Kinetic and Thermodynamic Analysis of Guaiacol Hydrodeoxygenation

Сульман, Александрина Михайловна; Mäki‐Arvela, Päivi; Bomont, Louis; Alda-Onggar, Moldir; Fedorov, V.S.; Russo, Vincenzo; Eränen, Kari; Peurla, Markus; Akhmetzyanova, Uliana; Skuhrovcová, Lenka; Tišler, Zdeněk; Grénman, Henrik; Wärnå, Johan; Murzin, Dmitry Yu.

doi:10.1007/s10562-019-02856-x

Cited by 34 publications

(16 citation statements)

References 38 publications

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“…Only 3% of ( 4) was seen at 3 h and none was detected at 6 h. This indicates that ( 4) is an intermediate in the production of (1). It has been reported that the hydrogenolysis of the methyl-oxygen bond (demethylation) of the methoxy group of GUA to form catechol is the first stage of the reaction, followed by a second stage leading to the elimination of one of the hydroxyl groups (deoxygenation) to produce phenol [12,63,64]. Over the BCR catalyst, phenol was also produced via the direct demethoxylation of GUA.…”

Section: Catalytic Hdo Of Guamentioning

confidence: 99%

Understanding the Surface Characteristics of Biochar and Its Catalytic Activity for the Hydrodeoxygenation of Guaiacol

Adilina¹,

Widjaya²,

Hidayati³

et al. 2021

Catalysts

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Biochar (BCR) was obtained from the pyrolysis of a palm-oil-empty fruit bunch at 773 K for 2 h and used as a catalyst for the hydrodeoxygenation (HDO) of guaiacol (GUA) as a bio-oil model compound. Brunauer–Emmet–Teller surface area analysis, NH3 and CO2-temperature-programmed desorption, scanning electron microscope–dispersive X-ray spectroscopy, CHN analysis and X-ray fluorescence spectroscopy suggested that macroporous and mesoporous structures were formed in BCR with a co-presence of hydrophilic and hydrophobic sites and acid–base behavior. A combination of infrared, Raman and inelastic neutron scattering (INS) was carried out to achieve a complete vibrational assignment of BCR. The CH–OH ratio in BCR is ~5, showing that the hydroxyl functional groups are a minority species. There was no evidence for any aromatic C–H stretch modes in the infrared, but they are clearly seen in the INS and are the majority species, with a ratio of sp3–CH:sp2–CH of 1:1.3. The hydrogen bound to sp2–C is largely present as isolated C–H bonds, rather than adjacent C–H bonds. The Raman spectrum shows the characteristic G band (ideal graphitic lattice) and three D bands (disordered graphitic lattice, amorphous carbon, and defective graphitic lattice) of sp2 carbons. Adsorbed water in BCR is present as disordered layers on the surface rather than trapped in voids in the material and could be removed easily by drying prior to catalysis. Catalytic testing demonstrated that BCR was able to catalyze the HDO of GUA, yielding phenol and cresols as the major products. Phenol was produced both from the direct demethoxylation of GUA, as well as through the demethylation pathway via the formation of catechol as the intermediate followed by deoxygenation.

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Section: Catalytic Hdo Of Guamentioning

confidence: 99%

Understanding the Surface Characteristics of Biochar and Its Catalytic Activity for the Hydrodeoxygenation of Guaiacol

Adilina¹,

Widjaya²,

Hidayati³

et al. 2021

Catalysts

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“…In work, Mo 2 C/SBA‐15 catalyst has been prepared using hexamethylenetetramine ammonium heptamolybdate complex as a precursor. Kinetics of guaiacol hydrodeoxygenation was studied using supported Mo 2 C/SBA‐15 under 30 bar hydrogen at 200 °C and 300 °C.…”

Section: Introductionmentioning

confidence: 99%

Hydrodeoxygenation of Guaiacol with Molybdenum‐Carbide‐Based Carbon Catalysts

2020

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Molybdenum carbide-based carbon materials were investigated as a catalyst for hydrodeoxygenation (HDO) of guaiacol. Mechanochemical synthesis has been used as a novel approach to obtain a fine molybdenum carbide-based carbon catalysts. Guaiacol was chosen as a bio-oil model compound to estimate the potential of the catalysts. The catalytic tests were carried out at 4 MPa initial hydrogen pressure, 320°C for 180 min in a batch autoclave reactor. Insert abstract text here. A feed mixture was 3.5 g guaiacol in 66.5 g hexadecane as a solvent.

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“…Aún hace falta información acerca del estudio termodinámico (∆ ,∆ ,Keq), Sulman et al [69] estimaron entalpías y la energía libre de Gibbs de las rutas de reacción involucradas en la HDO de guayacol (Figura 4.9), a partir de una base de datos ChemCAD v.5.0 a condiciones estándar y a temperaturas entre 200 y 300 °C, 25 bar. La Figura 4.9 muestra las vías de reacción global para la HDO de guayacol mientras que los compuestos encerrados en circulo son moléculas representativas visto en la HDO de anisol.…”

Section: Efecto De La Temperatura En La Hdo Anisolunclassified

Proceso de hidrodesoxigenación de anisol sobre catalizadores de Ni-Ru soportado en TiO2

Santos¹

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En este trabajo se determinó la actividad y selectividad de catalizadores monometálicos Ni, Ru y bimetálicos NiRu soportados en TiO2 (P-25) y SBA-15 en la HDO de anisol. Además, se realizó un estudio del efecto de las condiciones de reacción (T=250-350 °C, CA= 0.1-0.3 mol·L-1) en NiRu/TiO2 con el fin determinar la mayor selectividad para la obtención de productos desoxigenados y proponer un modelo cinético. Finalmente se realizó modificaciones en cuanto a la carga metálica de Ni a contenidos de 0.5, 1 y 5 % en peso de metal con el sistema NiRu/TiO2. Los catalizadores fueron preparados por impregnación en humedad incipiente a partir de soluciones de Ni·(NO3)2·6H2O y Ru·(NO)(NO3)3 como precursores metálicos, a un contenido nominal de rutenio 0.5 % y 5% peso de metal en níquel. Además de los catalizadores bimetálicos, se impregnaron de manera individual los metales de Ni y Ru con los soportes TiO2 y SBA15. Los catalizadores monometálicos de Ni y Ru soportados en SBA15 mostraron velocidades iniciales de reaccion de 3.3x10-5 y 1.85x10-5 mol·gcat·s-1, respectivamente, en la HDO de anisol. Al combinar ambos metales la velocidad se incrementó hasta el valor de 7.92x10-5 mol·gcat·s-1 superando la actividad de los catalizadores monometálicos dos veces más grande para Ni/SBA15 y cuatro para Ru/SBA15 lo que sugiere un efecto de promoción entre Ni y Ru. Por último, cuando se utilizó TiO2 como soporte, el Ni presentó una velocidad inicial de 2.0 x10-5 mol·gcat·s-1. Al evaluar el catalizador monometálico de Ru la velocidad observada fue de 8.3 x10-5 mol·gcat·s-1. con la adición del segundo metal, la velocidad fue 45% menos favorable comparado con Ru/TiO2 y 50% más grande que Ni/TiO2 mostrando un efecto desfavorable al combinar ambos metales. Finalmente, la selectividad cambio por el tipo de catalizador y soporte, los catalizadores de Ru/TiO2, Ru/SBA15 y NiRu/TiO2 obtuvieron como producto principal benceno lo que indicó que la ruta preferente para este tipo de sistemas fue la demetoxilación (DMO). Por último, para los catalizadores Ni/TiO2, Ni/SBA15 y NiRu/SBA15 la vía prioritaria fue la hidrogenación (HYD) por su alto contenido en metoxiciclohexano.

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Kinetic and Thermodynamic Analysis of Guaiacol Hydrodeoxygenation

Cited by 34 publications

References 38 publications

Understanding the Surface Characteristics of Biochar and Its Catalytic Activity for the Hydrodeoxygenation of Guaiacol

Understanding the Surface Characteristics of Biochar and Its Catalytic Activity for the Hydrodeoxygenation of Guaiacol

Hydrodeoxygenation of Guaiacol with Molybdenum‐Carbide‐Based Carbon Catalysts

Proceso de hidrodesoxigenación de anisol sobre catalizadores de Ni-Ru soportado en TiO2

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