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Kinetic Modelling of Photoconversion of Phenol by a Photo-Fenton Reagent and UV

  • Natalia Villota EMAIL logo , Luis Miguel Camarero , Jose Maria Lomas and Mikel Legaristi
Published/Copyright: May 31, 2014
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International Journal of Chemical Reactor Engineering
From the journal International Journal of Chemical Reactor Engineering Volume 12 Issue 1

Abstract

This study analyses the oxidation of phenol using Fenton reagent in presence of ultraviolet light, enhancing the mineralization capacity of the treatment. Phenol oxidation generates reaction intermediates more toxic and refractory than phenol itself. Thus, the reaction must be carried out under harder conditions, leading these compounds to biodegradable acids that can be dumped into public sewages. Then, this paper considers a complete kinetic modelling of the phenol oxidation stages, differentiating the formation rate of species generated through ortho, meta and para pathways. The model is based on a mechanism of series reactions, wherein a first step degrades into dihydroxylated intermediates (catechol, resorcinol and hydroquinone). A second stage leads to tri-hydroxylated rings (pyrogallol) and benzoquinones (o-benzoquinone and p-benzoquinone), and both species may coexist in the reaction mixture. Next, if conditions are sufficiently oxidizing, they decompose into biodegradable organic acids (muconic, formic or acetic acids). In this mechanism, the parallel reactions, due to the presence of the metal catalyst, are considered. So, on one hand, there is a formation of metal complexes between species ortho-substituted and ferric ions from the catalyst. On the other hand, there is a precipitation of part of the initial catalyst as ferric hydroxide, due to the presence of ultraviolet light, which is determined by the operation pH.

Studies have been performed on the selectivity of the oxidation in function of the reaction conditions. Then, when operating with pH = 3.0, oxidation was favoured via ortho-substituted compounds. Treatment is advisable within Pho = 100–300 mg/L, being necessary to apply molar ratios of oxidant above R = 6.0 mol H2O2/mol C6H5OH to degrade these intermediates. Moreover, kinetic constants of formation of generated species are estimated, supposing that follows an evolution comparable to first-order reactions. Analysis checks that these kinetic constants present some relation to the operating conditions. In this way, a mathematical estimation is presented, showing the dependence of the kinetics on the parameters controlling the process (pH, initial concentration of phenol, oxidant molar ratio, catalyst dosage and temperature). As a result, the behaviour of the system can be predicted within the considered range.

Keywords: benzoquinone; dihydroxylated rings; phenol; photo-Fenton; pyrogallol

Acknowledgements

The authors gratefully acknowledge the financial support of Basque Country University UPV/EHU at the Environmental and Chemical Engineering Department, Escuela de Ingenieria de Vitoria-Gasteiz, Spain.

Notation

Ac

organic acids, mg/L

Ca

catechol, mg/L

Fe

ferrous ion, mg/L

Hy

hydroquinone, mg/L

k

kinetic constant, min−1

obq

pyrogallol, mg/L

pBq

p-benzoquinone, mg/L

r2

regression coefficient

R

molar ratio, mol H2O2/mol C6H5OH

Ph

phenol concentration, mg/L

Re

resorcinol, mg/L

t

time, min

T

temperature, °C

Greek Letters
α

kinetic coefficient independent of reagents amount

λ

wavelength, nm

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Published Online: 2014-5-31
Published in Print: 2014-1-1

©2014 by De Gruyter

Articles in the same Issue

  1. Frontmatter
  2. Research Articles
  3. Simulation of CO Preferential Oxidation (COPrOx) Monolithic Reactors
  4. Simulation of a New Chemical-Looping Combustion Process without Sulfur Evolution Based on Ca-Based Oxygen Carrier
  5. Syngas Production from Reforming of Methane with CO2 and O2 over LaNi1–xCoxO3 Perovskites
  6. Investigation of the Effect of Outlet Structures on the Jet Flow Characteristics in the Circulating Jet Tank
  7. Transesterification of Sunflower Oil in Microreactors
  8. Influence of the Photoreactor Configuration and of Different Light Sources in the Photocatalytic Treatment of Highly Polluted Wastewater
  9. Stability and Emissions of a Lean Pre-Mixed Combustor with Rich Catalytic/Lean-burn Pilot
  10. Carica Papaya Seed as a Biosorbent for Removal of Cr (VI) and Ni (II) Ions from Aqueous Solution: Thermodynamics and Kinetic Analysis of Experimental Data
  11. Chemical Equilibrium Model and Prediction for Coal Hydrogasification
  12. Use of Experimental Designs to Establish a Kinetic Law for a Gas Phase Photocatalytic Process
  13. Application of Support Vector Machine Modeling on Phase Distribution in the Riser of an LSCFB Reactor
  14. Characteristics of the Bending Moment Acting on an Overhung Shaft in a Stirred Vessel
  15. Conversion of Glycerol into Value-Added Products Over Cu–Ni Catalyst Supported on γ-Al2O3 and Activated Carbon
  16. Analysis of Equilibrium Shifting by Inter-Stage Reactant Feeding in a Series of Isothermal Reactors
  17. Single and Multi-Channel Reactor for Oxidative Coupling of Methane
  18. Effect of Peak Temperature Limitations on the Design of Processes with Cooled Tubular Reactors
  19. Genetic Optimization of Energy Consumption of Pellet Shaft Furnace Combustor Based on Support Vector Machine (SVM)
  20. Effect of CuO on the Thermal Stability of Polyaniline Nanofibers
  21. Kinetics and Mechanism of Formaldehyde-Free Phenol-Glucose Novolac Resin Cured with an Epoxy
  22. Micromixing Characteristics in an Aerated Stirred Tank with Half Elliptical Blade Disk Turbine
  23. Application of Response Surface Methodology and Central Composite Rotatable Design for Modeling and Optimization of Catalyst Compositions in Ethanol Synthesis via CO Hydrogenation
  24. Accurate Measurement of the Photon Flux Received Inside Two Continuous Flow Microphotoreactors by Actinometry
  25. A Non-linear Inverse Problem in Estimating the Reaction Rate Function for an Annular-Bed Reactor
  26. Passive Microextractor with Internal Fluid Recirculation for Two Immiscible Liquids
  27. Oxidative Desulfurization of Dibenzothiophene by Zirconia-Based Catalysts
  28. Studies on Performance Analysis and Computer Aided Design of Inverse Fluidized Bed Bioreactors with Nanosupport Particles
  29. Modeling the Industrial Propylene–Ethylene Copolymerization FBR at Emergency Accidents
  30. Modelling of the Membrane Permeability Effect on the H2 Production Using CFD Method
  31. SBA-15 Supported Bimetallic Catalysts for Enhancement Isomers Production During n-Heptane Decomposition
  32. Effects of Microwave and Ultrasonic-Assisted Aging on the Synthesis of H-ZSM-5 Nanozeolite and Its Catalytic Performance in Methanol Dehydration
  33. Oxydehydrogenation of Ethylbenzene to Styrene: Membrane Reactor Analysis and Design
  34. Methanol Electrooxidation Study on Mesoporous Silica Supported Pt–Co Direct Methanol Fuel Cell Anode
  35. An Experimental Study of the Synthesis of Ultrafine Titania Powder in Plasmachemical Flow-Type Reactor
  36. Tesla Valves in Micromixers
  37. Kinetic Modelling of Photoconversion of Phenol by a Photo-Fenton Reagent and UV
  38. Overall Effectiveness Factor for Slab Geometry in a Three-Phase Reaction System
  39. Effect of Surface Chemistry and Structure of Sludge Particles on Their Co-slurrying Ability with Petroleum Coke
  40. CFD-DEM Modeling of CO2 Capture using Alkali Metal-Based Sorbents in a Bubbling Fluidized Bed
  41. Reaction Kinetics of Catalytic Esterification of Nonanoic Acid with Ethanol over Amberlyst 15
  42. Numerical and Experimental Investigation of the Effect of Geometrical Parameters on the Performance of a Contraction-Expansion Helical Mixer
  43. Comparative Study of Removal of Cadmium (II) and Chromium (III) Ions from Aqueous Solution Using Low-Cost Biosorbent
  44. Ethylation of Ethylbenzene with Ethanol over Mordenite-Based Catalysts: Effects of Acidity, Desilication and Kinetics Analysis
  45. A Two-Phase CFD Modeling Approach to Investigate the Flow Characteristics in Radial Flow Moving-Bed Reactors
  46. Esterification of Free Fatty Acids in Crude Palm Oil Using Sulfated Cobalt–Tin Mixed Oxide Catalysts
  47. Numerical Simulation of Chemical Stripping Process in Resid Fluid Catalytic Cracking Stripper
  48. Experiment on Simultaneous Absorption of NO and SO2 from Sintering Flue Gas by Oxidizing Agents of KMnO4/NaClO
  49. Analysis of the Simultaneous Gas–Liquid CO2 Absorption and Liquid–Gas NH3 Desorption in a Hydrometallurgical Waelz Oxides Purification Process
  50. Investigation on Fluidized Bed Bioreactor Treating Ice Cream Wastewater Using Response Surface Methodology and Artificial Neural Network
  51. Rapid Determination of the Residence Time Distribution (RTD) Function in an Oscillatory Baffled Reactor (OBR) Using a Design of Experiments (DoE) Approach
  52. α-Amylase Aspergillus oryzae Immobilized on Modified Expanded Perlite
  53. Diffusion and Equilibrium Adsorption Coefficients of Aromatic Hydrocarbon Species in Capillary Columns
  54. Design and Optimization of the Preparation of Calcium Carbonate from Calcium Sulfate and Ammonium Bicarbonate
  55. Short Communications
  56. Effect of Different Silicate Supports on the Catalytic Performance of MoVTeO Mixed Oxides in Partial Oxidation of Isobutane
  57. Liquid Flow and Mixing in Bottom Regions of Baffled and Unbaffled Vessels Agitated by Turbine-Type Impeller
  58. Review
  59. Progress in Reactors for High-Temperature Fischer–Tropsch Process: Determination Place of Intensifier Reactor Perspective
  60. Errata
  61. Erratum to Two-Dimensional Modeling of an Externally Irradiated Slurry Photoreactor
  62. Erratum to Photocatalytic Purification of Wastewater Polluted by Odorant Sulfur Compounds Using Titanium Oxide in a Continuous Photoreactor
https://doi.org/10.1515/ijcre-2013-0130
Keywords for this article
benzoquinone; dihydroxylated rings; phenol; photo-Fenton; pyrogallol

Articles in the same Issue

  1. Frontmatter
  2. Research Articles
  3. Simulation of CO Preferential Oxidation (COPrOx) Monolithic Reactors
  4. Simulation of a New Chemical-Looping Combustion Process without Sulfur Evolution Based on Ca-Based Oxygen Carrier
  5. Syngas Production from Reforming of Methane with CO2 and O2 over LaNi1–xCoxO3 Perovskites
  6. Investigation of the Effect of Outlet Structures on the Jet Flow Characteristics in the Circulating Jet Tank
  7. Transesterification of Sunflower Oil in Microreactors
  8. Influence of the Photoreactor Configuration and of Different Light Sources in the Photocatalytic Treatment of Highly Polluted Wastewater
  9. Stability and Emissions of a Lean Pre-Mixed Combustor with Rich Catalytic/Lean-burn Pilot
  10. Carica Papaya Seed as a Biosorbent for Removal of Cr (VI) and Ni (II) Ions from Aqueous Solution: Thermodynamics and Kinetic Analysis of Experimental Data
  11. Chemical Equilibrium Model and Prediction for Coal Hydrogasification
  12. Use of Experimental Designs to Establish a Kinetic Law for a Gas Phase Photocatalytic Process
  13. Application of Support Vector Machine Modeling on Phase Distribution in the Riser of an LSCFB Reactor
  14. Characteristics of the Bending Moment Acting on an Overhung Shaft in a Stirred Vessel
  15. Conversion of Glycerol into Value-Added Products Over Cu–Ni Catalyst Supported on γ-Al2O3 and Activated Carbon
  16. Analysis of Equilibrium Shifting by Inter-Stage Reactant Feeding in a Series of Isothermal Reactors
  17. Single and Multi-Channel Reactor for Oxidative Coupling of Methane
  18. Effect of Peak Temperature Limitations on the Design of Processes with Cooled Tubular Reactors
  19. Genetic Optimization of Energy Consumption of Pellet Shaft Furnace Combustor Based on Support Vector Machine (SVM)
  20. Effect of CuO on the Thermal Stability of Polyaniline Nanofibers
  21. Kinetics and Mechanism of Formaldehyde-Free Phenol-Glucose Novolac Resin Cured with an Epoxy
  22. Micromixing Characteristics in an Aerated Stirred Tank with Half Elliptical Blade Disk Turbine
  23. Application of Response Surface Methodology and Central Composite Rotatable Design for Modeling and Optimization of Catalyst Compositions in Ethanol Synthesis via CO Hydrogenation
  24. Accurate Measurement of the Photon Flux Received Inside Two Continuous Flow Microphotoreactors by Actinometry
  25. A Non-linear Inverse Problem in Estimating the Reaction Rate Function for an Annular-Bed Reactor
  26. Passive Microextractor with Internal Fluid Recirculation for Two Immiscible Liquids
  27. Oxidative Desulfurization of Dibenzothiophene by Zirconia-Based Catalysts
  28. Studies on Performance Analysis and Computer Aided Design of Inverse Fluidized Bed Bioreactors with Nanosupport Particles
  29. Modeling the Industrial Propylene–Ethylene Copolymerization FBR at Emergency Accidents
  30. Modelling of the Membrane Permeability Effect on the H2 Production Using CFD Method
  31. SBA-15 Supported Bimetallic Catalysts for Enhancement Isomers Production During n-Heptane Decomposition
  32. Effects of Microwave and Ultrasonic-Assisted Aging on the Synthesis of H-ZSM-5 Nanozeolite and Its Catalytic Performance in Methanol Dehydration
  33. Oxydehydrogenation of Ethylbenzene to Styrene: Membrane Reactor Analysis and Design
  34. Methanol Electrooxidation Study on Mesoporous Silica Supported Pt–Co Direct Methanol Fuel Cell Anode
  35. An Experimental Study of the Synthesis of Ultrafine Titania Powder in Plasmachemical Flow-Type Reactor
  36. Tesla Valves in Micromixers
  37. Kinetic Modelling of Photoconversion of Phenol by a Photo-Fenton Reagent and UV
  38. Overall Effectiveness Factor for Slab Geometry in a Three-Phase Reaction System
  39. Effect of Surface Chemistry and Structure of Sludge Particles on Their Co-slurrying Ability with Petroleum Coke
  40. CFD-DEM Modeling of CO2 Capture using Alkali Metal-Based Sorbents in a Bubbling Fluidized Bed
  41. Reaction Kinetics of Catalytic Esterification of Nonanoic Acid with Ethanol over Amberlyst 15
  42. Numerical and Experimental Investigation of the Effect of Geometrical Parameters on the Performance of a Contraction-Expansion Helical Mixer
  43. Comparative Study of Removal of Cadmium (II) and Chromium (III) Ions from Aqueous Solution Using Low-Cost Biosorbent
  44. Ethylation of Ethylbenzene with Ethanol over Mordenite-Based Catalysts: Effects of Acidity, Desilication and Kinetics Analysis
  45. A Two-Phase CFD Modeling Approach to Investigate the Flow Characteristics in Radial Flow Moving-Bed Reactors
  46. Esterification of Free Fatty Acids in Crude Palm Oil Using Sulfated Cobalt–Tin Mixed Oxide Catalysts
  47. Numerical Simulation of Chemical Stripping Process in Resid Fluid Catalytic Cracking Stripper
  48. Experiment on Simultaneous Absorption of NO and SO2 from Sintering Flue Gas by Oxidizing Agents of KMnO4/NaClO
  49. Analysis of the Simultaneous Gas–Liquid CO2 Absorption and Liquid–Gas NH3 Desorption in a Hydrometallurgical Waelz Oxides Purification Process
  50. Investigation on Fluidized Bed Bioreactor Treating Ice Cream Wastewater Using Response Surface Methodology and Artificial Neural Network
  51. Rapid Determination of the Residence Time Distribution (RTD) Function in an Oscillatory Baffled Reactor (OBR) Using a Design of Experiments (DoE) Approach
  52. α-Amylase Aspergillus oryzae Immobilized on Modified Expanded Perlite
  53. Diffusion and Equilibrium Adsorption Coefficients of Aromatic Hydrocarbon Species in Capillary Columns
  54. Design and Optimization of the Preparation of Calcium Carbonate from Calcium Sulfate and Ammonium Bicarbonate
  55. Short Communications
  56. Effect of Different Silicate Supports on the Catalytic Performance of MoVTeO Mixed Oxides in Partial Oxidation of Isobutane
  57. Liquid Flow and Mixing in Bottom Regions of Baffled and Unbaffled Vessels Agitated by Turbine-Type Impeller
  58. Review
  59. Progress in Reactors for High-Temperature Fischer–Tropsch Process: Determination Place of Intensifier Reactor Perspective
  60. Errata
  61. Erratum to Two-Dimensional Modeling of an Externally Irradiated Slurry Photoreactor
  62. Erratum to Photocatalytic Purification of Wastewater Polluted by Odorant Sulfur Compounds Using Titanium Oxide in a Continuous Photoreactor
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