylspartenium, and without calcining.
  • FIG. 6 shows the X-ray diffraction diagram of a sample of the microporous amorphous material of the invention, pure silica MAS-1, and prepared as per example 4, using N(16)-methylspartenium, and without calcining.
  • FIG. 7 shows the X-ray diffraction diagram of a sample of the microporous amorphous material of the invention, prepared as per example 5, known as MAS-2, using 1,8-bisquinuclidiniumoctane hydroxide, and without calcining.
  • FIG. 8 shows the IR spectrum of a sample of the microporous amorphous material of the invention, prepared as per example 5, using 1,8-bisquinuclidiniumoctane hydroxide, and without calcining.
  • FIG. 9 shows the pore distribution of a sample of the microporous amorphous material of the invention, prepared as per example 5, using 1,8-bisquinuclidiniumoctane hydroxide, and calcined.
  • FIG. 10 shows the X-ray diffraction diagram of a sample of the microporous amorphous material of the invention, prepared as per example 6, using 1,8-bisquinuclidiniumoctane hydroxide, and without calcining.
  • FIG. 11 shows the X-ray diffraction diagram of a sample of the microporous amorphous material of the invention, prepared as per example 7, known as MAS-3, using 1,4-biscyclohexylpyrrolidiniumbutane hydroxide, and without calcining.
  • FIG. 12 shows the IR spectrum of a sample of the microporous amorphous material of the invention, prepared as per example 7, using 1,4-biscyclohexylpyrrolidiniumbutane hydroxide, and without calcining.
  • FIG. 13 shows the pore distribution of a sample of the microporous amorphous material of the invention, prepared as per example 7, using 1,4-biscyclohexylpyrrolidiniumbutane hydroxide, and calcined.
  • FIG. 14 shows the X-ray diffraction diagram of a sample of the microporous amorphous material of the invention, prepared as per example 8, using 1,4-biscyclohexylpyrrolidiniumbutane hydroxide, and without calcining.
  • FIG. 15 shows the X-ray diffraction diagram of a sample of the microporous amorphous material of the invention, prepared as per example 9, known as MAS-4, using hexamethonium hydroxide, and without calcining.
  • FIG. 16 shows the IR spectrum of a sample of the microporous amorphous material of the invention, prepared as per example 9, using hexamethonium hydroxide, and without calcining.
  • FIG. 17 shows the pore distribution of a sample of the microporous amorphous material of the invention, prepared as per example 9, using hexamethonium hydroxide, and calcined.
  • FIG. 18 shows the X-ray diffraction diagram of a sample of the microporous amorphous material of the invention, prepared as per example 10, known as MAS-5, using tetraethylammonium hydroxide, and without calcining.
  • FIG. 19 shows the IR spectrum of a sample of the microporous amorphous material of the invention, prepared as per example 10, using tetraethylammonium hydroxide, and without calcining.
  • FIG. 20 shows the X-ray diffraction diagram of a sample of the microporous amorphous material of the invention, prepared as per example 11, using tetraethylammonium hydroxide, and without calcining.
  • the gel is heated at 175° C. statically for 16 hours in steel autoclaves with an internal Teflon lining.
  • the solid obtained after filtering, washing with distilled water and drying at 100° C. is MAS1.
  • the X-ray diffraction pattern of the solid obtained, measured by the powder method using a fixed divergence grating and employing K a from Cu, is shown in FIG. 1 and the IR spectrum in FIG. 2 .
  • the material is calcined at 580° C. for 3 hours in an air stream in order to eliminate organic matter and the fluoride ions occluded in its interior.
  • the solid known as MAS-1 displays a specific surface area of 738 m 2 /g and a micropore volume of 0.28 cm 3 /g.
  • the pore diameter is 7.5 ⁇ and the pore distribution measured by Ar adsorption following the Hovartz-Kavazoe formalism is shown in FIG. 3 .
  • the gel is heated for 16 hours in steel autoclaves with an internal Teflon lining at 175° C. statically.
  • the solid obtained after filtering, washing with distilled water and drying at 100° C. is MAS-1.
  • the X-ray diffraction pattern of the solid obtained is shown in FIG. 4 .
  • the solid After calcining at 580° C. in an air stream for 3 hours, the solid, known as MAS-1, displays a specific surface area of 643 m 2 /g and a micropore volume of 0.24 cm 3 /g.
  • the gel is heated at 175° C. statically for 3 days in steel autoclaves with an internal Teflon lining.
  • the solid obtained after filtering, washing with distilled water and drying at 100° C. is Ti-MAS1.
  • the X-ray diffraction pattern of the solid obtained is shown in FIG. 5 .
  • the gel is heated for 7 days in steel autoclaves with an internal Teflon lining at 175° C. with stirring.
  • the solid obtained after filtering, washing with distilled water and drying at 100° C. is MAS-2.
  • the X-ray diffraction pattern of the solid obtained is shown in FIG. 7 and the IR spectrum in FIG. 8 .
  • the material is calcined at 580° C. for 3 hours in an air stream in order to eliminate organic matter and the fluoride ions occluded in its interior.
  • the solid known as MAS-2 displays a specific surface area of 388 m 2 /g and a micropore volume of 0.14 cm 3 /g.
  • the pore diameter is 6.0 ⁇ and the pore distribution measured by Ar adsorption following the Hovartz-Kavazoe formalism is shown in FIG. 3 .
  • the gel is heated for 3 days in steel autoclaves with an internal Teflon lining at 150° C. with stirring.
  • the solid obtained after filtering, washing with distilled water and drying at 100° C. is MAS-2.
  • the X-ray diffraction pattern of the solid obtained is shown in FIG. 10 .
  • the gel is heated at 175° C. with stirring for 5 days in steel autoclaves with an internal Teflon lining.
  • the solid obtained after filtering, washing with distilled water and drying at 100° C. is MAS-3.
  • the X-ray diffraction pattern of the solid obtained is shown in FIG. 11 and the IR spectrum in FIG. 12 .
  • the material is calcined at 580° C. for 3 hours in an air stream in order to eliminate organic matter and the fluoride ions occluded in its interior.
  • the solid known as MAS-1 displays a specific surface area of 418 m 2 /g and a micropore volume of 0.15 cm 3 /g.
  • the pore diameter is 6.2 ⁇ and the pore distribution measured by Ar adsorption following the Hovartz-Kavazoe formalism is shown in FIG. 13 .
  • the gel is heated for 4 days in steel autoclaves with an internal Teflon lining at 175° C. with stirring.
  • the solid obtained after filtering, washing with distilled water and drying at 100° C. is MAS-3.
  • the X-ray diffraction pattern of the solid obtained is shown in FIG. 14 .
  • the gel is heated for 5 days in steel autoclaves with an internal Teflon lining at 135° C. with stirring.
  • the solid obtained after filtering, washing with distilled water and drying at 100° C. is MAS-4.
  • the X-ray diffraction pattern of the solid obtained is shown in FIG. 15 and the IR spectrum in FIG. 16 .
  • the material is calcined at 580° C. for 3 hours in an air stream in order to eliminate organic matter and the fluoride ions occluded in its interior.
  • the solid known as MAS-4 displays a specific surface area of 348 m 2 /g and a micropore volume of 0.13 cm 3 /g.
  • the pore diameter is 5.5 ⁇ and the pore distribution measured by Ar adsorption following the Hovartz-Kavazoe formalism is shown in FIG. 17 .
  • tetraethylorthosilicate 19.9 g of tetraethylorthosilicate are added to 14.39 g of an aqueous solution of tetraethylammonium hydroxide (TEAOH) at 40% by weight and 3 g of water, and the mixture is stirred. A solution is then added containing 0.32 g of metallic aluminium (99.95%) previously dissolved in 9 g of TEAOH (40%). The mixture is left to evaporate with stirring until complete elimination of the ethanol coming from the hydrolysis of the TEOS plus the quantity of water necessary for reaching the final composition that is stated. Finally, 2.15 g of an aqueous solution of fluorhydric acid (48% of HF by weight) is added. The composition of the gel is: SiO 2 :0.062 Al 2 O 3 :0.665 ROH:0.54 HF:7 H 2 O where ROH is tetraethylammonium hydroxide.
  • TEAOH tetraethylammonium
  • the mixture obtained is introduced into an autoclave provided with an internal polytetrafluorethylene lining and is heated at 140° C. for 6 days in a stove provided with a rotation system. After that time, it is recovered by means of filtering, washed with water and then dried at 100° C, giving 27.9 g of solid per 100 g of gel.
  • the solid obtained is MAS-5 and its X-ray diffraction pattern of the solid obtained is shown in FIG. 18 and the IR spectrum in FIG. 19 .
  • the material is calcined at 580° C. for 3 hours in an air stream in order to eliminate organic matter and the fluoride ions occluded in its interior.
  • tetraethylorthosilicate 15.00 grams of tetraethylorthosilicate are hydrolysed in 16.36 grams of a solution of tetraethylammonium hydroxide (TEAOH) at 40% by weight and 3 g of water, and the mixture is stirred. The solution obtained is kept being stirred allowing all the alcohol formed in the hydrolysis and the surplus water to evaporate. Afterwards, 1.56 g of a solution of fluorhydric acid (50% of HF by weight) is then added and evaporation is continued until the mixture reaches a final composition: SiO 2 :0.54 ROH:0.54 HF:7 H 2 O where ROH is tetraethylammonium hydroxide.
  • TEAOH tetraethylammonium hydroxide
  • the gel is heated at 175° C. with stirring for 4 hours in steel autoclaves with an internal Teflon lining.
  • the solid obtained after filtering, washing with distilled water and drying at 100° C. is MAS-5 and its X-ray diffraction pattern is shown in FIG. 20 .
  • This example shows the catalytic activity of a bifunctional catalyst formed from an acid function (MAS, prepared as per example 2) and a hydrogenating-dehydrogenating function (Pt 1.0% by weight), introduced by impregnation starting from an aqueous solution of hexachloroplatinic acid, for the hydrocracking of n-hexadecane.
  • the reaction was carried out in a fixed bed continuous reactor at 270° C., pressure 40 bars, with a molar ratio of H 2 /hexadecane of 95 and a contact time (W/F) of 0.27 hours.
  • This example shows the catalytic activity of a bifunctional catalyst formed from an acid function (MAS, prepared as per example 2) and a hydrogenating function (Pt 1% by weight), introduced by impregnation starting from an aqueous solution of hexachloroplatinic acid, for the hydrocracking of a hydrotreated gasoil containing 10.6% by weight of hydrocarbons with a boiling point between 250° C. and 380° C., and 89.4% with boiling point above 380° C., and a sulphur content of 87 ppm.
  • This example shows the catalytic activity for catalytic cracking of an MAS material prepared according to example 2, in which n-decane is used as reagent.
  • the reaction conditions were: atmospheric pressure, weight ratio of catalyst/feed of 0.70, temperature of 500° C. and reaction time of 60 seconds. Under these conditions the conversion was 33%.
  • This example shows the catalytic activity for cracking of a vacuum gasoil, of the MAS material prepared as per example 2.
  • the reaction conditions were: atmospheric pressure, weight ratio of catalyst/feed of 0.65, reaction temperature of 500° C. and reaction time of 60 seconds.
  • the conversion was 60% by weight, with a yield to gases, gasoline, diesel and coke of 19.1, 23.2, 14.0 and 3.7%, respectively, the propylene/propane ratio in the gases being 4.9, for a propylene yield of 7%.

Abstract

The invention relates to a microporous amorphous material which is characterised in that it has a chemical composition in the calcined and anhydrous state which can be represented by the empirical formula x (M1/nXO2):y YO2:SiO2, wherein: x has a value of less than 0.2 and can be equal to zero; y has a value of less than 0.2 and can be equal to zero; M is selected from among H+, one or more inorganic cations having a +n charge and a mixture of same; X is one or more chemical elements in oxidation state +3; and Y is one or more elements in oxidation state +4. The inventive material is also characterised in that it has a uniform pore distribution, a micropore volume of greater than or equal to 0.05 cm3.g−1 and a specific surface area of greater than 100 m2.g−1. The invention also relates to the preparation method thereof and use of same.

Description

    FIELD OF THE ART
  • Microporous molecular sieves.
    • STATE OF THE ART
  • Zeolites are microporous crystalline materials formed by a crystal lattice of TO4 tetrahedra which share all their vertices giving rise to a three-dimensional structure containing channels and/or cavities of molecular dimensions. They have variable composition, and T generally represents atoms with formal oxidation state of +3 or +4, such as for example Si, Ge, Ti, Al, B or Ga, among others.
  • The existence of channels and cavities of regular dimensions in the interior of the zeolites gives rise to a high specific area. The fact that the pore size is uniform and with a narrow distribution in these crystalline materials permits them to selectively adsorb molecules of a different size depending on the dimensions of the channels.
  • Moreover, the crystal structure of each zeolite, with a specific system of channels and cavities, gives rise to a characteristic X-ray diffraction pattern. So, the zeolites are differentiated among each other by their range of chemical composition and their X-ray diffraction pattern. Both characteristics (crystal structure and chemical composition) also determine the physico-chemical properties of each zeolite and its possible application in different industrial processes.
  • Amorphous micro- and mesoporous materials have been developed such as silicates, silicoaluminates and silicotitanates, among others, in an attempt to achieve molecular sieve properties, in other words very narrow pore distributions. In the case of microporous materials, when there existed a narrow distribution of pores, it was found that the materials could not be regarded as completely amorphous. In fact, although they did not possess any long range order, according to the X-ray diffractograms, they did indeed have short range order, as was highlighted by infrared (IR) spectroscopy, due to which the authors concluded that their material contained cores of a crystalline material, such as might be zeolite (Kragten, D. D.; Fedeyko, J. M.; Sawant, K. R.; Rimer, J. D.; Vlachos, D. G.; Lobo, R. F.; Tsapatsis, M. Journal of Physical Chemistry B (2003), 107(37), 10006-10016).
  • In the case of mesoporous materials, the synthesis of non-crystalline mesoporous molecular sieves developed by Kresge et al. using surfactants has opened up a new field of applications in adsorption, catalysis and electronics (Kresge, C. T.; Leonowicz, M. E.; Roth, W. J.: Vartuli, J. C.; Beck, J. S. Nature (1992), 359 (6397), 710-712).
  • It could thus be expected that the development of new non-crystalline mesoporous molecular sieves could open up new applications in the aforementioned fields when pores of less than 2 nm, and less than 1 nm even, are required.
    • DESCRIPTION OF THE INVENTION
  • The present invention relates to a microporous amorphous material characterised in that it has a chemical composition in the calcined and anhydrous state which can be represented by the following empirical formula:
    x(M1/nXO2):y YO2:SiO2
    wherein:
    • x has a value of less than 0.2, preferably less than 0.1, and can be equal to zero,
    • y has a value of less than 0.2, preferably less than 0.1, and can be equal to zero,
    • M is selected from among H+, one or more inorganic cations having a charge +n and a mixture of same;
    • X is one or more chemical elements in oxidation state +3; and
    • Y is one or more elements in oxidation state +4,
      which has a uniform pore distribution and a micropore volume of greater than or equal to 0.05 cm3.g−1 and
      which has a specific surface area of greater than 100 m2.g−1
  • In the microporous amorphous material, X is preferably selected from among Al, Ga, B, Fe, Cr and a mixture of same, and Y is preferably selected from among Ti, Ge, Sn, V and a mixture of same.
  • According to a preferred embodiment, said microporous amorphous material is characterised in that it has a chemical composition in the calcined and anhydrous state which can be represented by the following empirical formula:
    x(M1/nXO2):y YO2:SiO2
    wherein:
    • x has a value of less than 0.1, and can be equal to zero,
    • y has a value of less than 0.1, and can be equal to zero,
    • M is selected from among H+, one or more inorganic cations having a charge +n and a mixture of same;
    • X is one or more chemical elements in oxidation state +3; and
    • Y is one or more chemical elements with oxidation state +4.
  • The trivalent element or elements X are preferably selected from among Al, Ga, B, Fe, Cr and a mixture of same, Y is preferably selected from among Ti, Ge, Sn, V and a mixture of same, and among the inorganic cations which M can represent can be cited, for example, one or more alkaline, alkaline earth metals or mixtures of same.
  • According to a particular embodiment of the present invention, the microporous amorphous material can have a composition which corresponds to the formula:
    x(M1/nXO2):SIO2
    wherein:
    • x has a value of less than 0.2, and can be equal to zero,
    • M is selected from among H+, one or more inorganic cations having a charge +n and a mixture of same; and
    • X is one or more chemical elements in oxidation state +3.
  • According to a particular embodiment of the present invention, the microporous amorphous material has a composition in the calcined and anhydrous state which corresponds to the formula:
    y YO2:SiO2
    wherein:
    • y has a value of less than 0.2, preferably less than 0.1, and can be equal to zero; and
    • Y is one or more chemical elements with oxidation state +4, preferably Ti, Ge, Sn, V and a mixture of same.
  • According to a particular embodiment of the present invention, the microporous amorphous material has a composition in the calcined and anhydrous state which corresponds to the formula:
    x(HXO2):SiO2
    wherein:
    • x has a value of less than 0.2, preferably less than 0.1, and can be equal to zero; and
    • X is one or more chemical elements in oxidation state +3: preferably Al, Ga, B, Fe, Cr and a mixture of same.
  • According to a particular embodiment of the present invention, the microporous amorphous material has a composition in the calcined and anhydrous state which corresponds to the formula SiO2.
  • The microporous non-crystalline material of the present invention, which we shall generically call MAS, has a pore distribution that is narrow and uniform in the micropore range.
  • Said microporous non-crystalline material is characterised in that its X-ray diffraction pattern does not display any diffraction peaks and its IR spectrum does not show bands developed in the range between 400 and 600 cm−1, such bands being characteristic of crystalline silicates, such as for example zeolites.
  • The present invention also relates to a method for synthesising a microporous amorphous material defined earlier, comprising at least:
  • preparing a reaction mixture comprising at least:
      • a source of SiO2,
      • one or more organic compounds, and
      • water,
  • subjecting said mixture to heating with or without stirring at a temperature between 80 and 200° C., preferably between 100 and 200° C., until achieving the formation of the amorphous material, and in which the reaction mixture has a composition, in terms of molar ratios of oxides, lying between the intervals:
    • ROH/SiO2=0.01-3.0, preferably 0.1-1.0,
    • H2O/SiO2=1-100, preferably 1-50,
      where R is one or more organic compounds.
      The reaction mixture can optionally contain a source of fluoride ions, in which case fluorhydric acid or ammonium fluoride, for example, can be used as the source of fluoride ions.
  • According to a particular embodiment, the method for synthesising a microporous amorphous material comprises:
  • preparing a reaction mixture comprising at least:
      • a source of SiO2,
      • a source of one or more tetravalent elements Y,
      • one or more organic compounds,
      • water,
  • subjecting said mixture to heating with or without stirring at a temperature between 80 and 200° C., preferably between 100 and 200° C., until achieving the formation of the amorphous material, and in which the reaction mixture has a composition, in terms of molar ratios of oxides, lying between the intervals:
    • ROH/SiO2=0.01-3.0, preferably 0.1-1.0,
    • H2O/SiO2=1-100, preferably 1-50, and
    • YO2/SiO2=0.001-0.2
      where Y is one or more elements in an oxidation state +4, preferably Ti, Ge, Sn, V or a mixture of same, and R is one or more organic compounds. The addition of this or these elements, Y, can be done prior to heating the reaction mixture or at an intermediate moment during that heating. The reaction mixture can optionally contain a source of fluoride ions.
  • According to an additional particular embodiment, the method for synthesising a microporous amorphous material comprises:
  • preparing a reaction mixture comprising at least:
      • a source of SiO2,
      • a source of one or more trivalent elements X,
      • one or more organic compounds, and
      • water,
  • subjecting said mixture to heating with or without stirring at a temperature between 80 and 200° C., preferably between 100 and 200° C., until achieving the formation of the amorphous material, and in which the reaction mixture has a composition, in terms of molar ratios of oxides, lying between the intervals:
    • ROH/SiO2=0.01-3.0, preferably 0.1-1.0.
    • H2O/SiO2=1-100, preferably 1-50, and
    • X2O3/SiO2=0.001-0.1.
      where X is one or more elements in an oxidation state +3, preferably selected from among Al, Ga, B, Fe, Cr and a mixture of same, and R is one or more organic compounds. The addition of this or these trivalent elements can be done prior to heating the reaction mixture or at an intermediate moment during that heating.
      The reaction mixture can optionally contain a source of fluoride ions. In this case, the proportion of fluoride ions in the mixture is preferably HF/SiO2=0.05-3.0.
  • According to an additional particular embodiment, the method for synthesising a microporous amorphous material comprises:
  • preparing a reaction mixture comprising at least:
      • a source of SiO2,
      • a source of one or more trivalent elements X,
      • one or more elements M of charge +n,
      • one or more organic compounds, and
      • water,
  • subjecting said mixture to heating with or without stirring at a temperature between 80 and 200° C., preferably between 100 and 200° C., until achieving the formation of the amorphous material, and in which the reaction mixture has a composition, in terms of molar ratios of oxides, lying between the intervals:
    • ROH/SiO2=0.01-3.0, preferably 0.1-1.0,
    • H2O/SiO2=1-100,
    • X2O3/SiO2=0.001-0.1,
      where X is one or more elements in an oxidation state +3, M is selected from among H+, one or more inorganic cations of charge +n and mixtures of same; and R is one or more organic compounds. The addition of this or these trivalent elements X can be done prior to heating the reaction mixture or at an intermediate moment during that heating.
      The reaction mixture can optionally contain a source of fluoride ions. In this case, the proportion of fluoride ions in the mixture is preferably M1/nF/SiO2=0.05-3.0.
  • According to an additional particular embodiment, the method for synthesising a microporous amorphous material comprises:
  • preparing a reaction mixture comprising at least:
      • a source of SiO2,
      • a source of one or more trivalent elements X,
      • a source of one or more tetravalent elements Y,
      • one or more elements M of charge +n,
      • one or more organic compounds, and
      • water,
  • subjecting said mixture to heating with or without stirring at a temperature between 80 and 200° C., preferably between 100 and 200° C., until achieving the formation of the amorphous material, and in which the reaction mixture has a composition, in terms of molar ratios of oxides, lying between the intervals:
    • ROH/SiO2=0.01-3.0, preferably 0.1-1.0,
    • H2O/SiO2=1-100, preferably 1-50,
    • X2O3/SiO2=0.001-0.1, and
    • YO2/SiO2=0.001-0.2
      where X is one or more elements in an oxidation state +3. Y is one or more elements in an oxidation state +4, M is selected from among H+, one or more inorganic cations of charge +n and mixtures of same; and R is one or more organic compounds. The addition of this or these tri- and/or tetravalent elements X and Y can be done prior to heating the reaction mixture or at an intermediate moment during that heating.
      The reaction mixture can optionally contain a source of fluoride ions. In this case, the proportion of fluoride ions in the mixture is preferably M1/nF/SiO2=0.05-3.0.
  • According to a preferred particular embodiment, the reaction mixture has a composition, in terms of molar ratios of oxides, lying between the intervals:
    • ROH/SiO2=0.1-1.0,
    • M1/nF/SiO2=0-1.0
    • X2O3/SiO2=0.001-0.05
    • YO2/SiO2=0.001-0.1
    • H2O/SiO2=1-50
      where X is one or more trivalent elements selected from among Al, B, Ga, Fe and Cr and Y is one or more tetravalent elements selected from among Ti, Ge, Sn and V.
  • In the method of the present invention, among the sources of SiO2 can be mentioned, for example, tetraethylorthosilicate, colloidal silica and amorphous silica.
  • Among the elements in oxidation state +3, Al can be used; for example, aluminium alcoxides, aluminium oxides or aluminium salts can all be used as sources of aluminium.
  • In any of the embodiments of the preparation method for the amorphous material described above, the organic compound R is preferably in the form of hydroxide. Alternatively it is possible to use the organic cation in salt form (for example, a halide, preferably chloride, bromide or iodide).
  • According to a preferred embodiment of the synthesis method, the organic compound comprises one or more amine groups. Said organic compound can also comprise one or more ammonium groups.
  • According to a preferred embodiment of the synthesis method, the organic compound is selected from among N(16)-methylsparteinium, 1,4-biscyclohexylpyrrolidiniumbutane hydroxide, 1,8-bisquinuclidiniumoctane hydroxide, 1,4-biscyclohexylpyrrolidiniumbutane hydroxide, hexamethonium hydroxide and tetraethylammonium hydroxide.
  • The heat treatment of the reaction mixture can be carried out statically or with stirring of the mixture. Once the preparation of the microporous amorphous material is finished, the solid product is separated and dried. The later calcination at temperatures between 400 and 700° C., preferably between 450 and 600° C., shows that the materials are thermally stable, and the decomposition of the occluded organic remains and their exit is produced, leaving the pores free.
  • In general, the reaction mixture has a composition which accords with the empirical formula:
    a ROH:b M1/nF:x X2O3:y YO2:SiO2:w H2O
    where X is one or more elements in an oxidation state +3, Y is one or more elements in an oxidation state +4, M is selected from among H+, one or more inorganic cations of charge +n and mixtures of same; and R is one or more organic compounds, and the values a, b, x, y and w are in the ranges:
    • a=ROH/SiO2=0.01-3.0, preferably 0.1-1.0
    • b=M1/nF/SiO2=0-3.0, preferably 0.1-1.0
    • x=X2O3/SiO2=0-0.01, preferably 0-0.05
    • y=YO2/SiO2=0-0.2, preferably 0-0.1
    • w=H2O/SiO2=1-100, preferably 1-50, more preferably 1-20.
  • The present invention also refers to a method of use of the microporous amorphous material defined earlier as a catalyst in a conversion process for organic compounds consisting of placing a feed in contact with a quantity of that catalyst.
  • Said process can be a process of catalytic cracking of organic compounds, preferably hydrocarbons.
  • According to preferred embodiments the process is selected from among a hydrocracking process, gentle hydrocracking of hydrocarbons, gentle hydrocracking of functionalised hydrocarbons, gentle hydrocracking of hydrocarbons and functionalised hydrocarbons, hydroisomerisation of olefins, an isomerisation process of light paraffins, deparaffining, isodeparaffining and an alkylation process.
  • In the case of an alkylation process, said alkylation can be selected from among alkylation of isoparaffins with olefins, alkylation of olefins with isoparaffins, alkylation of aromatics with olefins or alcohols, alkylation of substituted aromatics with olefins or alcohols, alkylation of thiophenic compounds with olefins or alcohols, alkylation of alkylthiophenic compounds with olefins or alcohols and alkylation of alkylbenzothiophenic compounds with olefins or alcohols. In an especially preferred manner, said alkylation is the alkylation of benzene with propylene.
  • According to alternative embodiments of the method of use of the microporous amorphous material, it can act as a catalyst in a process which is an acylation reaction of substituted aromatic compounds using acids, acid chlorides or organic acid anhydrides as acylating agents.
  • According to an additional alternative embodiment, the process is a selective oxidation of organic compounds using an oxidising agent selected from among H2O2, organic peroxides and organic hydroperoxides.
  • According to an additional alternative embodiment, the process is selected from among a Meerwein-Pondorf-Verley type oxidation reaction and a Baeyer-Villiger type oxidation reaction.
  • In the case of containing Ti, said microporous amorphous material can be used as a catalyst in a process of epoxidation of olefins, oxidation of alkanes, oxidation of alcohols and oxidation of organic compounds containing sulphur and which can produce sulphoxides and sulphones, using organic or inorganic hydroperoxides, such as for example, H2O2, tertbutylhydroperioxide, cumene hydroperoxide or molecular oxygen as oxidising agents and in ammoximation of ketones, and more specifically of cyclohexanone to cyclohexanone oxime with NH3 and H2O2, or NH3 and O2.
  • In the case of containing Si, the microporous amorphous material of the present invention can be used as a catalyst in a Baeyer-Villiger type oxidation using H2O2 as the oxidising agent.
    • BRIEF DESCRIPTION OF THE FIGURES
  • FIG. 1 shows the X-ray diffraction diagram of a sample of the microporous amorphous material of the invention, prepared as per example 1, using N(16)-methylspartenium, and prior to calcining.
  • FIG. 2 shows the IR spectrum of a sample of the microporous amorphous material of the invention, known as MAS-1, prepared as per example 1, using N(16)-methylspartenium, and prior to calcining.
  • FIG. 3 shows the pore distribution of a sample of the microporous amorphous material of the invention, prepared as per example 1, using N(16)-methylspartenium, and calcined.
  • FIG. 4 shows the X-ray diffraction diagram of a sample of the microporous amorphous material of the invention, prepared as per example 2, using N(16)-methylspartenium, and prior to calcining.
  • FIG. 5 shows the X-ray diffraction diagram of a sample of the microporous amorphous material of the invention containing Ti, prepared as per example 3, using N(16)-methylspartenium, and without calcining.
  • FIG. 6 shows the X-ray diffraction diagram of a sample of the microporous amorphous material of the invention, pure silica MAS-1, and prepared as per example 4, using N(16)-methylspartenium, and without calcining.
  • FIG. 7 shows the X-ray diffraction diagram of a sample of the microporous amorphous material of the invention, prepared as per example 5, known as MAS-2, using 1,8-bisquinuclidiniumoctane hydroxide, and without calcining.
  • FIG. 8 shows the IR spectrum of a sample of the microporous amorphous material of the invention, prepared as per example 5, using 1,8-bisquinuclidiniumoctane hydroxide, and without calcining.
  • FIG. 9 shows the pore distribution of a sample of the microporous amorphous material of the invention, prepared as per example 5, using 1,8-bisquinuclidiniumoctane hydroxide, and calcined.
  • FIG. 10 shows the X-ray diffraction diagram of a sample of the microporous amorphous material of the invention, prepared as per example 6, using 1,8-bisquinuclidiniumoctane hydroxide, and without calcining.
  • FIG. 11 shows the X-ray diffraction diagram of a sample of the microporous amorphous material of the invention, prepared as per example 7, known as MAS-3, using 1,4-biscyclohexylpyrrolidiniumbutane hydroxide, and without calcining.
  • FIG. 12 shows the IR spectrum of a sample of the microporous amorphous material of the invention, prepared as per example 7, using 1,4-biscyclohexylpyrrolidiniumbutane hydroxide, and without calcining.
  • FIG. 13 shows the pore distribution of a sample of the microporous amorphous material of the invention, prepared as per example 7, using 1,4-biscyclohexylpyrrolidiniumbutane hydroxide, and calcined.
  • FIG. 14 shows the X-ray diffraction diagram of a sample of the microporous amorphous material of the invention, prepared as per example 8, using 1,4-biscyclohexylpyrrolidiniumbutane hydroxide, and without calcining.
  • FIG. 15 shows the X-ray diffraction diagram of a sample of the microporous amorphous material of the invention, prepared as per example 9, known as MAS-4, using hexamethonium hydroxide, and without calcining.
  • FIG. 16 shows the IR spectrum of a sample of the microporous amorphous material of the invention, prepared as per example 9, using hexamethonium hydroxide, and without calcining.
  • FIG. 17 shows the pore distribution of a sample of the microporous amorphous material of the invention, prepared as per example 9, using hexamethonium hydroxide, and calcined.
  • FIG. 18 shows the X-ray diffraction diagram of a sample of the microporous amorphous material of the invention, prepared as per example 10, known as MAS-5, using tetraethylammonium hydroxide, and without calcining.
  • FIG. 19 shows the IR spectrum of a sample of the microporous amorphous material of the invention, prepared as per example 10, using tetraethylammonium hydroxide, and without calcining.
  • FIG. 20 shows the X-ray diffraction diagram of a sample of the microporous amorphous material of the invention, prepared as per example 11, using tetraethylammonium hydroxide, and without calcining.
    • EXAMPLES Example 1
  • 0.272 grams of aluminium isopropoxide and 4.167 grams of tetraethylorthosilicate are hydrolysed in 11.00 grams of a solution of N(16)-methylsparteinium hydroxide with a concentration of 0.91 mols/kg. The solution obtained is kept being stirred allowing all the alcohol formed in the hydrolysis and the surplus water to evaporate. Afterwards, 0.416 g of a solution of fluorhydric acid (48.1% of HF by weight) is then added and evaporation is continued until the reaction mixture reaches a final composition:
    SiO2:0.033 Al2O3:0.50 ROH:0.50 HF:2 H2O
    where ROH is N(16)-methylsparteinium hydroxide.
  • The gel is heated at 175° C. statically for 16 hours in steel autoclaves with an internal Teflon lining. The solid obtained after filtering, washing with distilled water and drying at 100° C. is MAS1. The X-ray diffraction pattern of the solid obtained, measured by the powder method using a fixed divergence grating and employing Ka from Cu, is shown in FIG. 1 and the IR spectrum in FIG. 2.
  • The material is calcined at 580° C. for 3 hours in an air stream in order to eliminate organic matter and the fluoride ions occluded in its interior. The solid known as MAS-1 displays a specific surface area of 738 m2/g and a micropore volume of 0.28 cm3/g. The pore diameter is 7.5 Å and the pore distribution measured by Ar adsorption following the Hovartz-Kavazoe formalism is shown in FIG. 3.
    • Example 2
  • 52.08 g of tetraethylorthosilicate and 2.04 g of aluminium isopropoxide are hydrolysed in 132.98 g of a solution of N(16)-methylsparteinium hydroxide with a concentration of 0.94 mols/kg. The solution obtained is kept being stirred allowing the alcohol and the isopropanol formed in the hydrolysis to evaporate. Afterwards, 5.20 g of a solution of fluorhydric acid (48.1% of HF by weight) is then added and evaporation is continued until the mixture reaches the composition:
    SiO2:0.02 Al2O3:0.50 ROH:0.50 HF:2 H2O
    where ROH is N(16)-methylsparteinium hydroxide.
  • The gel is heated for 16 hours in steel autoclaves with an internal Teflon lining at 175° C. statically. The solid obtained after filtering, washing with distilled water and drying at 100° C. is MAS-1. The X-ray diffraction pattern of the solid obtained is shown in FIG. 4.
  • After calcining at 580° C. in an air stream for 3 hours, the solid, known as MAS-1, displays a specific surface area of 643 m2/g and a micropore volume of 0.24 cm3/g.
    • Example 3
  • 0.19 g of tetraethylorthotitanate and 8.33 g of tetraethylorthosilicate are hydrolysed in 24.39 g of a solution of N(16)-methylsparteinium hydroxide with a concentration of 0.86 mols/kg. The solution obtained is kept being stirred allowing all the alcohol formed in the hydrolysis and part of the surplus water to evaporate. Afterwards, 0.80 g of a solution of fluorhydric acid (50% of HF by weight) is then added. The final composition of the synthesis gel is:
    SiO2:0.02 TiO2:0.50 ROH:0.50 HF:2 H2O
    where ROH is N(16)-methylsparteinium hydroxide.
  • The gel is heated at 175° C. statically for 3 days in steel autoclaves with an internal Teflon lining. The solid obtained after filtering, washing with distilled water and drying at 100° C. is Ti-MAS1. The X-ray diffraction pattern of the solid obtained is shown in FIG. 5.
    • Example 4
  • 34.67 g of tetraethylorthosilicate are hydrolysed in 73.45 g of a solution of N(16)-methylsparteinium hydroxide with a concentration of 1.133 mols/kg, maintaining stirring and allowing all the ethanol formed in the hydrolysis to evaporate. Afterwards, 3.55 g of a solution of fluorhydric acid (46.9% of HF by weight) is then added and evaporation is continued until the reaction mixture reaches a final composition:
    SiO2:0.50 ROH:0.50 HF:3 H2O
    where ROH is N(16)-methylsparteinium hydroxide.
  • After 2 days of crystallisation at 175° C. with stirring in steel autoclaves with an internal Teflon lining, pure silica MAS-1 is obtained. The X-ray diffraction pattern of the solid obtained is shown in FIG. 6.
    • Example 5
  • 6.34 g of tetraethylorthosilicate and 0.12 g of aluminium isopropoxide are hydrolysed in 18.80 g of a solution of 1,8-bisquinuclidiniumoctane hydroxide with a concentration of 0.81 mols of OH/kg. The solution obtained is kept being stirred allowing the alcohol and the isopropanol formed in the hydrolysis to evaporate. Afterwards, 0.61 g of a solution of fluorhydric acid (49.8% of HF by weight) is then added and evaporation is continued until the mixture reaches the composition:
    SiO2:0.01 Al2O3:0.25 R(OH)2:0.50 HF:15 H2O
    where R(OH)2 is 1,8-bisquinuclidiniumoctane hydroxide.
  • The gel is heated for 7 days in steel autoclaves with an internal Teflon lining at 175° C. with stirring. The solid obtained after filtering, washing with distilled water and drying at 100° C. is MAS-2. The X-ray diffraction pattern of the solid obtained is shown in FIG. 7 and the IR spectrum in FIG. 8.
  • The material is calcined at 580° C. for 3 hours in an air stream in order to eliminate organic matter and the fluoride ions occluded in its interior. The solid known as MAS-2 displays a specific surface area of 388 m2/g and a micropore volume of 0.14 cm3/g. The pore diameter is 6.0 Å and the pore distribution measured by Ar adsorption following the Hovartz-Kavazoe formalism is shown in FIG. 3.
    • Example 6
  • 8.32 g of tetraethylorthosilicate and 0.16 g of aluminium isopropoxide are hydrolysed in 18.84 g of a solution of 1,8-bisquinuclidiniumoctane hydroxide with a concentration of 1.06 mols of OH/kg. The solution obtained is kept being stirred allowing the alcohol and the isopropanol formed in the hydrolysis to evaporate. Afterwards, 0.85 g of a solution of fluorhydric acid (46.9% of HF by weight) is then added and evaporation is continued until the mixture reaches the composition:
    SiO2:0.01 Al2O3:0.50 R(OH)2:0.50 HF:15 H2O
    where R(OH)2 is 1,8-bisquinuclidiniumoctane hydroxide.
  • The gel is heated for 3 days in steel autoclaves with an internal Teflon lining at 150° C. with stirring. The solid obtained after filtering, washing with distilled water and drying at 100° C. is MAS-2. The X-ray diffraction pattern of the solid obtained is shown in FIG. 10.
    • Example 7
  • 1.27 g of aluminium isopropoxide and 12.93 g of tetraethylorthosilicate are hydrolysed in 70.04 grams of a solution of 1,4-biscyclohexylpyrrolidiniumbutane hydroxide with a concentration of 0.47 mols OH/kg. The solution obtained is kept being stirred allowing all the alcohol formed in the hydrolysis and the surplus water to evaporate. Afterwards, 1.33 g of a solution of fluorhydric acid (50% of HF by weight) is then added and evaporation is continued until the reaction mixture reaches a final composition:
    SiO2:0.05 Al2O3:0.27 R(OH)2:0.54 HF:7.25 H2O
    where ROH is 1,4-biscyclohexylpyrrolidiniumbutane hydroxide.
  • The gel is heated at 175° C. with stirring for 5 days in steel autoclaves with an internal Teflon lining. The solid obtained after filtering, washing with distilled water and drying at 100° C. is MAS-3. The X-ray diffraction pattern of the solid obtained is shown in FIG. 11 and the IR spectrum in FIG. 12.
  • The material is calcined at 580° C. for 3 hours in an air stream in order to eliminate organic matter and the fluoride ions occluded in its interior. The solid known as MAS-1 displays a specific surface area of 418 m2/g and a micropore volume of 0.15 cm3/g. The pore diameter is 6.2 Å and the pore distribution measured by Ar adsorption following the Hovartz-Kavazoe formalism is shown in FIG. 13.
    • Example 8
  • 8.65 g of tetraethylorthosilicate and 0.34 g of aluminium isopropoxide are hydrolysed in 38.75 g of a solution of 1,4-biscyclohexylpyrrolidiniumbutane hydroxide with a concentration of 0.28 mols OH/kg. The solution obtained is kept being stirred allowing the ethanol and the isopropanol formed in the hydrolysis to evaporate. Afterwards, 0.88 g of a solution of fluorhydric acid (50% of HF by weight) is then added and evaporation is continued until the mixture reaches the composition:
    SiO2:0.02 Al2O3:0.27 R(OH)2:0.54 HF:7.25 H2O
    where ROH is 1,4-biscyclohexylpyrrolidiniumbutane hydroxide.
  • The gel is heated for 4 days in steel autoclaves with an internal Teflon lining at 175° C. with stirring. The solid obtained after filtering, washing with distilled water and drying at 100° C. is MAS-3. The X-ray diffraction pattern of the solid obtained is shown in FIG. 14.
    • Example 9
  • 0.24 g of GeO2 are dissolved in 39.01 g of a solution of hexamethonium hydroxide with a concentration of 0.84 mols OH/kg. 11.84 g of tetraethylorthosilicate are hydrolysed in the solution obtained and it is kept being stirred allowing the ethanol formed to evaporate. Afterwards, 1.37 g of a solution of fluorhydric acid (48.1% of HF by weight) is then added and evaporation is continued until the mixture reaches the composition:
    0.96 SiO2:0.04 GeO2:0.28 R(OH)2:0.56 HF:7 H2O
    where R(OH)2 is hexamethonium hydroxide.
  • The gel is heated for 5 days in steel autoclaves with an internal Teflon lining at 135° C. with stirring. The solid obtained after filtering, washing with distilled water and drying at 100° C. is MAS-4. The X-ray diffraction pattern of the solid obtained is shown in FIG. 15 and the IR spectrum in FIG. 16.
  • The material is calcined at 580° C. for 3 hours in an air stream in order to eliminate organic matter and the fluoride ions occluded in its interior. The solid known as MAS-4 displays a specific surface area of 348 m2/g and a micropore volume of 0.13 cm3/g. The pore diameter is 5.5 Å and the pore distribution measured by Ar adsorption following the Hovartz-Kavazoe formalism is shown in FIG. 17.
    • Example 10
  • 19.9 g of tetraethylorthosilicate are added to 14.39 g of an aqueous solution of tetraethylammonium hydroxide (TEAOH) at 40% by weight and 3 g of water, and the mixture is stirred. A solution is then added containing 0.32 g of metallic aluminium (99.95%) previously dissolved in 9 g of TEAOH (40%). The mixture is left to evaporate with stirring until complete elimination of the ethanol coming from the hydrolysis of the TEOS plus the quantity of water necessary for reaching the final composition that is stated. Finally, 2.15 g of an aqueous solution of fluorhydric acid (48% of HF by weight) is added. The composition of the gel is:
    SiO2:0.062 Al2O3:0.665 ROH:0.54 HF:7 H2O
    where ROH is tetraethylammonium hydroxide.
  • The mixture obtained is introduced into an autoclave provided with an internal polytetrafluorethylene lining and is heated at 140° C. for 6 days in a stove provided with a rotation system. After that time, it is recovered by means of filtering, washed with water and then dried at 100° C, giving 27.9 g of solid per 100 g of gel. The solid obtained is MAS-5 and its X-ray diffraction pattern of the solid obtained is shown in FIG. 18 and the IR spectrum in FIG. 19.
  • The material is calcined at 580° C. for 3 hours in an air stream in order to eliminate organic matter and the fluoride ions occluded in its interior.
    • Example 11
  • 15.00 grams of tetraethylorthosilicate are hydrolysed in 16.36 grams of a solution of tetraethylammonium hydroxide (TEAOH) at 40% by weight and 3 g of water, and the mixture is stirred. The solution obtained is kept being stirred allowing all the alcohol formed in the hydrolysis and the surplus water to evaporate. Afterwards, 1.56 g of a solution of fluorhydric acid (50% of HF by weight) is then added and evaporation is continued until the mixture reaches a final composition:
    SiO2:0.54 ROH:0.54 HF:7 H2O
    where ROH is tetraethylammonium hydroxide.
  • The gel is heated at 175° C. with stirring for 4 hours in steel autoclaves with an internal Teflon lining. The solid obtained after filtering, washing with distilled water and drying at 100° C. is MAS-5 and its X-ray diffraction pattern is shown in FIG. 20.
    • Example 12
  • This example shows the catalytic activity of a bifunctional catalyst formed from an acid function (MAS, prepared as per example 2) and a hydrogenating-dehydrogenating function (Pt 1.0% by weight), introduced by impregnation starting from an aqueous solution of hexachloroplatinic acid, for the hydrocracking of n-hexadecane. The reaction was carried out in a fixed bed continuous reactor at 270° C., pressure 40 bars, with a molar ratio of H2/hexadecane of 95 and a contact time (W/F) of 0.27 hours. Under these conditions the conversion of n-hexadecane was 84.6% with a selectivity to C16 isomers of 2.3% and a selectivity to hydrocracklng products of 97.7%. No products with one or two carbon atoms were detected among the hydrocracking products. The yield of C5-C7 products was 35.8%.
    • Example 13
  • This example shows the catalytic activity of a bifunctional catalyst formed from an acid function (MAS, prepared as per example 2) and a hydrogenating function (Pt 1% by weight), introduced by impregnation starting from an aqueous solution of hexachloroplatinic acid, for the hydrocracking of a hydrotreated gasoil containing 10.6% by weight of hydrocarbons with a boiling point between 250° C. and 380° C., and 89.4% with boiling point above 380° C., and a sulphur content of 87 ppm. The reaction conditions were 370° C. 0.2 hours contact time (W/F), pressure 50 bars and volume ratio under normal conditions of H2/gasoil=988.
  • After eight hours under these reaction conditions the conversion (380° C.) was 56.4% with yields to gases of 0.7%, to naphtha (65°-150° C.) of 12.5%, to kerosene (150°-250° C.) of 20.1% and to mean distillates (250°-380° C.) of 23.0%.
    • Example 14
  • This example shows the catalytic activity for catalytic cracking of an MAS material prepared according to example 2, in which n-decane is used as reagent. The reaction conditions were: atmospheric pressure, weight ratio of catalyst/feed of 0.70, temperature of 500° C. and reaction time of 60 seconds. Under these conditions the conversion was 33%.
    • Example 15
  • This example shows the catalytic activity for cracking of a vacuum gasoil, of the MAS material prepared as per example 2. The reaction conditions were: atmospheric pressure, weight ratio of catalyst/feed of 0.65, reaction temperature of 500° C. and reaction time of 60 seconds. The conversion was 60% by weight, with a yield to gases, gasoline, diesel and coke of 19.1, 23.2, 14.0 and 3.7%, respectively, the propylene/propane ratio in the gases being 4.9, for a propylene yield of 7%.

Claims (32)

1. A microporous amorphous material wherein it has a chemical composition in the calcined and anhydrous state which can be represented by the following empirical formula:

x(M1/nXO2):y YO2:SiO2
wherein:
x has a value of less than 0.2, and can be equal to zero,
y has a value of less than 0.2, and can be equal to zero,
M is selected from among H+, one or more inorganic cations having a charge +n and a mixture of same;
X is one or more chemical elements in oxidation state +3; and
Y is one or more elements in oxidation state +4,
which has a uniform pore distribution and a micropore volume of greater than or equal to 0.05 cm3.g−1 and
which has a specific surface area of greater than 100 m2.g−1
2. A microporous amorphous material according to claim 1, wherein it has a chemical composition in the calcined and anhydrous state which can be represented by the following empirical formula:

x(M1/nXO2):y YO2:SiO2
wherein:
x has a value of less than 0.1, and can be equal to zero,
y has a value of less than 0.1, and can be equal to zero,
M is selected from among H+, one or more inorganic cations having a charge +n and a mixture of same;
X is one or more chemical elements in oxidation state +3; and
Y is one or more chemical elements with oxidation state +4.
3. A microporous amorphous material according to claim 1, wherein X is selected from among Al, Ga, B, Fe, Cr and a mixture of same.
4. A microporous amorphous material according to claim 1, wherein Y is selected from among Ti, Ge, Sn, V and a mixture of same.
5. A microporous amorphous material according to claim 1, wherein its composition corresponds to the formula:

x(M1/nXO2):SiO2
where:
x has a value of less than 0.2, and can be equal to zero,
M is selected from among H+, one or more inorganic cations having a charge +n and a mixture of same, and
X is one or more chemical elements in oxidation state +3.
6. A microporous amorphous material according to claim 1, wherein its composition in the calcined and anhydrous state can be represented by the formula:

y YO2:SiO2
where:
y has a value of less than 0.2, and can be equal to zero; and
Y is one or more chemical elements with oxidation state +4.
7. A microporous amorphous material according to claim 1, wherein its chemical composition in the calcined and anhydrous state can be represented by the empirical formula:

x(HXO2):SiO2
where:
x has a value of less than 0.2, and can be equal to zero; and
X is one or more chemical elements in oxidation state +3.
8. A microporous amorphous material according to claim 1, wherein its chemical composition in the calcined and anhydrous state is represented by the formula SiO2.
9. A method for synthesising a microporous amorphous material defined in claim 1, comprising:
preparing a reaction mixture comprising at least:
a source of SiO2,
one or more organic compounds, and
water,
subjecting said mixture to heating with or without stirring at a temperature between 80 and 200° C., until achieving the formation of the amorphous material, and in which the reaction mixture has a composition, in terms of molar ratios of oxides, lying between the intervals:
ROH/SiO2=0.01-3.0,
H2O/SiO2=1-100,
where R is one or more organic compounds.
10. A method for synthesising an amorphous material according to claim 9, wherein the reaction mixture furthermore comprises a source of fluoride ions.
11. A method for synthesising an amorphous material according to claim 9, comprising:
preparing a reaction mixture comprising at least:
a source of SiO2,
a source of one or more tetravalent elements Y,
one or more organic compounds,
water,
subjecting said mixture to heating with or without stirring at a temperature between 80 and 200° C., until achieving the formation of the amorphous material, and in which the reaction mixture has a composition, in terms of molar ratios of oxides, lying between the intervals:
ROH/SiO2=0.01-3.0,
H2O/SiO2=1-100, and
YO2/SiO2=0.001-0.2
where Y is one or more elements in an oxidation state +4, and R is one or more organic compounds.
12. A method for synthesising an amorphous material according to claim 9, comprising:
preparing a reaction mixture comprising at least:
a source of SiO2,
a source of one or more trivalent elements X,
one or more organic compounds, and
water,
subjecting said mixture to heating with or without stirring at a temperature between 80 and 200° C., until achieving the formation of the amorphous material, and in which the reaction mixture has a composition, in terms of molar ratios of oxides, lying between the intervals:
ROH/SiO2=0.01-3.0,
H2O/SiO2=1-100, and
X2O3/SiO2=0.001-0.1,
where X is one or more elements in an oxidation state +3 and R is one or more organic compounds.
13. A method for synthesising an amorphous material according to claim 9, comprising:
preparing a reaction mixture comprising at least:
a source of SiO2,
a source of one or more trivalent elements X,
one or more elements M of charge +n,
one or more organic compounds, and
water,
subjecting said mixture to heating with or without stirring at a temperature between 80 and 200° C., until achieving the formation of the amorphous material, and in which the reaction mixture has a composition, in terms of molar ratios of oxides, lying between the intervals:
ROH/SiO2=0.01-3.0,
H2O/SiO2=1-100, and
X2O3/SiO2=0.001-0.1,
where X is one or more elements in an oxidation state +3, M is selected from among H+, one or more inorganic cations of charge +n and mixtures of same; and R is one or more organic compounds.
14. A method for synthesising an amorphous material according to claim 9, comprising:
preparing a reaction mixture comprising at least:
a source of SiO2,
a source of one or more trivalent elements X,
a source of one or more tetravalent elements Y,
one or more elements M of charge +n,
one or more organic compounds, and
water,
subjecting said mixture to heating with or without stirring at a temperature between 80 and 200° C., until achieving the formation of the amorphous material, and in which the reaction mixture has a composition, in terms of molar ratios of oxides, lying between the intervals:
ROH/SiO2=0.01-3.0,
H2O/SiO2=1-100,
X2O3/SiO2=0.001-0.1,
YO2/SiO2=0.001-0.2
where X is one or more elements in an oxidation state +3, Y is one or more elements in an oxidation state +4, M is selected from among H+, one or more inorganic cations of charge +n and mixtures of same; and R is one or more organic compounds.
15. A method for synthesising an amorphous material according to claim 14, wherein the reaction mixture has a composition, in terms of molar ratios of oxides, lying between the intervals
ROH/SiO2=0.1-1.0,
X2O3/SiO2=0.001-0.05
YO2/SiO2=0.001-0.1
H2O/SiO2=1-50
where X is one or more trivalent elements selected from among Al, B, Ga, Fe and Cr and Y is one or more tetravalent elements selected from among Ti, Ge, Sn and V.
16. A method for synthesising an amorphous material according to claim 14, wherein the reaction mixture has a composition which accords with the empirical formula:

a ROH:b M1/nF:x X2O3:y YO2:SiO2:w H2O
where X is one or more elements in an oxidation state +3, Y is one or more elements in an oxidation state +4, M is selected from among H+, one or more inorganic cations of charge +n and mixtures of same; and R is one or more organic compounds,
and the values a, b, x, y and w are in the ranges:
a=ROH/SiO2=0.1-3.0,
b=M1/nF/SiO2=0.1-3.0,
x=X2O3/SiO2=0-0.05,
y=YO2/SiO2=0-0.1, and
w=H2O/SiO2=1-50,
17. A method for synthesising an amorphous material according to claim 9, wherein the mixture is subjected to heating with or without stirring at a temperature between 100 and 200° C.
18. A method for synthesising an amorphous material according to claim 9, wherein the organic compound R is in hydroxide form.
19. A method for synthesising an amorphous material according to claim 9, wherein the organic compound comprises one or more amine groups.
20. A method for synthesising an amorphous material according to claim 9, wherein the organic compound comprises one or more ammonium groups.
21. A method for synthesising an amorphous material according to claim 9, wherein the organic compound is selected from among N(16)-methylsparteinium, 1,4-biscyclohexylpyrrolidiniumbutane hydroxide, 1,8-bisquinuclidiniumoctane hydroxide, 1,4-biscyclohexylpyrrolidiniumbutane hydroxide, hexamethonium hydroxide and tetraethylammonium hydroxide.
22. Method of use of an amorphous material of claim 1, as catalyst in a conversion process for organic compounds consisting of placing a feed in contact with a quantity of that catalyst.
23. Method of use according to claim 22, wherein the process can be a process of catalytic cracking of organic compounds.
24. Method of use of an amorphous material according to claim 23, wherein said organic compounds are hydrocarbons.
25. Method of use of an amorphous material according to claim 22, wherein the process is selected from among a hydrocracking process, gentle hydrocracking of hydrocarbons, gentle hydrocracking of functionalised hydrocarbons, gentle hydrocracking of hydrocarbons and functionalised hydrocarbons, hydroisomerisation of olefins, an isomerisation process of light paraffins, deparaffining, isodeparaffining and an alkylation process.
26. Method of use of an amorphous material according to claim 25, wherein the alkylation process is selected from among alkylation of isoparaffins with olefins, alkylation of olefins with isoparaffins, alkylation of aromatics with olefins or alcohols, alkylation of substituted aromatics with olefins or alcohols, alkylation of thiophenic compounds with olefins or alcohols, alkylation of alkylthiophenic compounds with olefins or alcohols, alkylation of alkylbenzothiophenic compounds with olefins or alcohols.
27. Method of use of an amorphous material according to claim 25, wherein the alkylation process is the alkylation of benzene with propylene.
28. Method of use of an amorphous material according to claim 22, wherein the process is an acylation reaction of substituted aromatic compounds using acids, acid chlorides or organic acid anhydrides as acylating agents.
29. Method of use of an amorphous material according to claim 22, wherein the process is a selective oxidation of organic compounds using an oxidising agent selected from among H2O2, organic peroxides and organic hydroperoxides.
30. Method of use of an amorphous material according to claim 22, wherein the process is selected from among a Meerwein-Pondorf-Verley type oxidation reaction and a Baeyer-Villiger type oxidation reaction.
31. Method of use of an amorphous material according to claim 22, wherein said amorphous material contains Ti and the process is selected from among:
a process of epoxidation of olefins,
oxidation of alkanes, oxidation of alcohols,
oxidation of organic compounds containing sulphur and which can produce sulphoxides and sulphones, using organic or inorganic hydroperoxides or molecular oxygen as oxidising agents and
ammoximation of ketones.
32. Method of use of an amorphous material according to claim 22, wherein said amorphous material contains Sn and the process is an oxidation in Baeyer-Villiger reactions using H2O2 as oxidising agent.
US11/547,805 2004-04-07 2005-04-05 Microporous Amorphous Material, Preparation Method Thereof and Use of Same in the Catalytic Conversion of Organic Compounds Abandoned US20080035524A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
ES200400968A ES2247921B1 (en) 2004-04-07 2004-04-07 A MICROPOROUS AMORFO MATERIAL, PREPARATION PROCEDURE AND ITS USE IN THE CATALYTIC CONVERSION OF ORGANIC COMPOUNDS.
ESP200400968 2004-04-07
PCT/ES2005/070039 WO2005097679A1 (en) 2004-04-07 2005-04-05 Microporous amorphous material, preparation method thereof and use of same in the catalytic conversion of organic compounds

Publications (1)

Publication Number Publication Date
US20080035524A1 true US20080035524A1 (en) 2008-02-14

Family

ID=35124968

Family Applications (1)

Application Number Title Priority Date Filing Date
US11/547,805 Abandoned US20080035524A1 (en) 2004-04-07 2005-04-05 Microporous Amorphous Material, Preparation Method Thereof and Use of Same in the Catalytic Conversion of Organic Compounds

Country Status (5)

Country Link
US (1) US20080035524A1 (en)
EP (1) EP1783099A1 (en)
JP (1) JP2007532451A (en)
ES (1) ES2247921B1 (en)
WO (1) WO2005097679A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010042397A3 (en) * 2008-10-10 2010-07-01 Chevron U.S.A. Inc. Molecular sieve ssz-82 composition of matter and synthesis thereof
US20110081416A1 (en) * 2008-04-28 2011-04-07 Formac Pharmaceuticals N.V. Ordered mesoporous silica material
US8900548B2 (en) 2011-10-12 2014-12-02 Exxonmobil Research And Engineering Company Synthesis of MSE-framework type molecular sieves
US8916130B2 (en) 2011-10-12 2014-12-23 Exxonmobil Research And Engineering Company Synthesis of MSE-framework type molecular sieves

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2263369B1 (en) * 2005-02-02 2007-12-16 Universidad Politecnica De Valencia MICROPOROUS CRYSTAL MATERIAL OF ZEOLITIC NATURE, ZEOLITA ITQ-32, PREPARATION AND USE PROCEDURE.
US20100194265A1 (en) 2007-07-09 2010-08-05 Katholieke Universiteit Leuven Light-emitting materials for electroluminescent devices
US8395008B2 (en) 2008-01-14 2013-03-12 Catalytic Distillation Technologies Process and catalyst for cracking of ethers and alcohols
US7682599B2 (en) * 2008-10-10 2010-03-23 Chevron U.S.A. Inc. Method for preparing NES-type zeolites using novel structure directing agents
US7648694B2 (en) * 2008-10-10 2010-01-19 Chevron U.S.A. Inc. Method for preparing SSZ-26/33 zeolites using novel structure directing agents
US8367028B2 (en) 2008-12-05 2013-02-05 Exxonmobil Research And Engineering Company Amorphous acidic materials, their synthesis and use
WO2012025624A1 (en) * 2010-08-27 2012-03-01 Formac Pharmaceuticals N.V. Processes for producing microporous silica materials
EP3507243B1 (en) * 2016-09-01 2020-05-13 Chevron U.S.A. Inc. Synthesis of aluminosilicate zeolite ssz-26 via interzeolite transformation

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6121187A (en) * 1995-12-02 2000-09-19 Studiengesellschaft Kohle Mbh Amorphous, microporous mixed oxide catalysts with controlled surface polarity for selective heterogeneous catalysis, adsorption and material separation
US6573131B2 (en) * 2000-07-13 2003-06-03 The Regents Of The University Of California Silica zeolite low-k dielectric thin films and methods for their production

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1219692B (en) * 1988-05-06 1990-05-24 Eniricerche Spa SILICA GEL AND CATALYTICALLY ACTIVE ALUMINUM AND PROCEDURE FOR ITS PREPARATION
IT1217525B (en) * 1988-05-06 1990-03-22 Enichem Sintesi PROCEDURE FOR THE PREPARATION OF CUMENE
EP0987220A1 (en) * 1998-09-17 2000-03-22 Technische Universiteit Delft Mesoporous amorphous silicate materials and process for the preparation thereof
JP2733860B2 (en) * 1989-10-19 1998-03-30 日東化学工業株式会社 Manufacturing method of wear-resistant silica media
IT1248985B (en) * 1990-06-22 1995-02-11 Eniricerche Spa PROCEDURE FOR OLIGOMERIZING LIGHT OLEFINS
JPH0742097B2 (en) * 1992-05-15 1995-05-10 工業技術院長 Synthetic porous body
JP3471514B2 (en) * 1996-02-01 2003-12-02 水澤化学工業株式会社 Resin composition for semiconductor encapsulation and hygroscopic filler used therein
JP3647959B2 (en) * 1996-02-01 2005-05-18 水澤化学工業株式会社 Method for producing amorphous silica-based regular particles
JPH09295811A (en) * 1996-04-30 1997-11-18 Lion Corp Amorphous porous body and its production
JP4099360B2 (en) * 2002-07-17 2008-06-11 財団法人ファインセラミックスセンター Method for producing amorphous silica porous material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6121187A (en) * 1995-12-02 2000-09-19 Studiengesellschaft Kohle Mbh Amorphous, microporous mixed oxide catalysts with controlled surface polarity for selective heterogeneous catalysis, adsorption and material separation
US6573131B2 (en) * 2000-07-13 2003-06-03 The Regents Of The University Of California Silica zeolite low-k dielectric thin films and methods for their production

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110081416A1 (en) * 2008-04-28 2011-04-07 Formac Pharmaceuticals N.V. Ordered mesoporous silica material
WO2010042397A3 (en) * 2008-10-10 2010-07-01 Chevron U.S.A. Inc. Molecular sieve ssz-82 composition of matter and synthesis thereof
US8900548B2 (en) 2011-10-12 2014-12-02 Exxonmobil Research And Engineering Company Synthesis of MSE-framework type molecular sieves
US8916130B2 (en) 2011-10-12 2014-12-23 Exxonmobil Research And Engineering Company Synthesis of MSE-framework type molecular sieves
US9035058B2 (en) 2011-10-12 2015-05-19 Exxonmobil Research And Engineering Company Synthesis of MSE-framework type molecular sieves

Also Published As

Publication number Publication date
EP1783099A1 (en) 2007-05-09
WO2005097679A1 (en) 2005-10-20
ES2247921B1 (en) 2007-06-16
ES2247921A1 (en) 2006-03-01
JP2007532451A (en) 2007-11-15

Similar Documents

Publication Publication Date Title
US20080035524A1 (en) Microporous Amorphous Material, Preparation Method Thereof and Use of Same in the Catalytic Conversion of Organic Compounds
RU2293058C2 (en) Synthetic porous crystalline material itq-13, synthesis and application of this material
CA2427614C (en) Crystalline aluminosilicate zeolitic composition: uzm-4 and processes using the composition
JP5271266B2 (en) UZM-22 aluminosilicate zeolite, method for its preparation and method for using UZM-22
CN109081359B (en) Molecular sieve SCM-15, its synthesis method and use
RU2617353C2 (en) Material of molecular sieve, its synthesis and use
HU181955B (en) Process for preparing synthetic substances on silicon dioxide base
ES2346521T3 (en) MICROPOROUS CRYSTAL MATERIAL OF ZEOLITIC NATURE (ZEOLITA ITQ-22) ITS SYNTHESIS METHOD AND ITS USE AS A CATALYST.
JPS63162521A (en) Novel synthesis of ferric silicate type zeolites, obtained substances and their uses
JPH10501515A (en) Rare earth-ZSM-5 / ZSM-11 eutectic zeolite
CA2516046C (en) Porous crystalline material (zeolite itq-24), preparation method thereof and use of same in the catalytic conversion of organic compounds
GB1574840A (en) Zeolites and process for preparing same
US6916459B2 (en) Zeolite ITQ-16
AU2002302660B2 (en) Porous crystalline material (zeolite itq-21), the preparation method thereof and use of the same in the catalytic conversion of organic compounds
JPS58145616A (en) Novel crystalline aluminosilicate zeolite and its preparation
JP7138697B2 (en) Molecular sieve SSZ-112, its synthesis and use
US6896869B2 (en) Microporous crystalline material (ITQ-17), method for the preparation thereof and its use in processes for separating and transforming organic compounds
JPS623090B2 (en)
CA2468767C (en) Porous crystalline material (itq-21) and the method of obtaining same in the absence of fluoride ions
US6409986B1 (en) Zeolite ITQ-5
JP5118482B2 (en) UZM-16: crystalline aluminosilicate zeolitic material
JP6525958B2 (en) Molecular sieve, COK-5, its synthesis and use
EP2130586A1 (en) Process for making crystalline metallosilicates
US5683673A (en) Process for the manufacture of a zeolite
EP0739308B1 (en) Process for the manufacture of a zeolite

Legal Events

Date Code Title Description
AS Assignment

Owner name: UNIVERSIDAD POLITECNICA DE VALENCIA, SPAIN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:CORMA CANOS, AVELINO;DIAZ CABANAS, MARIA JOSE;REEL/FRAME:019364/0051;SIGNING DATES FROM 20070208 TO 20070209

Owner name: CONSEJO SUPERIOR DE INVESTIGACIONES CIENTIFICAS, S

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:CORMA CANOS, AVELINO;DIAZ CABANAS, MARIA JOSE;REEL/FRAME:019364/0051;SIGNING DATES FROM 20070208 TO 20070209

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION