Classifications

• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
  • B01J20/16—Alumino-silicates
  • B01J20/18—Synthetic zeolitic molecular sieves
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
• • 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
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
  • C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • 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
  • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
• • 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
  • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
  • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
  • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
  • C07C4/04—Thermal processes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
  • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
  • C07C4/06—Catalytic processes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C7/00—Purification; Separation; Use of additives
  • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
  • C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
• • 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
  • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
  • C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
  • C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with 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
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
  • C10G3/42—Catalytic treatment
  • C10G3/44—Catalytic treatment characterised by the catalyst used
  • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
  • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, 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
  • C10G35/00—Reforming naphtha
  • C10G35/04—Catalytic reforming
  • C10G35/06—Catalytic reforming characterised by the catalyst used
  • C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2529/00—Catalysts comprising molecular sieves
  • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
  • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
• • 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
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/20—C2-C4 olefins
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/40—Ethylene production

Definitions

• Zeolites are microporous crystalline materials of variable composition characterized by a crystalline network of TO tetrahedra (where T represents atoms with a formal oxidation state +3 or +4, such as Si, Ti, Al, Ge, B, Ga, .. .) that share all its vertices giving rise to a three-dimensional structure that contains channels and / or cavities of molecular dimensions.
• T represents atoms with a formal oxidation state +3 or +4, such as Si, Ti, Al, Ge, B, Ga, .. .
• the crystalline network formed has negative charges that are compensated by the presence in the channels or cavities of organic or inorganic cations.
• the chemical composition of the zeolites can be represented by the following empirical formula: x (M .. n XO 2 ): yYO 2 : zR: wH 2 O
• M is one or more organic or inorganic charge cations + n;
• X is one or more trivalent elements; And it is one or several tetravalent elements, generally Si; and R is one or more organic substances.
• M, X, Y and R and the values of x, y, z, and w can, in general, be varied by post-synthesis treatments, the chemical composition of a zeolite (as synthesized or after calcination) ) has a characteristic range of each zeolite and its method of production.
• a zeolite is also characterized by its crystalline structure, which defines a system of channels and cavities and gives rise to a specific X-ray diffraction pattern. In this way, the zeolites differ
• SUBSTITUTE SHEET RULE 26 each other by its range of chemical composition plus its X-ray diffraction pattern. Both characteristics (crystalline structure and chemical composition) also determine the physicochemical properties of each zeolite and its applicability in different industrial processes.
• the present invention relates to a microporous crystalline material of a zeolitic nature, called ITQ-3, its method of production and its applications.
• ITQ-3 a microporous crystalline material of a zeolitic nature
• the material is characterized by its chemical composition and its X-ray diffraction pattern.
• the chemical composition of ITQ-3 can be represented by the empirical formula:
• x has a value of less than 0.15, and can be equal to zero; and has a value of less than 0.1, and can also be equal to zero; M is H + or an inorganic cation of charge + n; X is a chemical element with an oxidation state +3 (such as Al, Ga, B, Cr) and Y is a chemical element with an oxidation state +4 (such as Ti, Ge, V).
• ITQ-3 has the composition, in a calcined and anhydrous state.
• X is a trivalent element and x has a value less than 0.1 and can be equal to zero, in which case the material can be described by the formula SiO 2 . It is possible, however, depending on the method of synthesis and its calcination or subsequent treatments, the existence of defects in the crystalline network, which are manifested by the presence of Si-OH groups (silanoles).
• ITQ-3 has a very low concentration of this type of defects (silane concentration less than 15% with respect to the total Si atoms, preferably less than 6%, measured by resonance spectroscopy nuclear magnetic of 29 Si in magic angle).
• the X-ray diffraction pattern of ITQ-3 as synthesized obtained by the powder method, using a slit of varying divergence and the radiation K ⁇ of the Cu, is characterized by the following values of angle 2 ⁇ and relative intensities (I / U):
• the positions and relative intensities of the peaks depend to some extent on the chemical composition of the material (the pattern represented in Table I refers to the material whose network is exclusively composed of silicon oxide, SiO 2 and synthesized using a quaternary ammonium cation as structure managing agent).
• the relative intensities may also be affected by phenomena of preferential orientation of the crystals, produced in the preparation of the sample, while the precision in the measurement of interplanar spacing depends on the quality of alignment of the goniometer.
• the present invention also relates to the method of preparation of ITQ-3 This comprises a heat treatment at a temperature between 80 and 200 ° C, preferably between 130 and 180 ° C, of a reaction mixture containing a source of SiO 2 (as , for example, tetraethylorthosilicate, colloidal silica, amorphous silica), an organic cation in the form of hydroxide, preferably N, N-dimethyl-6-azonium-1, 3,3-trimethylbicyclo (3.2.1.) octane (I ), hydrofluoric acid and water.
• a source of SiO 2 as , for example, tetraethylorthosilicate, colloidal silica, amorphous silica
• an organic cation in the form of hydroxide preferably N, N-dimethyl-6-azonium-1, 3,3-trimethylbicyclo (3.2.1.) octane (I )
• hydrofluoric acid
• SUBSTITUTE SHEET RULE 26 characterized by its relatively low pH, pH ⁇ 12, preferably pH ⁇ 11, and can also be neutral or slightly acidic.
• it is a source of another tetravalent element Y and / or trivalent X, preferably Ti or Al.
• This element can be done prior to heating the reaction mixture or at an intermediate time during said heating.
• ITQ-3 crystals up to 15% by weight with respect to the set of inorganic oxides, preferably up to 10% by weight
• the composition of the reaction mixture in the form of oxides responds to the general formula
• X is one or more trivalent elements, preferably Al; And it is one or several tetravalent elements; R is an organic cation, preferably N, N-dimethyl-6-azonium-1, 3,3-trimethyl-6-bicyclo (3.2.1.) Octane hydroxide, and the values of r, a, x, and and w are in the ranges
• the heat treatment of the reaction mixture can be carried out in static or with stirring of the mixture. Once the crystallization is finished
• SUBSTITUTE SHEET RULE 26 Separate the solid product and dry. Subsequent calcination at temperatures between 400 and 650 ° C, preferably between 450 and 600 ° C, causes the decomposition of the organic residues occluded in the zeolite and leaves the zeolitic channels free.
• This method of synthesis of zeolite ITQ-3 has the particularity that it does not require the introduction into the reaction medium of alkali cations.
• the organic cation R is the only cation that compensates for network charges when the zeolite contains a trivalent element in its crystalline network.
• x has a value of less than 0.15, and can be equal to zero; and has a value of less than 0.1, and can also be equal to zero;
• X is a chemical element with oxidation state +3 and Y is a chemical element with oxidation state +4.
• the crystalline material of the present invention can be used in various applications, for example, in processes of separation of linear and branched paraffin compounds.
• a mixture of isobutane and n-butane or isopentane and n-pentane can be enriched in the most branched isomer by selective adsorption of the linear paraffin by the microporous material object of the present invention.
• Said material is particularly suitable for application in this type of process due to its high adsorption capacity (micropore volume determined by adsorption of
• the n-olefins can be separated by selective adsorption of mixtures containing normal and isoolefins, enriching the output stream in isoolefins.
• this material would allow the separation of organic compounds, containing or not heteroatoms, and with sizes smaller than about 5-5.5% present in mixtures, also containing organic compounds of larger sizes.
• ITQ-3 would allow selective adsorption of organic compounds with a kinetic diameter of less than 5-5.5 present in polar media, such as aqueous media.
• this material prepared in acid form and containing or not supported transition metals such as Pt, Pd or Ni, allows the cracking and selective hydrocracking of linear alkanes against branched or larger hydrocarbons , being therefore suitable as a catalyst or catalytic cracking additive and as a catalyst in "selectoforming" processes, which entails hydrocracking the current from the reforming unit in order to eliminate n-paraffins.
• ITQ-3 gives good results as a catalyst for alkanes and alkenes in order to produce high yields of ethylene, propylene and butene, being therefore suitable as a catalyst for production processes of short olefins by catalytic steam cracking ("catalytic steam” cracking ").
• catalytic steam cracking
• its possibilities of selectively cracking linear paraffins make it a good catalyst for dewaxing processes.
• this material is a good catalyst in processes of transformation of methanol into olefins.
• SUBSTITUTE SHEET RULE 26 As described in example 1, 12.08g of tetraethylorthosilicate (TEOS) is added and stirred, allowing the evaporation of ethanol produced in the hydrolysis of TEOS, together with some water. After 6 hours of agitation (weight loss 18.99g) 0.57g of water and 1.21 g of HF (aq.) (48%, Aldrich) are added. The paste obtained is introduced into an autoclave coated internally with polytetrafluoroethylene and remains at 150 ° C and in rotation (60 rpm) for 19 days. Then, the autoclave is cooled, the content is filtered and the solid is washed with water and dried at 100 ° C.
• TEOS tetraethylorthosilicate
• N2 adsorption measures indicate a surface area of 455 m2 / g (BET method) and a micropore volume of 0.23 cc / g.

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