Hydrogenation of phenol in aqueous phase with palladium on activated carbon catalysts

Abstract The hydrogenation of phenol in aqueous phase was studied in a continuous trickle bed reactor using commercial and some home-made Pd/activated carbon (AC) catalysts with the aim to explore a possible way for the treatment of phenolic wastewaters. The ranges studied for temperature, pressure and space-time (τ) were 110–170 °C, 2–9 bar and 0.5–3.1 kg cat  h/mol, respectively. The inlet concentration of phenol was always 1000 mg/L. High conversion values for phenol were obtained at 150 °C and 9 bar in the case of the commercial catalyst. This catalyst has shown a convenient chemical stability in long-term experiments, being Pd leaching almost negligible. Different home-made catalysts were prepared and the influence of Pd load and precursor as well as the preparation conditions on the activity and selectivity have been investigated. The highest phenol conversion values were obtained with the catalysts calcined at 250 °C and reduced in hydrogen atmosphere at 150 °C, using palladium chloride as precursor. Moreover, these conditions led to a higher selectivity towards cyclohexanol, the less toxic product of the reaction pathway. The introduction of oxygen groups on the surface of the activated carbon through oxidation with nitric acid also improved the selectivity to cyclohexanol, thus leading to a higher reduction of the ecotoxicity.

[1]  Martin Reinhard,et al.  Hydrodechlorination and hydrogenation of aromatic compounds over palladium on alumina in hydrogen-saturated water , 1998 .

[2]  K. Bhattacharyya,et al.  Hydrogenation of phenol over supported platinum and palladium catalysts , 1993 .

[3]  N. Mahata,et al.  Gas phase hydrogenation of phenol over supported palladium catalysts , 1999 .

[4]  Eun-Jae Shin,et al.  Gas-phase hydrogenation/hydrogenolysis of phenol over supported nickel catalysts , 2000 .

[5]  C. Moreno-Castilla,et al.  Carbon materials as adsorbents in aqueous solutions , 2000 .

[6]  J. Casas,et al.  Hydrodechlorination of 4-chlorophenol in aqueous phase using Pd/AC catalysts prepared with modified active carbon supports , 2006 .

[7]  F. Rodríguez-Reinoso,et al.  The effect of oxygen surface groups of the support on platinum dispersion in Pt/carbon catalysts , 1989 .

[8]  Cheng Lu,et al.  An analysis of the combined effects of organic toxicants. , 2002, The Science of the total environment.

[9]  J. Dojlido,et al.  Chemistry of water and water pollution , 1993 .

[10]  N. Mahata,et al.  Influence of Palladium Precursors on Structural Properties and Phenol Hydrogenation Characteristics of Supported Palladium Catalysts , 2000 .

[11]  Salvatore Scirè,et al.  Selective hydrogenation of phenol to cyclohexanone over supported Pd and Pd-Ca catalysts: an investigation on the influence of different supports and Pd precursors , 2002 .

[12]  F. García-Ochoa,et al.  Route of the catalytic oxidation of phenol in aqueous phase , 2002 .

[13]  F. Carrasco-Marín,et al.  The creation of acid carbon surfaces by treatment with (NH4)2S2O8 , 1997 .

[14]  Y. Sasson,et al.  Conversion of chlorophenols into cyclohexane by a recyclable Pd-Rh catalyst , 2005 .

[15]  S. Galvagno,et al.  Effect of the acid–base properties of Pd–Ca/Al2O3 catalysts on the selective hydrogenation of phenol to cyclohexanone: FT-IR and TPD characterization , 1998 .

[16]  J. Casas,et al.  Treatment of chlorophenols-bearing wastewaters through hydrodechlorination using Pd/activated carbon catalysts , 2004 .

[17]  J. Casas,et al.  Effects of Support Surface Composition on the Activity and Selectivity of Pd/C Catalysts in Aqueous-Phase Hydrodechlorination Reactions , 2005 .

[18]  P. Rao,et al.  Selectivity dependence on the alloying element of carbon supported Pt-alloy catalysts in the hydrogenation of phenol† , 1994 .

[19]  M. Ilori Utilization of cyclohexanol by bacteria in a tropical estuarine water , 2008, Folia Microbiologica.

[20]  E. Shin,et al.  Catalytic Hydrogen Treatment of Aromatic Alcohols , 1998 .

[21]  Paul Grange,et al.  Evidence of textural modifications of an activated carbon on liquid-phase oxidation treatments , 1997 .

[22]  Colin W. Park,et al.  Catalyst support effects: gas-phase hydrogenation of phenol over palladium. , 2003, Journal of colloid and interface science.

[23]  M. Sheintuch,et al.  Catalytic Abatement of Water Pollutants , 1998 .

[24]  N. Christofi,et al.  Combination ecotoxicity and testing of common chemical discharges to sewer using the Vibrio fischeri luminescence bioassay , 2003, International microbiology : the official journal of the Spanish Society for Microbiology.

[25]  F. Carrasco-Marín,et al.  Activated Carbon Surface Modifications by Nitric Acid, Hydrogen Peroxide, and Ammonium Peroxydisulfate Treatments , 1995 .

[26]  C. Louis,et al.  Remarkable hydrodechlorination activity over silica supported nickel/gold catalysts , 2005 .

[27]  G. Neri,et al.  Hydrogenation of phenol to cyclohexanone over palladium and alkali-doped palladium catalysts , 1994 .

[28]  M. Keane A review of catalytic approaches to waste minimization: case study—liquid‐phase catalytic treatment of chlorophenols , 2005 .

[29]  Jaime Giménez,et al.  Degradation of chlorophenols by means of advanced oxidation processes: a general review , 2004 .

[30]  F. Rodríguez-Reinoso,et al.  The role of carbon materials in heterogeneous catalysis , 1998 .

[31]  J. Marinas,et al.  Hydrogenolysis of organohalogen compounds over palladium supported catalysts , 2001 .

[32]  J J Rodríguez,et al.  Chemical pathway and kinetics of phenol oxidation by Fenton's reagent. , 2005, Environmental science & technology.

[33]  V. Likholobov,et al.  Palladium catalysts on activated carbon supports: Influence of reduction temperature, origin of the support and pretreatments of the carbon surface , 2000 .