Catalytic wet air oxidation of low molecular weight carboxylic acids using a carbon supported platinum catalyst

Aqueous solutions of low molecular weight carboxylic acids, such as acetic, propionic and butyric acids, were treated by catalytic wet air oxidation (CWAO) using a carbon supported platinum catalyst. Oxidation in the presence of the catalyst, in a stirred reactor, was carried out at 200°C and 6.9 bar of oxygen partial pressure, with conversions (after 2 h) ranging from 59.4 to 75%, and selectivities to gaseous products of up to 100%. Initial rates for conversion varied from 184 (butyric acid) to 260 mmol h⁻¹ g_Pt⁻¹ (propionic acid). The activation energy for butyric acid conversion was found to be 56.7 kJ mol⁻¹.     

Catalytic oxidation of odorous organic acids

Emissions of volatile organic acids is a significant problem in rural communities. So far no one has considered catalytic solutions to the problem but catalytic alternatives look quite reasonable. In this paper we present the results of the first study of the oxidation of a series of odorous organic acids on copper catalysts. We find that the organic acids are easily oxidized on commercial copper on alumina catalysts. Light-off temperatures vary from 180°C for n-butyric acid to 220°C for acetic acid. The rate of oxidation of acetic and i-butyric acid show simple power law dependence on the concentrations of the reactants. In contrast, the oxidation of n-butyric, i-valeric and n-valeric acids show rates which reach a maximum at intermediate oxygen concentrations. Analysis of the data indicates that the copper can exist in two different states: a more active and a less active state.

These results provide the first evidence that catalytic processes are viable for emissions control in rural communities.     

Catalytic wet air oxidation of butyric acid solutions using carbon-supported iridium catalysts

Aqueous solutions of butyric acid were treated by catalytic wet air oxidation using carbon-supported iridium catalysts in a stirred reactor. Under the operating conditions of 6.9 bar of oxygen partial pressure and 200 °C of temperature, conversions up to 52.9% after 2 h were obtained depending on the type of catalyst used. The effects of butyric acid initial concentration, loading of catalyst, oxygen partial pressure and temperature were investigated and the empirical rate law for acid conversion is presented. Oxidation intermediates such as propionic and acetic acid were identified. The heterogeneous catalyzed free-radical oxidation of butyric acid is discussed.     

Catalytic oxidation of maleic and oxalic acids under potential control of platinum catalysts

The oxidation of maleic and oxalic acids in diluted aqueous solutions and with platinum catalysts under potential control was studied with the purpose of defining the influence of potential on the catalytic activity. This control was achieved either by an external device or was spontaneously established in the presence of the reactants. The effect of the composition and of the pH was also investigated.

Oxalic acid can be oxidized in mild experimental conditions (T=333 K, P_O2≤1 bar) and at potential values of the catalyst comprised between 0.7<E<1.8 V/RHE with a maximum catalytic activity at 1.3 V/RHE. The catalytic oxidation of this compound under external control of catalyst potential occurs following the same mechanism as the electrocatalytic oxidation. Oxalic acid is weakly adsorbed and its oxidation is inhibited by strongly adsorbed anions.

Maleic acid needs more severe experimental condition to be oxidized (T=383 K, P_O2=1–5 bars) and catalyst potentials in the range of 0.4≤E<1.1 V/RHE. In the same potential range an active adsorbed species was detected.

The catalytic oxidation of maleic acid follows the same mechanism with and without external control of catalyst potential which should be different from the mechanism of the electrocatalytic oxidation.     

Wet air oxidation of long-chain carboxylic acids

The wet air oxidation of long-chain carboxylic acids has been studied. Caprylic acid and oleic acid were selected for the degradation studies. The effectiveness of the process has been followed in terms of the disappearance of carboxylic acids and in terms of COD removal. The oxidation process was studied in the temperature range 473–573 K with a total pressure of 15 MPa of synthetic air, which means an oxygen excess. The oxidation process was found to be pseudo-first order with respect to the carboxylic acid concentration and the activation energies were 55.5 kJ/mol for caprylic acid and 53.8 kJ/mol for oleic acid. Acetic acid was found to be the main intermediate in the oxidation process and, therefore, a generalized kinetic model based on the formation and elimination of acetic acid has also been applied to the experimental data.     

Catalytic wet air oxidation of acetic acid over different ruthenium catalysts

Ruthenium catalysts were prepared by impregnation of different supports: ZrO₂, CeO₂, TiO₂, ZrO₂–CeO₂ and TiO₂–CeO₂. Their activities for acetic acid oxidation in aqueous solution were investigated in a stirred reactor at a reaction temperature of 200 °C and total pressure of 4 MPa. The order of the catalyst activity obtained was RuO₂/ZrO₂–CeO₂ > RuO₂/CeO₂ > RuO₂/TiO₂–CeO₂ > RuO₂/ZrO₂ > RuO₂/TiO₂, which corresponds to surface concentration of non-lattice oxygen (defect-oxide or hydroxyl-like group) of these catalysts. The non-lattice oxygen on the catalyst surface plays an important role in the catalytic activity.     

Catalytic wet air oxidation of dye pollutants by polyoxomolybdate nanotubes under room condition

In order to develop a catalyst with high activity and stability for catalytic wet air oxidation of pollutant dyes at room condition, a new polyoxometalate Zn_1.5PMo₁₂O₄₀ with nanotube structure was prepared using biological template. The structure and morphology were characterized using infrared (IR) spectra, UV–vis diffuse reflectance spectra (DR-UV–vis), elemental analyses, X-ray powder diffraction (XRD), and transmission electron microscopy (TEM). And the degradation of Safranin-T (ST), a hazardous textile dye, under air at room temperature and atmospheric pressure was studied as a model experiment to evaluate the catalytic activity of this polyoxomolybdate catalyst. The results show that the catalyst has an excellent catalytic activity in treatment of wastewater containing 10 mg/L ST, and 98% of color and 95% of chemical oxygen demand (COD) can be removed within 40 min. And the organic pollutant of ST was totally mineralized to simple inorganic species such as HCO₃⁻, Cl⁻ and NO₃⁻ during this time (total organic carbon (TOC) decreased 92%). The structure and morphology of the catalyst under different cycling runs show that the catalyst are stable under such operating conditions and the leaching tests show negligible leaching effect owning to the lesser dissolution. So this polyoxomolybdate nanotube is proved to be a heterogeneous catalyst in catalytic wet air oxidation of organic dye.     

Rectorite as catalyst for wet air oxidation of phenol

Rectorite was characterized by XRF, BET, XRD, FT-IR, SEM and TPR, and investigated as catalyst for wet air oxidation of phenol in a batch reactor at 150 °C. The iron impurity, mainly presented as highly dispersed hematite, acted as active centers and showed good performance without significant iron leaching. The catalyst can be also used as adsorbent to remove leached iron in solution.     

Catalytic wet air oxidation of aqueous solution of 2-chlorophenol over Ru/zirconia catalysts

Ru loaded zirconia catalysts (Ru/ZrO₂) were found to be active in the catalytic wet air oxidation (CWAO) of 2-chlorophenol (2-CP) at relatively mild temperature. To optimize the reaction conditions, the effects of different operating parameters, such as the rotation speed, the reaction temperature, the total pressure, the initial concentration and the pH of the initial 2-CP solution on the catalytic activity of 3 wt.% Ru/ZrO₂ were evaluated. The activation energy for the CWAO of 2-CP over Ru/ZrO₂ was calculated to be 36 kJ mol⁻¹. The 2-CP removal rate is zero order with respect to the initial 2-CP concentration. The CWAO of 2-CP changes from first order (oxygen diffusion control) to zero order (kinetic control) with respect to the oxygen partial pressure when the total pressure is higher than 4 MPa. The conversion of 2-CP increases with the pH of the initial 2-CP solution. The dechlorination reaction is promoted at higher pH. However, too high pH limits the total mineralization of 2-CP because the adsorption of the reaction intermediates is hindered. It was also confirmed that Ru(NO)(NO₃)₃ is better than RuCl₃ to act as a ruthenium precursor.     

Catalytic membrane structure influence on the pressure effects in an interfacial contactor catalytic membrane reactor applied to wet air oxidation

This paper deals with the influence of catalytic membrane structure on the way the gas pressure affects the efficiency of a catalytic membrane reactor (CMR). The CMR is an interfacial contactor, used for wet air oxidation, formic acid solution and air being fed separately from both sides of the catalytic membrane. The gas overpressure can shift the gas–liquid interface into the membrane wall, closer to the catalytic zone, and therefore greatly increase the reaction rate. It has been confirmed that this was not an oxygen partial pressure effect. When compared to a conventional slurry reactor, the contactor CMR showed a reaction rate more than three times higher.     

催化湿式氧化处理头孢氨苄废水

采用催化湿式氧化处理头孢氨苄废水,考察反应温度、进水pH及Cl-含量对RCT催化剂性能的影响,并对液体样品及催化剂进行了HPLC、TOC/TN、GC-MS、N2物理吸附-脱附及XRF表征。通过正交实验,得出最佳的工艺条件为:进水pH=4.8,Cl-浓度1 500 mg·L-1,反应温度260℃;对催化剂进行300 h连续寿命考察,废水TOC及TN去除率均超过90%,催化剂稳定性高,活性组分流失较少;废水经催化湿式氧化处理,水中残留的主要有机物均可生化降解。     

催化湿式氧化山梨酸生产废水催化剂的研究

以过渡金属氧化物CuO为主活性组分通过对Cr2O3的复合和掺入电子助剂La2O3的考察,研制出适用于催化湿式氧化处理山梨酸生产废水的复合催化剂。考察了各组分浸渍液浓度、焙烧温度和焙烧时间等制备条件对催化剂的催化活性和稳定性的影响,确定了最佳制备条件。结果表明:优化制备的CuO-Cr2O3-La2O3/TiO2催化剂,用于处理山梨酸生产废水时具有良好的催化活性和稳定性,在θ=220℃,p(O2)=2.5 MPa,反应时间t=120 min,山梨酸生产废水初始CODCr=10 030 mg/L条件下CODCr去除率达到96.6%,而在相同条件下未加催化剂的湿式氧化CODCr去除率只有60.8%。     

Comparison of a contactor catalytic membrane reactor with a conventional reactor: example of wet air oxidation

A wet air oxidation reaction was carried out in a gas/liquid catalytic membrane reactor of the contactor type. The oxidation of formic acid was used as a model reaction. The mesoporous top-layer of a ceramic tubular membrane was used as catalyst (Pt) support, and was placed at the interface of the gas (air) and liquid (HCOOH solution) phases.

A similar reaction was carried out in a conventional batch reactor, using a steering rate high enough to avoid gas-diffusion limitations, and exactly identical conditions than for the CMR (amount of catalyst, pressure, etc.). At room temperature, the CMR showed an initial activity three to six times higher than the conventional reactor. This activity increase was attributed to an easier oxygen access to the catalytic sites. Nevertheless, the catalytic membrane gradually deactivated after a few hours of operation. Different deactivation mechanisms are presented.     

Carbon supported platinum catalysts for catalytic wet air oxidation of refractory carboxylic acids

Carbon supported platinum (1% wt) catalysts were prepared by the incipient wetness impregnation method and by organometallic chemical vapor deposition. Catalyst characterization was carried out by means of adsorption and thermogravimetric techniques, and by electron microscopy. The catalyst with higher metal dispersion was produced by incipient wetness impregnation. The catalysts were tested in the catalytic wet air oxidation (200°C and 6.9 bar of oxygen partial pressure) of aqueous solutions containing low molecular weight (C₂ to C₄) carboxylic acids. Significant conversions (greater than 60% over 2 h) and 100% selectivity towards water and non-carboxylic acid products were observed for both systems. The initial reaction rate was used to compare the performance of the two catalytic materials and direct correspondence to the metal dispersion was found. No metal leaching was observed during reaction and no significant deactivation occurred in three successive catalytic oxidation runs. A kinetic model based on the Langmuir–Hinshelwood formulation was applied and the results were analyzed in terms of a heterogeneously catalyzed free radical mechanism.     

Reaction pathway of the catalytic wet air oxidation of phenol with a Fe/activated carbon catalyst

Catalytic wet air oxidation (CWAO) of phenol with molecular oxygen using a home-made Fe/activated carbon catalyst at mild operating conditions (100–127 °C; 8 atm) has been studied in a trickle-bed reactor. Ring compounds (hydroquinone, p-benzoquinone and p-hydroxybenzoic acid) and short-chain organic acids (maleic, malonic, oxalic, acetic and formic) have been identified as intermediate oxidation products. CWAO experiments using each one of these intermediates as starting compound have been carried out (at 127 °C and 8 atm) in order to elucidate the reaction pathway. It was found that phenol is oxidized through two different ways. It can be either para-hydroxylated to hydroquinone, which is instantaneously oxidized to p-benzoquinone or para-carboxylated to p-hydroxybenzoic acid. p-Benzoquinone is majorly mineralized to CO₂ and H₂O through oxalic acid formation whereas p-hydroxybenzoic acid gives rise to short-chain acids. Only acetic acid showed to be refractory to CWAO under the operating conditions used in this work. The catalyst avoids the presence of ring-condensation products in the reactor effluent which were formed in absence of it. This is an additional important feature because of the ecotoxicity of such compounds.     

Catalytic wet air oxidation of olive oil mill effluents: 4. Treatment and detoxification of real effluents

Olive oil mill wastewater (OMW) generated by the olive oil extraction industry constitutes a major pollutant, posing severe environmental threats. It contains a high organic load and phytotoxic and antibacterial phenolic compounds which resist biological degradation. Platinum and ruthenium supported titania or zirconia were studied in the catalytic wet air oxidation (CWAO) of OMWs in a batch reactor and in a continuous trickle-bed reactor. CWAO experiments at 190 °C and 70 bar total air pressure confirmed the effective elimination of the TOC (total organic carbon) and of the phenolic content of actual diluted OMW. Simultaneously, toxicity towards Vibrio fischeri was reduced and a decrease in phytotoxicity occurred. The ruthenium catalysts were found stable over a long period of operation in a trickle-bed reactor.The biodegradability of the oxidized waste has been enhanced and this study also examined the feasibility of coupling CWAO and an anaerobic digestion treatment. The pretreatment of the OMW in the presence of a ruthenium catalyst reduced considerably the total phenolic contents of the wastewater, and produced an effluent suitable to be treated by anaerobic treatment with increased biomethane production compared to the untreated effluent.     

Catalytic oxidation of naphthalene using a Pt/Al2O3 catalyst

Polycylic aromatic hydrocarbons (PAHs) are listed as carcinogenic and mutagenic priority pollutants, belonging to the environmental endocrine disrupters. Most PAHs in the environment stem from the atmospheric deposition and diesel emission. Consequently, the elimination of PAHs in the off-gases is one of the priority and emerging challenges. Catalytic oxidation has been widely used in the destruction of organic compounds due to its high efficiency (or conversion of reactants), its economic benefits and good applicability.

This study investigates the application of the catalytic oxidation using Pt/γ-Al₂O₃ catalysts to decompose PAHs and taking naphthalene (the simplest and least toxic PAH) as a target compound. It studies the relationships between conversion, operating parameters and relevant factors such as treatment temperatures, catalyst sizes and space velocities. Also, a related reaction kinetic expression is proposed to provide a simplified expression of the relevant kinetic parameters.

The results indicate that the Pt/γ-Al₂O₃ catalyst used accelerates the reaction rate of the decomposition of naphthalene and decreases the reaction temperature. A high conversion (over 95%) can be achieved at a moderate reaction temperature of 480 K and space velocity below 35,000 h⁻¹. Non-catalytic (thermal) oxidation achieves the same conversion at a temperature beyond 1000 K. The results also indicate that Rideal–Eley mechanism and Arrhenius equation can be reasonably applied to describe the data by using the pseudo-first-order reaction kinetic equation with activation energy of 149.97 kJ/mol and frequency factor equal to 3.26 × 10¹⁷ s⁻¹.     

Progress in performance and stability of a contactor-type Catalytic Membrane Reactor for wet air oxidation

Catalytic Membrane Reactors combine a membrane that controls transfers and a catalyst that provides conversion. This paper focuses on the catalytic performance stability of interfacial contactor membranes in the wet air oxidation of formic acid. Stable catalytic membranes with high activity have been developed.     

Wet air oxidation of p-coumaric acid over promoted ceria catalysts

The catalytic wet air oxidation (WAO) of p-coumaric acid (PCA) has been investigated over Fe- and Zn-promoted ceria catalysts. The catalysts have been prepared by the coprecipitation method and have been characterized by X-ray diffraction (XRD), BET surface area, SEM–EDX and temperature programmed reduction (TPR). The oxidation reaction was carried out in a batch reactor under an air pressure of 2 MPa and in the temperature range 353–403 K. Fe-CeO₂ catalysts, with 20–50 mol% of iron, were found more effective than the unpromoted and Zn-promoted ceria catalysts. On the basis of characterization data, it has been suggested that the higher activity of the Fe-promoted catalysts is related to the modification of the structural and redox properties of the ceria oxide catalyst on addition of iron.     

Catalytic wet air oxidation of olive mill wastewater

Au-based catalysts, known for ambient temperature CO oxidation, have to provide stable performance of up to 5000 h in order to be commercially applicable in automotive fuel cells. In this report, the on-line deactivation characteristics of Au/TiO₂ in unconventional PROX conditions are discussed. As opposed to CO removal from air, results in this report suggests that carbonates have a minor effect on deactivation of Au/TiO₂ in dry H₂-rich conditions. Also, no conclusive correlation between surface hydration and deactivation was observed. Rather, deactivation appeared to have occurred as a result of an intrinsic transformation in the oxidation state of the active species in the reducing operating conditions; a process which was reversible in an oxidizing atmosphere.