Procedimiento de obtencion de una formulacion catalitica para la produccion de diesel de ultrabajo azufre, el producto obtenido y su aplicacion

Patent metadata

Field	Value
Publication number	US-2016008792-A1
Application number	US-201514742000-A
Country	US
Kind code	A1
Filing date	Jun 17, 2015
Priority date	Jun 20, 2014
Publication date	Jan 14, 2016
Grant date	—

Abstract

The present invention relates to a catalytic formulation used in the hydroprocessing of light and middle oil fractions, preferably in hydrodesulfurization and hydrodenitrogenation reactions to obtain diesel with ultra low sulfur content less than or equal to 15 ppm in weight. The catalytic formulation, object of the present invention, consists of at least one metal of Group VI B and at least one metal of Group VIII B and one element of Group V A of the periodic table deposited on a support based on surface modified alumina with an inorganic oxide of a metal of Group II A, IV A and/or IV B. And containing an impregnated organic compound containing at least one hydroxyl group and at least one carboxyl group and that can contain or not at least one sulfide group in its structure. The catalytic formulation, object of the present invention, allows processing of the oil fractions with initial and final boiling temperatures between 150 and 450° C., with initial nitrogen and sulfur content between 1 and 3% by weight and 200 to 600 ppm, respectively, reducing sulfur content to concentrations lower or equal to 15 ppm and nitrogen concentrations to lower than 1 ppm.

First claim

1 - 63 . (canceled)

64 . A process for obtaining a catalytic formulation for the production of ultra low sulfur diesel (ULSD), where in the catalytic formulation consists of at least one non-noble metal of Group VIII B and at least one metal of Group VI B, and an element of Group V A, deposited on a support comprising aluminum oxide modified on its surface by at least one inorganic compound of Group II A, IV A or IV B, and a organic compound that forms a charge-transfer complex ligand-metal with the metal component of Group VI B, the process comprising the following steps:
a) preparing and/or obtaining a hydroxylated and/or hydrated alumina precursor, b) formulating the alumina precursor material obtained in step a) into cylindrical or trilobular or tetralobular extrudates; c) heat treating the extrudates obtained in step b) by calcination in dynamic air atmosphere at temperatures ranging between 500 and 700° C.; d) solubilizing a metal-organic compound containing the element of Group II A, or the element of Group IV A or the element of Group IV B in a low molecular weight protic solvent; e) preparing a solution containing a hydrolysis catalyst comprising an inorganic acid, water and a protic solvent; f) adding the solution prepared in step e) to the solution prepared in subsection d) by slow dripping; g) performing thermal digestion consisting of refluxing the solution prepared in subsection f) at temperature between 20 and 80° C. for a period of time between 0 and 8 h; h) contacting the solution prepared in step g) with the material obtained in c) for a period of time between 0.5 and 8 h at room temperature (25° C.); i) filtering the resulting extrudate material obtained in subsection h); j) drying the material obtained in step i) at temperature between 80 and 120° C. for a period of 6 to 18 h; k) heat treating the material obtained in step j) by calcination in dynamic air atmosphere at a temperature between 300 and 600° C. for a period of time between 4 and 18 h; l) preparing an aqueous suspension containing a compound of the metal component of Group VI B and a compound containing the element of Group V A; m) diluting the suspension in step l) by heat treatment at reflux temperature between 60 and 90° C., until a clear solution is obtained, with the salt of metal component of Group VI B completely dissolved; n) adding or not an organic compound that forms a charge-transfer complex ligand-metal with the metal of Group VI B, to the solution prepared in step m); o) adding a compound containing the element of Group VIII B to the solution obtained in step n); p) stirring the solution obtained in step p) and thermal digestion consisting of refluxing for a period between 1 and 6 h; q) concentrating the solution obtained in step p) by evaporation until the volume required to perform impregnation of the support by incipient wetness is obtained; r) impregnating the solution obtained in step q) to the material on the extrudated material obtained in step k); s) drying the material obtained in step r) at temperature between 80 and 120° C. for a period of time between 4 and 18 h; t) sulfiding the material obtained in step s) if the inorganic compound is added in step n); u) submitting the material obtained in step s), but added the organic compound in subsection n), to heat treatment in dynamic air atmosphere at temperature between 300 and 500° C.; v) preparing a solution of an organic compound containing at least one hydroxyl group and at least one carboxylic group and that may or may not contain a sulfide group in its structure and that forms charge-transfer complexes ligand-metal with the element of Group VI B, in the presence of a protic solvent; w) impregnating the solution obtained in step v) to the material obtained in subsection t); x) drying the material obtained in step w) at a temperature between 60 and 100° C.; y) said procedure performing followed by the sequence of subsections a), c) to subsection i); subsequently perform the extrusion step of step b) and continue with the step sequence of subsection j) to subsection x).

65 . The process according to claim 64 , wherein the hydroxylated and/or hydrated alumina is selected from the group consisting of boehmite, gibbsite, pseudoboehmite and bayerite.

66 . The process according to claim 64 , further comprising a formulating step in cylindrical, trilobular or tetralobular extrudates from powdered alumina precursor.

67 . The process according to claim 64 , further comprising transformation of the hydroxylated alumina extrudates to an dehydroxylated one in gamma, chi, eta, or theta phase by calcination process under static or dynamic air atmosphere at a temperature between 400 and 800° C., for a period of time between 4 and 24 h.

68 . The process according to claim 64 , further comprising the surface modification of extrudates of alumina or hydroxylated alumina or hydrated alumina with an inorganic oxide containing one element of the Groups II A, IV A and/or IV B of the periodic table.

69 . The process according to claim 64 , wherein the modification with an inorganic oxide is carried out by impregnating a solution containing hydrolyzed sols of one of the elements of Groups II A, IV A and/or IV B obtained by the sol-gel method.

70 . The process according to claim 64 further comprising the dissolution of an organometallic compound of an element of Groups II A, IV A and/or IV B of the periodic table, selected from the group consisting of methoxide, ethoxide, propoxide, isopropoxide, tetraethoxide, tetramethoxide, tetrapropoxide and tetrabutoxide, in a protic solvent selected from a low molecular weight alcohol selected from the group consisting of methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol and ter-butanol.

71 . The process according to claim 64 , further comprising the preparation of a solution containing hydrolyzed sols of one element of Groups II A, IV A and/or IV B of the periodic Table, by sol-gel method, maintaining a metal-organic/solvent molar ratio between 20 and 80, water/metal-organic between 0.1 and 1.0 and acid/metal-organic between 0.01 and 0.02.

72 . The process according to claim 64 , wherein the acid used as hydrolysis catalyst is either inorganic or organic, selected from the group consisting of nitric acid, hydrochloric acid, acetic acid, sulfuric acid, phosphoric acid and hydrofluoric acid.

73 . The process according to claim 64 , further comprising a polymerization step of the solution containing hydrolyzed sols of one element of Groups II A, IV A and/or IV B of the periodic table, which consists of a heat treatment at reflux at temperature between 25 and 90° C., for a period of time between 0 and 8 h.

74 . The process according to claim 64 , further comprising a heat treatment step under dynamic air atmosphere of the extrudates of alumina modified with an inorganic oxide of an element of Groups II A, IV A and/or IV B of the periodic table, at a temperature between 300 and 600° C., for a period of time between 2 and 24 h, for obtaining an inorganic oxide-surface modified support.

75 . The process according to claim 64 , wherein in one of its steps comprises the preparation of an aqueous solution containing at least one element of Group VI B and at least one non-noble element of Group VIII B and one element of Group V A of the periodic table, through the dissolution of salts or acids of said elements by thermal digestion consisting of refluxing at temperature between 40 and 100° C., for a period of time between 2 and 24 h.

76 . The process according to claim 64 further comprising the addition of an organic compound cont

Assignees

• Mexicano Inst Petrol
• Univ Mexico Nacional Autonoma

Inventors

• Cortes Jacome Maria Antonia
• Toledo Antonio Jose Antonio
• Escobar Aguilar Jose
• Lopez Salinas Esteban
• Angeles Chavez Carlos
• Torres Garcia Enelio
• Hernandez Cortez Jose Gonzalo
• Mosqueira Mondragon Maria De Lourdes Araceli
• Perez Luna Miguel
• Ferrat Torres Gerardo
• Ramirez Solis Jorge Fernando
• Gutierrez Alejandre Aida

Classifications

• B01J35/61

  Surface area · CPC title

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J2235/00

  Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties · CPC title

• B01J35/55

  Cylinders or rings · CPC title

• B01J35/37

  Crush or impact strength · CPC title