Navegar

Colección

Datos Estadísticas

Artículo

Estamos trabajando para incorporar este artículo al repositorio
Consulte el artículo en la página del editor
Consulte la política de Acceso Abierto del editor

Abstract:

In this paper, we report that the hydrogenolysis of glycerol can be carried out at atmospheric pressure and low temperature with high selectivity to 1,2-propanediol (1,2-PDO) over reduced copper catalyst. The vapor-phase reaction was carried out over the copper-based catalysts supported on alumina at ambient pressure, and the effects of temperature, space time, and H2 molar fraction in the feed were analyzed. The textural and structural characteristics of the catalysts with increasing copper loading were determined by N2 sorptometry (BET), inductively coupled plasma-atomic spectroscopy (ICP-AES), powder X-ray diffraction (PXRD), temperature-programmed reduction (TPR), and N2O chemisorption (metallic area). On the basis of both characterization and activity results, it was possible to conclude that the hydrogenolysis of glycerol to 1,2-propanediol in vapor phase at atmospheric pressure over copper-based catalysts is a structure sensitive reaction. Activity results suggests that the most probable pathway for the glycerol conversion into 1,2-propanediol under the employed conditions is glycerol is dehydration to hydroxyacetone (acetol), followed by its hydrogenation into 1,2-propanediol. Complete glycerol conversion and a selectivity of 60% to 1,2-propanediol was achieved, using a catalyst with 15 wt % CuO at 200°C, H2 molar fraction of 61%, and atmospheric pressure. © 2016 American Chemical Society.

Registro:

Documento: Artículo
Título:Vapor-Phase Hydrogenolysis of Glycerol to 1,2-Propanediol over Cu/Al2O3 Catalyst at Ambient Hydrogen Pressure
Autor:Dieuzeide, M.L.; Jobbagy, M.; Amadeo, N.
Filiación:ITHES, UBA, CONICET, Laboratorio de Procesos Catalíticos, Departamento de Ing. Química, Facultad de Ingeniería, Universidad de Buenos Aires, Pabellón de Industrias, Ciudad Universitaria, Ciudad Autónoma de Buenos Aires, 1428, Argentina
INQUIMAE, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellón II, Ciudad Universitaria, Ciudad Autónoma de Buenos Aires, 1428, Argentina
Palabras clave:Alumina; Atmospheric pressure; Atmospheric structure; Atmospheric temperature; Atomic emission spectroscopy; Atomic spectroscopy; Catalysts; Copper; Glycerol; Hydrogenolysis; Hydrolysis; Inductively coupled plasma; Temperature; Vapor phase epitaxy; X ray diffraction; Copper-based catalysts; Effects of temperature; Glycerol conversions; Powder X-ray diffraction (pXRD); Structural characteristics; Structure sensitive reactions; Temperature-programmed reduction; Vapor phase reactions; Catalyst selectivity
Año:2016
Volumen:55
Número:9
Página de inicio:2527
Página de fin:2533
DOI: http://dx.doi.org/10.1021/acs.iecr.5b03004
Título revista:Industrial and Engineering Chemistry Research
Título revista abreviado:Ind. Eng. Chem. Res.
ISSN:08885885
CODEN:IECRE
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_08885885_v55_n9_p2527_Dieuzeide

Referencias:

  • Pagliaro, M., Ciriminna, R., Kimura, H., Rossi, M., Della Pina, C., From Glycerol to value-added products (2007) Angew. Chem., Int. Ed., 46, pp. 4434-4440
  • Chaminand, J., Djakovitch, L., Gallezot, P., Marion, P., Pinel, C., Rosier, C., Glycerol hydrogenolysis on heterogeneous catalysts (2004) Green Chem., 6, pp. 359-361
  • Dasari, M.A., Kiatsimkul, P., Sutterlin, W.R., Suppes, G.J., Low-pressure hydrogenolysis of glycerol to propylene glycol (2005) Appl. Catal., A, 281, pp. 225-231
  • Kusunoki, Y., Miyazawa, T., Kunimori, K., Tomishige, K., Highly active metal-acid bifunctional catalyst system for hydrogenolysis of glycerol under mild reaction conditions (2005) Catal. Commun., 6, pp. 645-649
  • Sato, S., Akiyama, M., Takahashi, R., Hara, T., Inui, K., Yokota, M., Vapor-phase reaction of polyols over copper catalysts (2008) Appl. Catal., A, 347, pp. 186-191
  • Huang, L., Zhu, Y.L., Zheng, H.Y., Li, Y.W., Zeng, Z.Y., Continuous production of 1,2-propanediol by the selective hydrogenolysis of solvent-free glycerol under mild conditions (2008) J. Chem. Technol. Biotechnol., 83, pp. 1670-1675
  • Yuan, Z., Wang, J., Wang, L., Xie, W., Chen, P., Hou, Z., Zheng, X., Biodiesel derived glycerol hydrogenolysis to 1,2-propanediol on Cu/MgO catalysts (2010) Bioresour. Technol., 101, pp. 7088-7092
  • Montassier, C., Giraud, D., Barbier, J., (1988) Stud. Surf. Sci. Catal., 41, pp. 165-170
  • Montassier, C., Dumas, J.M., Granger, P., Barbier, J., Deactivation of supported copper based catalysts during polyol conversion in aqueous phase (1995) Appl. Catal., A, 121, pp. 231-244
  • Sato, S., Akiyama, M., Inui, K., Yokota, M., Selective Conversion of Glycerol into 1,2-Propanediol at Ambient Hydrogen Pressure (2009) Chem. Lett., 38, pp. 560-561
  • Akiyama, M., Sato, S., Takahashi, R., Inui, K., Yokota, M., Dehydration-hydrogenation of glycerol into 1,2-propanediol at ambient hydrogen pressure (2009) Appl. Catal., A, 371, pp. 60-66
  • Guo, L., Zhou, J., Mao, J., Guo, X., Zhang, S., Supported Cu catalysts for the selective hydrogenolysis of glycerol to propanediols (2009) Appl. Catal., A, 367, pp. 93-98
  • Maris, E.P., Davis, R.J., Hydrogenolysis of glycerol over carbon-supported Ru and Pt catalysts (2007) J. Catal., 249, pp. 328-337
  • Wang, S., Zhang, Y., Liu, H., Selective Hydrogenolysis of Glycerol to Propylene Glycol on Cu-ZnO Composite Catalysts: Structural Requirements and Reaction Mechanism (2010) Chem. - Asian J., 5, pp. 1100-1111
  • Xiao, Z., Wang, X., Xiu, J., Wang, Y., Williams, C., Liang, C., Synergetic effect between CuO and Cu+ in the Cu-Cr catalysts forhydrogenolysis of glycerol (2014) Catal. Today, 234, pp. 200-207
  • Balaraju, M., Rekha, V., Sai Prasad, S., Prasad, R.B.N., Lingaiah, N., Selective Hydrogenolysis of Glycerol to 1, 2 Propanediol over Cu-ZnO Catalysts (2008) Catal. Lett., 126, pp. 119-124
  • Wang, S., Liu, H., Selective hydrogenolysis of glycerol to propylene glycol on Cu-ZnO catalysts (2007) Catal. Lett., 117, pp. 62-67
  • Vasiliadou, E., Eggenhuisen, T., Munnik, P., De Jongh, P., De Jong, K.P., Lemonidou, A., Synthesis and performance of highly dispersed Cu/SiO2 catalysts for thehydrogenolysis of glycerol (2014) Appl. Catal., B, 145, pp. 108-119
  • Vila, F., Lopez Granados, M., Ojeda, M., Fierro, J.L.G., Mariscal, R., Glycerol hydrogenolysis to 1,2-propanediol with Cu/γ-Al2O3: Effect of the activation process (2012) Catal. Today, 187, pp. 122-128
  • Bienholz, A., Hofmann, H., Claus, P., Selective hydrogenolysis of glycerol over copper catalysts both in liquid and vapour phase: Correlation between the copper surface area and the catalyst's activity (2011) Appl. Catal., A, 391, pp. 153-157
  • Feng, Y., Yin, H., Wang, A., Shen, L., Yu, L., Jiang, T., Gas phase hydrogenolysis of glycerol catalyzed by Cu/ZnO/MOx (MOx = Al2O3, TiO2, and ZrO2) catalysts (2011) Chem. Eng. J., 168, pp. 403-412
  • Sato, S., Takahashi, R., Sodesawa, T., Yuma, K., Obata, Y., Distinction between Surface and Bulk Oxidation of Cu through N2O Decomposition (2000) J. Catal., 196, pp. 195-199
  • Gervasini, A., Bennici, S., Dispersion and surface states of copper catalysts by temperature-programmed-reduction of oxidized surfaces (s-TPR) (2005) Appl. Catal., A, 281, pp. 199-205
  • Dow, W., Wang, Y., Huang, T., TPR and XRD studies of yttria-doped ceria/g-alumina-supported copper oxide catalyst (1996) J. Catal., 160, pp. 155-170
  • Lopez-Suarez, F.E., Bueno-Lopez, A., Illán-Gómez, M.J., Cu/Al2O3 catalysts for soot oxidation: Copper loading effect (2008) Appl. Catal., B, 84, pp. 651-658
  • Huang, Z., Liu, H., Cui, F., Zuo, J., Chen, J., Xia, Ch., Effects of the precipitation agents and rare earth additives on thestructure and catalytic performance in glycerol hydrogenolysis of Cu/SiO2 catalysts prepared by precipitation-gel method (2014) Catal. Today, 234, pp. 223-232
  • Vasiliadou, E.S., Lemonidou, A.A., Investigating the performance and deactivation behaviour of silica-supported copper catalysts in glycerol hydrogenolysis (2011) Appl. Catal., A, 396, pp. 177-185
  • Chiu, C.W., Tekeei, A., Ronco, J.M., Banks, M.L., Suppes, G.J., Reducing Byproduct formation during Conversion of Glycerol to Propylene Glycol (2008) Ind. Eng. Chem. Res., 47, pp. 6878-6884
  • Miyazawa, T., Koso, S., Kunimori, K., Tomishige, K., Glycerol hydrogenolysis to 1,2-propanediol catalyzed by a heat-resistant ion-exchange resin combined with Ru/C (2007) Appl. Catal., A, 329, pp. 30-35

Citas:

---------- APA ----------
Dieuzeide, M.L., Jobbagy, M. & Amadeo, N. (2016) . Vapor-Phase Hydrogenolysis of Glycerol to 1,2-Propanediol over Cu/Al2O3 Catalyst at Ambient Hydrogen Pressure. Industrial and Engineering Chemistry Research, 55(9), 2527-2533.
http://dx.doi.org/10.1021/acs.iecr.5b03004
---------- CHICAGO ----------
Dieuzeide, M.L., Jobbagy, M., Amadeo, N. "Vapor-Phase Hydrogenolysis of Glycerol to 1,2-Propanediol over Cu/Al2O3 Catalyst at Ambient Hydrogen Pressure" . Industrial and Engineering Chemistry Research 55, no. 9 (2016) : 2527-2533.
http://dx.doi.org/10.1021/acs.iecr.5b03004
---------- MLA ----------
Dieuzeide, M.L., Jobbagy, M., Amadeo, N. "Vapor-Phase Hydrogenolysis of Glycerol to 1,2-Propanediol over Cu/Al2O3 Catalyst at Ambient Hydrogen Pressure" . Industrial and Engineering Chemistry Research, vol. 55, no. 9, 2016, pp. 2527-2533.
http://dx.doi.org/10.1021/acs.iecr.5b03004
---------- VANCOUVER ----------
Dieuzeide, M.L., Jobbagy, M., Amadeo, N. Vapor-Phase Hydrogenolysis of Glycerol to 1,2-Propanediol over Cu/Al2O3 Catalyst at Ambient Hydrogen Pressure. Ind. Eng. Chem. Res. 2016;55(9):2527-2533.
http://dx.doi.org/10.1021/acs.iecr.5b03004