Fenton and Fenton‐like oxidation of CI Basic Yellow 51: a comparative study

When ferric ions are substituted for ferrous ions in Fenton’s reagent, the reactions which occur are called Fenton‐like reactions. This study describes the relative efficiency of Fenton (with ferrous ions) and Fenton‐like (with ferric ions) reactions for the degradation of a basic dyestuff, CI Basic Yellow 51, in aqueous solution. Comparisons were made on the basis of the observed reductions in chemical oxygen demand and visible absorption of the dye solutions at optimum reaction conditions. It was found that the Fenton process with 2.63 mm ferrous ion and 39.96 mm hydrogen peroxide at the optimum pH (3.0) eliminated 92.2% of chemical oxygen demand and 98.9% of colour in 22 min, whereas 43.2% of chemical oxygen demand and 64.6% of colour was eliminated by the Fenton‐like process within the same time period, but at pH 4. The efficiency of the latter was significantly improved (to 96.6% removal of colour and 99.7% removal of chemical oxygen demand) by an increase in temperature of 35 °C (from 15 to 50 °C), while no improvements were observed in the efficiency of the Fenton process by temperature elevations.     

Efficient Acylation of Anisole over Hierarchical Porous ZSM‐5 Structure

Friedel‐Crafts acylation is one of the most important methods to prepare aromatic ketones which are used in manufacturing fine and speciality chemicals, as well as pharmaceuticals. Herein, we report an efficient and convenient procedure for the acylation of anisole with acetic anhydride, using a hierarchical porous ZSM‐5 catalyst. The hierarchical porous ZSM‐5 catalyst was synthesized using styrene butadiene rubber (SBR) as macroporous template. The catalysts were characterized for their structural features by using XRD, SEM, and FT‐IR analyses. The effect of temperature, molar ratio, and catalyst weight on the acylation of anisole was studied in detail. The reaction parameters such as anisole‐to‐acetic anhydride mole ratio, catalyst weight, and reaction temperature were optimized as 5:1, 0.2 g, and 70 °C, respectively. The method described here is environmentally benign and replaces the conventional catalyst by a highly active and reusable catalyst.     

Fenton‐like degradation of rhodamine B over highly durable Cu‐embedded alumina: Kinetics and mechanism

Cu‐embedded mesoporous alumina, as a Fenton‐like catalyst prepared via a sol‐gel method, showed excellent activity and durability for the degradation of refectory compounds. The origin of active sites for the generation of hydroxyl radicals (?OH) were thoroughly studied using multitechniques. Cu, as the only active element, could be penetrated into the bulk of alumina and some Cu atoms were embedded into the framework. The dynamic structure of surface Cu species (the variety of Cu⁺/Cu²⁺ ratio) during the reaction were determined as well. Furthermore, the structure plasticity of catalyst has proved by optimizing preparation and reaction conditions. A 98.53% degradation of RhB was recorded within 30 min, following a pseudo‐first‐order reaction rate expression. Electron spin resonance spectra and ?OH scavenging experiments have confirmed that ?OH is the main reactive oxidant for the elimination of RhB. By the surface‐enhanced Raman spectroscopy and gas chromatography‐mass spectrometer results, plausible pathways of RhB degradation were elaborated. © 2017 American Institute of Chemical Engineers AIChE J, 64: 538–549, 2018     

Deoxygenation of Methanol over ZSM‐5 in a High‐Pressure Catalytic Pyroprobe

Deoxygenation is a critical step in making hydrocarbon‐rich biofuels from biomass constituents. Although the thermal effects of oxygenate aromatization have been widely reported, the effect of pressure on this critical reaction has not yet been closely investigated, one primary reason being the unavailability of a reactor that can pyrolyze oxygenates, especially those in solid form, under pressurized conditions. Here, the first of a series of studies on how oxygenates behave when catalytically pyrolyzed under elevated pressure and temperature conditions is reported. Methanol, the simplest alcohol, was selected as the candidate to study the chemical phenomena that occur under pressurized catalytic pyrolysis. The reactions were carried out over the shape‐selective catalyst ZSM‐5 (SiO₂/Al₂O₃ = 30) under varying pressure (0 to 2.0684 MPa (300 psi) in 0.3447 MPa (50 psi) increments) and temperature (500 to 800 °C in 50 °C increments) conditions. Benzene, toluene, ethyl benzene, and xylenes (BTEX) were analyzed as the deoxygenated products of the reaction. The results indicate that the reactor pressure significantly affects deoxygenated product composition.     

A new reactor coupling heterogeneous Fenton‐like catalytic oxidation with membrane separation for degradation of organic pollutants

BACKGROUND: There is growing interest in employing heterogeneous Fenton‐like catalysts in slurry to obtain higher activity. However, fine size particles create problems associated with recovery from the treated water. Therefore, it is highly desirable to develop a novel Fenton‐like process that not only has high degradation efficiency of organic pollutants, but also allows for easily reusing the catalysts. RESULT: A new reactor was investigated by coupling the heterogeneous Fenton‐like oxidation with membrane separation. Results showed that the FeY catalyst could be almost filtrated by a submerged micro‐filtration membrane in the reactor to continuously activate H₂O₂. For a FeY dose of 1 g L^?1 and a residence time of 120 min, the degradation efficiency of AO II reached 97%. CONCLUSIONS: In the new reactor, degradation of AO II occurred continuously and efficiently without an additional FeY separation process. The treatment capacity of this FeY catalyst for wastewater containing 100 mg L^?1 AO II in the reactor was estimated to be 82 times that of a reactor in which the catalyst could not be reused. The distinguishing technical feature of this reactor was the reuse of the Fenton‐like catalyst. Copyright © 2011 Society of Chemical Industry     

Esterification of Renewable Levulinic Acid to n‐Butyl Levulinate over Modified H‐ZSM‐5

The synthesis of n‐butyl levulinate, one of the most important biodiesel additives, by catalytic esterification of biomass‐derived levulinic acid (LA) with n‐butanol over modified H‐ZSM‐5 (micro/meso‐HZ‐5) in a closed‐batch system is reported for the first time. The optimization of the reaction conditions such as the reactant molar ratio, the catalyst loading, the reaction time and the temperature was performed in view to maximize the yield of n‐butyl levulinate. Micro/meso‐HZ‐5 was found to be the most efficient catalyst, with 98 % yield of n‐butyl levulinate and a reusability for six cycles, which is higher than reported in the literature. A possible catalytic mechanism for the esterification reaction is also proposed. A second‐order pseudo‐homogeneous model with R² > 0.97 confirmed that the esterification reaction is performed in the kinetic regime due to the high activation energy of 23.84 kJ mol^?1.     

Kinetics of glycerol conversion to hydrocarbon fuels over Pd/H‐ZSM‐5 catalyst

The utilization of glycerol, primary byproduct of biodiesel production, is important to enhance process economics. In our recent prior work, it was shown that glycerol can be converted to hydrocarbon fuels over bifunctional catalysts, containing a noble metal supported on H‐ZSM‐5. Over Pd/H‐ZSM‐5 catalyst, an optimal ～60% yield of hydrocarbon fuels was obtained. In the present work, based on experimental data over Pd/H‐ZSM‐5 catalyst, a lumped reaction network and kinetic model are developed. Using differential kinetic experiments over the temperature range 300–450°C, the rate constants, reaction orders, and activation energies are obtained for each reaction step. The predicted values match well with experimental data for glycerol conversion up to ～90%. © 2017 American Institute of Chemical Engineers AIChE J, 63: 5445–5451, 2017     

Selective Catalytic Reduction of NOx with Ammonia over Fe‐Mo/ZSM‐5 Catalysts

The Fe‐Mo/ZSM‐5 catalysts were prepared by an impregnation method. A comparison of the catalytic activity for the reduction of NO_x with ammonia over Fe‐Mo/ZSM‐5, Fe‐ZSM‐5 and Mo/ZSM‐5 catalysts was carried out. Also, the effects of the conditions used for calcination as well as of the Fe/Mo ratio on the catalytic performance of Fe‐Mo/ZSM‐5 catalysts were studied. It was found that Fe‐Mo/ZSM‐5 is more active than Fe‐ZSM‐5 and Mo/ZSM‐5 separately. Fe‐Mo/ZSM‐5 exhibited the best performance for SCR reaction with a Fe/Mo ratio of 1.5 and yielded the highest NO_x conversion of 96 % at a temperature of 430 °C. The results also showed that the performance of Fe‐Mo/ZSM‐5 is sensitive to the conditions used during calcination. The bulk phase and surface composition of the Fe‐Mo/ZSM‐5 catalysts were determined by XRD, BET, and XPS techniques, respectively. The results revealed that the surface Mo percentage is the largest when the Fe/Mo ratio is 1.5, which may be related to its higher activity for catalytic reduction of NO_x. XRD results indicate that the best catalytic performance of the Fe/Mo = 1.5 sample results from a strong interaction among Fe, Mo and HZSM‐5. In addition, it can be tentatively presumed that the surface nitrous species from the calcinations play an important role in SCR of NO_x over Fe‐Mo/ZSM‐5 catalysts.     

Treatment of paper and pulp wastewater and removal of odorous compounds by a Fenton‐like process at the pilot scale

A Fenton‐like process, involving oxidation and coagulation, was evaluated for the removal of odorous compounds and treatment of a pulp and paper wastewater. The main parameters that govern the complex reactive system [pH and Fe(III) and hydrogen peroxide concentrations] were studied. Concentrations of Fe(III) between 100 and 1000 mg L^?1 and of H₂O₂ between 0 and 2000 mg L^?1 were chosen. The main mechanism for color removal was coagulation. The maximum COD, color and aromatic compound removals were 75, 98 and 95%, respectively, under optimal operating conditions ([Fe(III)] = 400 mg L^?1; [H₂O₂] = 500–1000 mg L^?1; pH = 2.5; followed by coagulation at pH 5.0). The biodegradability of the wastewater treated increased from 0.4 to 0.7 under optimal conditions and no residual hydrogen peroxide was found after treatment. However, partially or non‐oxidized compounds present in the treated wastewater presented higher acute toxicity to Artemia salina than the untreated wastewater. Based on the optimum conditions, pilot‐scale experiments were conducted and revealed a high efficiency in relation to the mineralization of organic compounds. Terpenes [(1S)‐α‐pinene, β‐pinene, (1R)‐α‐pinene and limonene] were identified in the wastewater and were completely eliminated by the Fenton‐like treatment. Copyright © 2006 Society of Chemical Industry     

Aromatic Compounds from Lignin Liquefaction over ZSM‐5 Catalysts in Supercritical Ethanol

A systematic research about the liquefaction of alkali lignin in supercritical ethanol using ZSM‐5 zeolite catalysts is reported, which includes the synergistic effect of temperature, catalytic content, and reaction time on product yield and distribution. Fourier transform infrared and gas chromatography‐mass spectrometry analysis were carried out to evaluate the compositions of bio‐oil and solid residue. Under moderate condition, maximum conversion and yield of bio‐oil were satisfactorily high. With the help of ZSM‐5 catalyst, lignin could be successfully converted into aromatic compounds.     

Catalytic Evaluation of CuO/[Si]MCM‐41 in Fenton‐like Reactions

CuO/[Si]MCM‐41 catalysts with various Si/Cu molar ratios were prepared and characterized by X‐ray diffraction, nitrogen physisorption, temperature‐programmed reduction by H₂, and UV‐vis and Raman spectroscopy. The effects of copper loading and pH on their activity in the decolorization of methyl orange were studied in a heterogeneous Fenton‐like process. With decreasing Si/Cu ratio, dye decolorization increased from 18 to 75 % at pH 3. CuO/[Si]MCM‐41 catalysts showed 75, 50, and 40 % conversion of methyl orange at pH 3, 5, and 7, respectively. This is a significant improvement to Fenton‐like reactions involving copper, and thus CuO/[Si]MCM‐41 catalysts are quite promising for pollutant degradation.