Nuevos precursores Al-X-Mo/W (X = Al, Co, V, P) vía síntesis reticular: Caracterización por 27Al NMR y Raman Microprobe.Aplicación en desulfurización oxidativa (ODS).

MERCEDES MUÑOZ; GUSTAVO ROMANELLI; IRMA L. BOTTO; CARMEN I. CABELLO; CAROLE LAMONIER; MICKAEL CAPRON; PASCALE BARANEK; PASCAL BLANCHARD; EDMOND PAYEN

Gramado, Brasil

Simposio; XX Simposio Iberoamericano de Catálisis; 2006

Se investigó la actividad de nuevos precursores trimetálicos obtenidos por síntesis reticular, en dos diferentes reacciones de desulfurización oxidativa (ODS): difenilsulfuro a difenilsulfona en presencia de H2O2 y de dibenzotiofeno DBTs mediante terbutilhidroperóxido (t-BuOOH). Se prepararon diversas fases de fórmula general A113-[XMo6] (X= Al (III), Co(III), V(V) y Al13-X[WO4]n combinando el isopolication Keggin [AlO4Al12(OH)24(H2O)12]7+ (Al13) e iso ó heteropolimetalatos del tipo: [XMo6O24H6]3-; [Co2Mo10O38H4]6-; [WO4]n , [PW9O34]9-, [V2W4O19]6-. La caracterización se llevó a cabo por XRD, 27Al NMR, FTIR y Raman Microprobe. La estabilidad térmica se estudió por TGA-DTA. Los tests catalíticos se realizaron en batch entre 75 y 80 °C. Los resultados preliminares indican que la actividad ODS aumenta con la densidad electrónica del S en el sustrato, siendo mayor para difenilsulfuro que para DBT. Los catalizadores a base de heteropolimolibdatos presentan una mejor performance en ambas reacciones, mientras el heteroátomo parece mejorar la polarización del enlace Mo-O2t. Catalizadores a base de iso y politungstatos no mostraron actividad excepto aquel conteniendo P como heteroátomo. Asimismo se comprobó por Raman Microprobe, que las fases empleadas conservan su estructura después de la reacción, mostrando la interesante posibilidad de reutilización. The activity of new trimetallic precursors obtained by reticular synthesis was investigated in two different oxidizing desulfurization reactions (ODS): diphenilsulfide to diphenilsulfone in presence of H2O2 and dibenzothiophene DBTs to DBTO by means of tert-butyl hydroperoxide (t-BuOOH). Several phases of general formula were prepared: A113-[XMo6] (X= Al (III), Co(III), V(V) and Al13-P[WO4]n combining the isopolycation Keggin [AlO4Al12(OH)24(H2O)12]7+ (Al13) and iso or heteropolymetalates such as [XMo6O24H6]3-; [Co2Mo10O38H4]6-; [WO4]n, [PW9O34]9-, [V2W4O19]6-. The characterization was carried out by XRD, 27Al NMR, FTIR and Raman Microprobe. The thermal stability was studied by TGA-DTA. The catalytic tests were carried out in batch between 75 and 80º C. The preliminary results indicated that ODS activity increased as the electronic density of the sulfur substrate increased, being higher for diphenilsulfide than for DBT. The catalysts based on heteropolymolybdates presented a better performance in both reactions, whereas the heteroatom seemed to enhance the polarization of Mo-O2t bond. Catalysts based on iso and polytungstates did not show activity except for that containing P as heteroatom. Besides, it was verified by Raman Microprobe that the used phases kept their structure after reaction, showing the interesting possibility of re-use.2O2 y de dibenzotiofeno DBTs mediante terbutilhidroperóxido (t-BuOOH). Se prepararon diversas fases de fórmula general A113-[XMo6] (X= Al (III), Co(III), V(V) y Al13-X[WO4]n combinando el isopolication Keggin [AlO4Al12(OH)24(H2O)12]7+ (Al13) e iso ó heteropolimetalatos del tipo: [XMo6O24H6]3-; [Co2Mo10O38H4]6-; [WO4]n , [PW9O34]9-, [V2W4O19]6-. La caracterización se llevó a cabo por XRD, 27Al NMR, FTIR y Raman Microprobe. La estabilidad térmica se estudió por TGA-DTA. Los tests catalíticos se realizaron en batch entre 75 y 80 °C. Los resultados preliminares indican que la actividad ODS aumenta con la densidad electrónica del S en el sustrato, siendo mayor para difenilsulfuro que para DBT. Los catalizadores a base de heteropolimolibdatos presentan una mejor performance en ambas reacciones, mientras el heteroátomo parece mejorar la polarización del enlace Mo-O2t. Catalizadores a base de iso y politungstatos no mostraron actividad excepto aquel conteniendo P como heteroátomo. Asimismo se comprobó por Raman Microprobe, que las fases empleadas conservan su estructura después de la reacción, mostrando la interesante posibilidad de reutilización. The activity of new trimetallic precursors obtained by reticular synthesis was investigated in two different oxidizing desulfurization reactions (ODS): diphenilsulfide to diphenilsulfone in presence of H2O2 and dibenzothiophene DBTs to DBTO by means of tert-butyl hydroperoxide (t-BuOOH). Several phases of general formula were prepared: A113-[XMo6] (X= Al (III), Co(III), V(V) and Al13-P[WO4]n combining the isopolycation Keggin [AlO4Al12(OH)24(H2O)12]7+ (Al13) and iso or heteropolymetalates such as [XMo6O24H6]3-; [Co2Mo10O38H4]6-; [WO4]n, [PW9O34]9-, [V2W4O19]6-. The characterization was carried out by XRD, 27Al NMR, FTIR and Raman Microprobe. The thermal stability was studied by TGA-DTA. The catalytic tests were carried out in batch between 75 and 80º C. The preliminary results indicated that ODS activity increased as the electronic density of the sulfur substrate increased, being higher for diphenilsulfide than for DBT. The catalysts based on heteropolymolybdates presented a better performance in both reactions, whereas the heteroatom seemed to enhance the polarization of Mo-O2t bond. Catalysts based on iso and polytungstates did not show activity except for that containing P as heteroatom. Besides, it was verified by Raman Microprobe that the used phases kept their structure after reaction, showing the interesting possibility of re-use.13-[XMo6] (X= Al (III), Co(III), V(V) y Al13-X[WO4]n combinando el isopolication Keggin [AlO4Al12(OH)24(H2O)12]7+ (Al13) e iso ó heteropolimetalatos del tipo: [XMo6O24H6]3-; [Co2Mo10O38H4]6-; [WO4]n , [PW9O34]9-, [V2W4O19]6-. La caracterización se llevó a cabo por XRD, 27Al NMR, FTIR y Raman Microprobe. La estabilidad térmica se estudió por TGA-DTA. Los tests catalíticos se realizaron en batch entre 75 y 80 °C. Los resultados preliminares indican que la actividad ODS aumenta con la densidad electrónica del S en el sustrato, siendo mayor para difenilsulfuro que para DBT. Los catalizadores a base de heteropolimolibdatos presentan una mejor performance en ambas reacciones, mientras el heteroátomo parece mejorar la polarización del enlace Mo-O2t. Catalizadores a base de iso y politungstatos no mostraron actividad excepto aquel conteniendo P como heteroátomo. Asimismo se comprobó por Raman Microprobe, que las fases empleadas conservan su estructura después de la reacción, mostrando la interesante posibilidad de reutilización. The activity of new trimetallic precursors obtained by reticular synthesis was investigated in two different oxidizing desulfurization reactions (ODS): diphenilsulfide to diphenilsulfone in presence of H2O2 and dibenzothiophene DBTs to DBTO by means of tert-butyl hydroperoxide (t-BuOOH). Several phases of general formula were prepared: A113-[XMo6] (X= Al (III), Co(III), V(V) and Al13-P[WO4]n combining the isopolycation Keggin [AlO4Al12(OH)24(H2O)12]7+ (Al13) and iso or heteropolymetalates such as [XMo6O24H6]3-; [Co2Mo10O38H4]6-; [WO4]n, [PW9O34]9-, [V2W4O19]6-. The characterization was carried out by XRD, 27Al NMR, FTIR and Raman Microprobe. The thermal stability was studied by TGA-DTA. The catalytic tests were carried out in batch between 75 and 80º C. The preliminary results indicated that ODS activity increased as the electronic density of the sulfur substrate increased, being higher for diphenilsulfide than for DBT. The catalysts based on heteropolymolybdates presented a better performance in both reactions, whereas the heteroatom seemed to enhance the polarization of Mo-O2t bond. Catalysts based on iso and polytungstates did not show activity except for that containing P as heteroatom. Besides, it was verified by Raman Microprobe that the used phases kept their structure after reaction, showing the interesting possibility of re-use.13-X[WO4]n combinando el isopolication Keggin [AlO4Al12(OH)24(H2O)12]7+ (Al13) e iso ó heteropolimetalatos del tipo: [XMo6O24H6]3-; [Co2Mo10O38H4]6-; [WO4]n , [PW9O34]9-, [V2W4O19]6-. La caracterización se llevó a cabo por XRD, 27Al NMR, FTIR y Raman Microprobe. La estabilidad térmica se estudió por TGA-DTA. Los tests catalíticos se realizaron en batch entre 75 y 80 °C. Los resultados preliminares indican que la actividad ODS aumenta con la densidad electrónica del S en el sustrato, siendo mayor para difenilsulfuro que para DBT. Los catalizadores a base de heteropolimolibdatos presentan una mejor performance en ambas reacciones, mientras el heteroátomo parece mejorar la polarización del enlace Mo-O2t. Catalizadores a base de iso y politungstatos no mostraron actividad excepto aquel conteniendo P como heteroátomo. Asimismo se comprobó por Raman Microprobe, que las fases empleadas conservan su estructura después de la reacción, mostrando la interesante posibilidad de reutilización. The activity of new trimetallic precursors obtained by reticular synthesis was investigated in two different oxidizing desulfurization reactions (ODS): diphenilsulfide to diphenilsulfone in presence of H2O2 and dibenzothiophene DBTs to DBTO by means of tert-butyl hydroperoxide (t-BuOOH). Several phases of general formula were prepared: A113-[XMo6] (X= Al (III), Co(III), V(V) and Al13-P[WO4]n combining the isopolycation Keggin [AlO4Al12(OH)24(H2O)12]7+ (Al13) and iso or heteropolymetalates such as [XMo6O24H6]3-; [Co2Mo10O38H4]6-; [WO4]n, [PW9O34]9-, [V2W4O19]6-. The characterization was carried out by XRD, 27Al NMR, FTIR and Raman Microprobe. The thermal stability was studied by TGA-DTA. The catalytic tests were carried out in batch between 75 and 80º C. The preliminary results indicated that ODS activity increased as the electronic density of the sulfur substrate increased, being higher for diphenilsulfide than for DBT. The catalysts based on heteropolymolybdates presented a better performance in both reactions, whereas the heteroatom seemed to enhance the polarization of Mo-O2t bond. Catalysts based on iso and polytungstates did not show activity except for that containing P as heteroatom. Besides, it was verified by Raman Microprobe that the used phases kept their structure after reaction, showing the interesting possibility of re-use.6O24H6]3-; [Co2Mo10O38H4]6-; [WO4]n , [PW9O34]9-, [V2W4O19]6-. La caracterización se llevó a cabo por XRD, 27Al NMR, FTIR y Raman Microprobe. La estabilidad térmica se estudió por TGA-DTA. Los tests catalíticos se realizaron en batch entre 75 y 80 °C. Los resultados preliminares indican que la actividad ODS aumenta con la densidad electrónica del S en el sustrato, siendo mayor para difenilsulfuro que para DBT. Los catalizadores a base de heteropolimolibdatos presentan una mejor performance en ambas reacciones, mientras el heteroátomo parece mejorar la polarización del enlace Mo-O2t. Catalizadores a base de iso y politungstatos no mostraron actividad excepto aquel conteniendo P como heteroátomo. Asimismo se comprobó por Raman Microprobe, que las fases empleadas conservan su estructura después de la reacción, mostrando la interesante posibilidad de reutilización. The activity of new trimetallic precursors obtained by reticular synthesis was investigated in two different oxidizing desulfurization reactions (ODS): diphenilsulfide to diphenilsulfone in presence of H2O2 and dibenzothiophene DBTs to DBTO by means of tert-butyl hydroperoxide (t-BuOOH). Several phases of general formula were prepared: A113-[XMo6] (X= Al (III), Co(III), V(V) and Al13-P[WO4]n combining the isopolycation Keggin [AlO4Al12(OH)24(H2O)12]7+ (Al13) and iso or heteropolymetalates such as [XMo6O24H6]3-; [Co2Mo10O38H4]6-; [WO4]n, [PW9O34]9-, [V2W4O19]6-. The characterization was carried out by XRD, 27Al NMR, FTIR and Raman Microprobe. The thermal stability was studied by TGA-DTA. The catalytic tests were carried out in batch between 75 and 80º C. The preliminary results indicated that ODS activity increased as the electronic density of the sulfur substrate increased, being higher for diphenilsulfide than for DBT. The catalysts based on heteropolymolybdates presented a better performance in both reactions, whereas the heteroatom seemed to enhance the polarization of Mo-O2t bond. Catalysts based on iso and polytungstates did not show activity except for that containing P as heteroatom. Besides, it was verified by Raman Microprobe that the used phases kept their structure after reaction, showing the interesting possibility of re-use.27Al NMR, FTIR y Raman Microprobe. La estabilidad térmica se estudió por TGA-DTA. Los tests catalíticos se realizaron en batch entre 75 y 80 °C. Los resultados preliminares indican que la actividad ODS aumenta con la densidad electrónica del S en el sustrato, siendo mayor para difenilsulfuro que para DBT. Los catalizadores a base de heteropolimolibdatos presentan una mejor performance en ambas reacciones, mientras el heteroátomo parece mejorar la polarización del enlace Mo-O2t. Catalizadores a base de iso y politungstatos no mostraron actividad excepto aquel conteniendo P como heteroátomo. Asimismo se comprobó por Raman Microprobe, que las fases empleadas conservan su estructura después de la reacción, mostrando la interesante posibilidad de reutilización. The activity of new trimetallic precursors obtained by reticular synthesis was investigated in two different oxidizing desulfurization reactions (ODS): diphenilsulfide to diphenilsulfone in presence of H2O2 and dibenzothiophene DBTs to DBTO by means of tert-butyl hydroperoxide (t-BuOOH). Several phases of general formula were prepared: A113-[XMo6] (X= Al (III), Co(III), V(V) and Al13-P[WO4]n combining the isopolycation Keggin [AlO4Al12(OH)24(H2O)12]7+ (Al13) and iso or heteropolymetalates such as [XMo6O24H6]3-; [Co2Mo10O38H4]6-; [WO4]n, [PW9O34]9-, [V2W4O19]6-. The characterization was carried out by XRD, 27Al NMR, FTIR and Raman Microprobe. The thermal stability was studied by TGA-DTA. The catalytic tests were carried out in batch between 75 and 80º C. The preliminary results indicated that ODS activity increased as the electronic density of the sulfur substrate increased, being higher for diphenilsulfide than for DBT. The catalysts based on heteropolymolybdates presented a better performance in both reactions, whereas the heteroatom seemed to enhance the polarization of Mo-O2t bond. Catalysts based on iso and polytungstates did not show activity except for that containing P as heteroatom. Besides, it was verified by Raman Microprobe that the used phases kept their structure after reaction, showing the interesting possibility of re-use.2t. Catalizadores a base de iso y politungstatos no mostraron actividad excepto aquel conteniendo P como heteroátomo. Asimismo se comprobó por Raman Microprobe, que las fases empleadas conservan su estructura después de la reacción, mostrando la interesante posibilidad de reutilización. The activity of new trimetallic precursors obtained by reticular synthesis was investigated in two different oxidizing desulfurization reactions (ODS): diphenilsulfide to diphenilsulfone in presence of H2O2 and dibenzothiophene DBTs to DBTO by means of tert-butyl hydroperoxide (t-BuOOH). Several phases of general formula were prepared: A113-[XMo6] (X= Al (III), Co(III), V(V) and Al13-P[WO4]n combining the isopolycation Keggin [AlO4Al12(OH)24(H2O)12]7+ (Al13) and iso or heteropolymetalates such as [XMo6O24H6]3-; [Co2Mo10O38H4]6-; [WO4]n, [PW9O34]9-, [V2W4O19]6-. The characterization was carried out by XRD, 27Al NMR, FTIR and Raman Microprobe. The thermal stability was studied by TGA-DTA. The catalytic tests were carried out in batch between 75 and 80º C. The preliminary results indicated that ODS activity increased as the electronic density of the sulfur substrate increased, being higher for diphenilsulfide than for DBT. The catalysts based on heteropolymolybdates presented a better performance in both reactions, whereas the heteroatom seemed to enhance the polarization of Mo-O2t bond. Catalysts based on iso and polytungstates did not show activity except for that containing P as heteroatom. Besides, it was verified by Raman Microprobe that the used phases kept their structure after reaction, showing the interesting possibility of re-use.2O2 and dibenzothiophene DBTs to DBTO by means of tert-butyl hydroperoxide (t-BuOOH). Several phases of general formula were prepared: A113-[XMo6] (X= Al (III), Co(III), V(V) and Al13-P[WO4]n combining the isopolycation Keggin [AlO4Al12(OH)24(H2O)12]7+ (Al13) and iso or heteropolymetalates such as [XMo6O24H6]3-; [Co2Mo10O38H4]6-; [WO4]n, [PW9O34]9-, [V2W4O19]6-. The characterization was carried out by XRD, 27Al NMR, FTIR and Raman Microprobe. The thermal stability was studied by TGA-DTA. The catalytic tests were carried out in batch between 75 and 80º C. The preliminary results indicated that ODS activity increased as the electronic density of the sulfur substrate increased, being higher for diphenilsulfide than for DBT. The catalysts based on heteropolymolybdates presented a better performance in both reactions, whereas the heteroatom seemed to enhance the polarization of Mo-O2t bond. Catalysts based on iso and polytungstates did not show activity except for that containing P as heteroatom. Besides, it was verified by Raman Microprobe that the used phases kept their structure after reaction, showing the interesting possibility of re-use.13-[XMo6] (X= Al (III), Co(III), V(V) and Al13-P[WO4]n combining the isopolycation Keggin [AlO4Al12(OH)24(H2O)12]7+ (Al13) and iso or heteropolymetalates such as [XMo6O24H6]3-; [Co2Mo10O38H4]6-; [WO4]n, [PW9O34]9-, [V2W4O19]6-. The characterization was carried out by XRD, 27Al NMR, FTIR and Raman Microprobe. The thermal stability was studied by TGA-DTA. The catalytic tests were carried out in batch between 75 and 80º C. The preliminary results indicated that ODS activity increased as the electronic density of the sulfur substrate increased, being higher for diphenilsulfide than for DBT. The catalysts based on heteropolymolybdates presented a better performance in both reactions, whereas the heteroatom seemed to enhance the polarization of Mo-O2t bond. Catalysts based on iso and polytungstates did not show activity except for that containing P as heteroatom. Besides, it was verified by Raman Microprobe that the used phases kept their structure after reaction, showing the interesting possibility of re-use.13-P[WO4]n combining the isopolycation Keggin [AlO4Al12(OH)24(H2O)12]7+ (Al13) and iso or heteropolymetalate