Hydrogenolysis of glycerol to propanediols over a Pt/ASA catalyst: The role of acid and metal sites on product selectivity and the reaction mechanism

Gandarias, Iñaki; Arias, P.L.; Requies, J.; Güemez, M.B.; Fierro, J.L.G.

doi:10.1016/j.apcatb.2010.04.008

Cited by 203 publications

(155 citation statements)

References 24 publications

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“…4 The XPS core-level spectra for Co 2p of (a) the oxide and (b) the Co-673 catalyst sample was treated in glycerol aqueous solution, under N 2 atmosphere instead of hydrogen, the CoO species remained unchanged, even after 12 h. The particle size was only 9.4 nm compared to the reduced sample in Fig 1c. This confirms that the CoO species in the as-prepared Co-673 catalyst was readily reduced to Co particles by H 2 under glycerol hydrogenolysis conditions, and that glycerol significantly promoted the reduction process. This could be related to the facilitated dissolution of H 2 in glycerol solution rather than in pure water as reported by Gandarias et al [30].…”

Section: Glycerol Hydrogenolysismentioning

confidence: 73%

Glycerol Hydrogenolysis over Co Catalysts Derived from a Layered Double Hydroxide Precursor

Guo

Song

et al. 2011

Catal Lett

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Co catalysts, obtained from a layered double Co-Zn-Al hydroxide, are highly active and stable towards the hydrogenolysis of glycerol to 1,2-propanediol (1,2-PDO) in aqueous media. The Co-673 catalyst, containing a CoO species, provided a glycerol conversion of 67.7% and a 1,2-PDO selectivity of 50.5%. The Co-873 catalyst comprising 16 nm Co nanoparticles gave a glycerol conversion of 70.6% and a 1,2-PDO selectivity of 57.8%. It was revealed that the CoO species in the Co-673 catalyst was readily converted to 50 nm Co particles under the glycerol hydrogenolysis conditions. The Co catalysts maintained a stable size and phase in recycling tests.

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Section: Glycerol Hydrogenolysismentioning

confidence: 73%

Glycerol Hydrogenolysis over Co Catalysts Derived from a Layered Double Hydroxide Precursor

Guo

Song

et al. 2011

Catal Lett

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“…The effects of acidity have been widely discussed for the hydrogenolysis of glycerol. It was suggested that the surface acid site could benefit from the formation of an intermediate acetol, which is then converted to 1,2-PDO [5,17,31,32]. In other words, the selectivity to 1,2-PDO may depend on the amount of surface acid sites.…”

Section: Influence Of Ni Metal State On the Catalytic Performancementioning

confidence: 99%

Effect of Phosphine Doping and the Surface Metal State of Ni on the Catalytic Performance of Ni/Al2O3 Catalyst

Cheng

Liang

et al. 2015

Catalysts

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Ni-based catalysts as replacement for noble metal catalysts are of particular interest in the catalytic conversion of biomass due to their cheap and satisfactory catalytic activity. The Ni/SiO2 catalyst has been studied for the hydrogenolysis of glycerol, and doping with phosphorus (P) found to improve the catalytic performance significantly because of the formation of Ni2P alloys. However, in the present work we disclose a different catalytic phenomenon for the P-doped Ni/Al2O3 catalyst. We found that doping with P has a significant effect on the state of the active Ni species, and thus improves the selectivity to 1,2-propanediol (1,2-PDO) significantly in the hydrogenolysis of glycerol, although Ni-P alloys were not observed in our catalytic system. The structure and selectivity correlations were determined from the experimental data, combining the results of X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), hydrogen temperature-programmed reduction (H2-TPR) and ammonia temperature-programmed desorption (NH3-TPD). The presence of NiO species, formed from P-doped Ni/Al2O3 catalyst, was shown to benefit the formation of 1,2-PDO. This was supported by the results of the Ni/Al2O3 catalyst containing NiO species with incomplete reduction. Furthermore, the OPEN ACCESSCatalysts 2015, 5 760 role the NiO species played in the reaction and the potential reaction mechanism over the P-doped Ni/Al2O3 catalyst is discussed. The new findings in the present work open a new vision for Ni catalysis and will benefit researchers in designing Ni-based catalysts.

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“…Entre los procesos mencionados se destaca la reducción selectiva de glicerol a 1,2-PD o propilenglicol (PG) y etilenglicol (EG) [3][4][5][6][7][8]. Ambos glicoles actualmente se obtienen de derivados del petróleo como propileno y etileno y son materias primas importantes utilizadas sobre todo en la producción de intermediarios como resinas no saturadas y epoxi; el 1,2-PD es además empleado en humectantes, anticongelantes y resinas de poliéster.…”

Section: Introductionunclassified

“…Esta reacción también ha sido estudiada utilizando catalizadores, como Ru/C, Pt/C, Ni/C, cromita de cobre, Ni/Sílice-Alúmina [9]. Catalizadores de metales nobles como Ru, Rh y Pt se emplean para dicha reacción de reducción selectiva en fase líquida [3][4][5][6]. Pt soportado sobre sílice-alúmina amorfa alcanzó 19% de conversión de glicerol y 32% de selectividad a PG, luego de 24 horas de reacción a 220ºC y 45 bars de presión de H 2 [5].…”

Section: Introductionunclassified

“…Catalizadores de metales nobles como Ru, Rh y Pt se emplean para dicha reacción de reducción selectiva en fase líquida [3][4][5][6]. Pt soportado sobre sílice-alúmina amorfa alcanzó 19% de conversión de glicerol y 32% de selectividad a PG, luego de 24 horas de reacción a 220ºC y 45 bars de presión de H 2 [5]. Con Ru sobre carbón activado se alcanzó 15,6 y 62,2% de conversión y selectividad a 1,2-PD, respectivamente, tras 8 horas de reacción a 200ºC y 15 bars [6].…”

Section: Introductionunclassified

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Catalizadores de cobre soportado parareducción selectiva de glicerol

Ferrari¹,

Comelli²

2015

Matéria (Rio J.)

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RESUMENLa industria del biodiesel ha traído aparejada una oferta creciente de glicerol, el cual es el subproducto del proceso, generando una caída de su precio. La transformación del glicerol en compuestos con valor agregado interesa pues mejoraría la ecuación económica global de la producción del biocombustible permitiendo un desarrollo ambiental sustentable al utilizar materia prima renovable. En Argentina, la provincia de Santa Fe tiene una capacidad instalada de 2,5 millones de toneladas/año de biodiesel, con las consiguientes 250.000 tn/año de glicerol, por lo que la temática es de sumo interés para el medio socio-productivo regional. Una ruta para valorizar el glicerol es a través de la reacción catalítica de hidrogenólisis, mejor llamada reducción selectiva, para obtener propanodioles. Catalizadores del tipo metal soportado fueron reportados como activos para conducir la hidrogenólisis en fase líquida, encontrando escasa información para la reacción en fase gas. Por este motivo, se prepararon catalizadores del tipo Metal/Soporte por impregnación por humedad incipiente, siendo evaluados en fase líquida en un sistema con reactor de acero inoxidable y operación semicontinua y en fase gas en un sistema continuo con reactor de lecho fijo y flujo descendente. La reacción se siguió por cromatografía de gases, siendo en línea para la fase no condensada. El rango de condiciones de operación evaluado fue 170-240°C y presiones 1-30 kg cm -2 . Para fase líquida, los niveles de actividad y selectividad a 1,2-propanodiol alcanzados fueron similares a los reportados, mejorando la conversión con el incremento de temperatura y presión. Para fase gas, conversión y selectividad fueron fuertemente influenciadas por las condiciones de reacción, siendo el principal co-producto el acetol, indicado como intermediario de la reacción. Los materiales que presentaron mejor comportamiento fueron caracterizados por RTP, DRX y FTIR para determinar sus características, relacionar la actividad catalítica y optimizar la preparación.Palabras clave: Glicerol, Propanodioles, Cu/Alúmina, Cu/Ferrierita, Cromita de cobre. ABSTRACTThe biodiesel industry has brought with it an oversupply of glycerol, which is the byproduct of the process, generating a fall in its price. The transformation of glycerol into value-added compounds interest as it would improve the overall economic balance of biofuel production enabling environmentally sustainable development by using renewable raw material. In Argentina, the province of Santa Fe has an installed capacity of 2.5 million TM/year of biodiesel, with consequent 250,000 TM/year of glycerol, so the topic is of great interest to the regional socio-productive means. One route to valorize glycerol is the catalytic hydrogenolysis reaction, better called selective reduction, to obtain propanediols. Metal supported catalysts were reported as assets to drive the liquid phase hydrogenolysis, finding little information for the gas phase reaction. For this reason, Metal/Support type catalysts were prepared by impregna...

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Hydrogenolysis of glycerol to propanediols over a Pt/ASA catalyst: The role of acid and metal sites on product selectivity and the reaction mechanism

Cited by 203 publications

References 24 publications

Glycerol Hydrogenolysis over Co Catalysts Derived from a Layered Double Hydroxide Precursor

Glycerol Hydrogenolysis over Co Catalysts Derived from a Layered Double Hydroxide Precursor

Effect of Phosphine Doping and the Surface Metal State of Ni on the Catalytic Performance of Ni/Al2O3 Catalyst

Catalizadores de cobre soportado parareducción selectiva de glicerol

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