Phenol oxidation over CuO/Al2O3 in supercritical water

Phenol was oxidized in supercritical water at 380–450°C and 219–300 atm, using CuO/Al₂O₃ as a catalyst in a packed-bed flow reactor. The CuO catalyst has the desired effects of accelerating the phenol disappearance and CO₂ formation rates relative to non-catalytic supercritical water oxidation (SCWO). It also simultaneously reduced the yield of undesired phenol dimers at a given phenol conversion. The rates of phenol disappearance and CO₂ formation are sensitive to the phenol and O₂ concentrations, but insensitive to the water density. A dual-site Langmuir–Hinshelwood–Hougen–Watson rate law used previously for catalytic SCWO of phenol over other transition metal oxides and the Mars–van Krevelen rate law can correlate the catalytic kinetics for phenol disappearance over CuO. The supported CuO catalyst exhibited a higher activity, on a mass of catalyst basis, for phenol disappearance and CO₂ formation than did bulk MnO₂ or bulk TiO₂. The CuO catalyst had the lowest activity, however, when expressed on the basis of fresh catalyst surface area. The CuO catalyst exhibited some initial deactivation, but otherwise maintained its activity throughout 100 h of continuous use. Both Cu and Al were detected in the reactor effluent, however, which indicates the dissolution or erosion of the catalyst at reaction conditions.     

Reactivity of a spray-dried NiO/NiAl2O4 oxygen carrier for chemical-looping combustion

Kinetic data of a promising oxygen carrier of NiO/NiAl₂O₄ have been established from experiments in a small fluidized bed batch reactor using methane. The particles were prepared by spray-drying using commercially available raw material and selected as the best candidates from an earlier screening study. The particles clearly showed high reactivity, with a maximum gas yield between 86% and 93% in the temperature interval 750 °C to 950 °C when using a bed mass and a gas flow corresponding to only 6 kg/MW_fuel. A comparison of the reactivity with data from TGA experiments showed that the reactivity generally was faster in the batch fluidized bed in the investigated temperature interval. A simple reactor model using kinetic data from the batch fluidized bed reactor and the TGA predicted a minimum mass of 9–24 kg/MW_fuel of oxygen carrier particles for full gas yield of methane to carbon dioxide in the fuel reactor. Comparison with experiments performed in a 10 and 120 kW CLC reactor with the same type of oxygen carrier showed that even when employing 13 to 50 times the amount of oxygen carrier theoretically needed for complete gas conversion, full gas yield was not obtained in the circulating systems. Hence it is of great importance to consider the fluid dynamics and gas-solid contact when modeling the fuel reactor of a chemical-looping combustor.     

Kinetics of geopolymerization: Role of Al2O3 and SiO2

The early-stage reaction kinetics of metakaolin/sodium silicate/sodium hydroxide geopolymer system have been investigated. The setting and early strength development characteristics, and associated mineral and microstructural phase development of mixtures containing varying SiO₂/Al₂O₃ ratios, cured at 40 °C for up to 72 h, were carefully studied. It was observed that setting time of the geopolymer systems was mainly controlled by the alumina content. Essentially, the setting time increased with increasing SiO₂/Al₂O₃ ratio of the initial mixture. Up to a certain limit, the SiO₂/Al₂O₃ ratio was also found to be responsible for observed high-strength gains at later stages. An increase in the Al₂O₃ content, i.e. for low SiO₂/Al₂O₃ ratio, led to products of low strength, accompanied by microstructures with increased amounts of Na-Al-Si-containing “massive” phases (grains). EDAX analyses showed that the SiO₂/Al₂O₃ ratios of geopolymer gel phases were quite similar to those of the starting mixtures, but with an overall lower Na content. Most importantly, this study clearly demonstrates that the properties of resulting geopolymer systems can be drastically affected by minor changes in the available Si and Al concentrations during synthesis.     

Reactivity of a NiO/Al2O3 oxygen carrier prepared by impregnation for chemical-looping combustion

The reactivity of a Ni-based oxygen carrier prepared by hot incipient wetness impregnation (HIWI) on α-Al₂O₃ with a NiO content of 18 wt% was studied in this work. Pulse experiments with the reduction period divided into 4-s pulses were performed in a fluidized bed reactor at 1223 K using CH₄ as fuel. The number of pulses was between 2 and 12. Information about the gaseous product distribution and secondary reactions during the reduction was obtained. In addition to the direct reaction of the combustible gas with the oxygen carrier, CH₄ steam reforming also had a significant role in the process, forming H₂ and CO. This reaction was catalyzed by metallic Ni in the oxygen carrier and H₂ and CO acted as intermediate products of the combustion. No evidence of carbon deposition was found in any case. Redox cycles were also carried out in a thermogravimetric analyzer (TGA) with H₂ as fuel. Both tests showed that there was a relation between the solid conversion reached during the reduction and the relative amount of NiO and NiAl₂O₄ in the oxygen carrier. When solid conversion increased, the NiO content also increased, and consequently NiAl₂O₄ decreased. Approximately 20% of the reduced nickel was oxidized to NiAl₂O₄, regardless ΔX_s. NiAl₂O₄ was also an active compound for the combustion reaction, but with lower reactivity than NiO. Further, the consequences of these results with respect to the design of a CLC system were investigated. When formation of NiAl₂O₄ occurred, the average reactivity in the fuel reactor decreased. Therefore, the presence of both NiO and NiAl₂O₄ phases must be considered for the design of a CLC facility.     

NiO/Al2O3 oxygen carriers for chemical-looping combustion prepared by impregnation and deposition-precipitation methods

Ni-based oxygen carriers (OC) with different NiO content were prepared by incipient wet impregnation, at ambient (AI), and hot conditions (HI) and by deposition-precipitation (DP) methods using γ-Al₂O₃ and α-Al₂O₃ as supports. The OC were characterized by BET, Hg porosimetry, mechanical strength, TPR, XRD and SEM/EDX techniques. Reactivity of the OC was measured in a thermogravimetric analyzer and methane combustion selectivity towards CO₂ and H₂O, attrition rate, and agglomeration behavior were analyzed in a batch fluidized bed reactor during multicycle reduction-oxidation tests.XRD and TPR analysis showed the presence of both free NiO and NiAl₂O₄ phases in most of the OC. The interaction of the NiO with the alumina during OC preparation formed NiAl₂O₄ that affected negatively to the OC reactivity and methane combustion selectivity towards CO₂ and H₂O during the reduction reaction. The NiO-alumina interaction was more affected by the support type than by the preparation method used. The NiO-alumina interaction was stronger in the OC prepared on γ-Al₂O₃.The OC were evaluated in the fluidized bed reactor with respect to the agglomeration process. OC prepared by the AI and HI methods with NiO contents up to 25 wt%, OC prepared by the DP method on γ-Al₂O₃ with NiO content lower than 30 wt%, and OC prepared by the DP method on α-Al₂O₃ with a NiO content lower than 26 wt% did not agglomerated. OC that agglomerated showed an external layer of NiO over the particles. It seems that the most important factor affecting to the formation of the external NiO layer on the OC, and so to the agglomeration process, was the metal content of the OC. The attrition rates of the OC prepared using γ-Al₂O₃ as support were higher than the ones prepared using α-Al₂O₃ as support, and in general the attrition rates of all the OC were low.The OC prepared by AI, HI or DP methods on α-Al₂O₃ as support had appropriated characteristics to be used in the chemical-looping combustion process.     

Steam reforming of methanol over a CuO/ZnO/Al2O3 catalyst, part I: Kinetic modelling

A kinetic study of the methanol steam reforming reaction was performed over a commercial CuO/ZnO/Al₂O₃ catalyst (Süd-Chemie, G66 MR), in the temperature range of 200–300 °C. The reactions considered in this work were methanol steam reforming (MSR) and reverse water gas shift (rWGS). Several MSR kinetic rate models developed by different authors were compared and the one was determined that best fitted the experimental data. A kinetic Langmuir–Hinshelwood model was proposed based on the work by Peppley et al. (1999a) . The kinetic expressions that presented the best fit were used to simulate the packed bed reactor with a one-dimensional model. A good agreement between the mathematical model and the experimental data was observed.     

Reactivity and stability of Ni/Al2O3 oxygen carrier for chemical-looping combustion (CLC)

Chemical-looping combustion (CLC) is a technology that reduces the carbon dioxide emissions from fossil fuel power stations. A nickel supported on -alumina oxygen carrier is investigated in this study, for use in a CLC process. Oxygen carriers with various nickel loadings on alumina are prepared according to the incipient wetness technique. The reactivity and stability of the prepared oxygen carrier samples, during repeated reduction–oxidation cycles, is demonstrated using temperature programmed reduction and oxidation. Pulse chemisorption results show that the dispersion and active crystallite diameter of the nickel particles remain constant over multiple reduction–oxidation cycles, indicating that no agglomeration occurs up to a nickel loading of 20 wt% supported on alumina. The stability and reactivity of the oxygen carriers, under industrial relevant conditions, are also investigated using the CREC fluidized bed riser simulator. It is observed that a 20 wt% nickel supported on alumina oxygen carrier is stable under industrial relevant fluidized bed reaction conditions, converting 76% of methane to carbon dioxide and water vapor, the combustion products. The metal support interaction is assessed by H₂ temperature programmed desorption, which shows that the metal-support interaction decreases as more nickel is loaded onto the alumina support.     

Fe-zeolites as catalysts for chemical oxidation of MTBE in water with H2O2

The heterogeneous catalytic wet oxidation of methyl tert-butyl ether (MTBE) with hydrogen peroxide, catalyzed by the iron-containing zeolites Fe-ZSM5 and Fe-Beta, was studied at ambient conditions and pH 7. The kinetics of MTBE degradation could be well-fitted to a pseudo-first-order model. Using Fe-ZSM5, the dependence of the reaction rate constant on hydrogen peroxide and catalyst concentration was determined. Furthermore, the formation and oxidation of tert-butyl alcohol and tert-butyl formate as intermediates of MTBE oxidation were studied. A comparison of the reaction rates of MTBE, trichloroethylene and diethyl ether in the Fe-ZSM5/H₂O₂ system revealed that adsorption plays a positive role for the degradation reaction.Comparing the two types of Fe-containing zeolites applied in this study, Fe-Beta showed a lower catalytic activity for H₂O₂ decomposition and also MTBE degradation. However, in terms of utilization of H₂O₂ for MTBE degradation Fe-Beta is advantageous over Fe-ZSM5. This could be explained by the stronger adsorptive enrichment of MTBE on the Fe-Beta zeolite. This study shows that Fe-containing zeolites are promising catalysts for oxidative degradation of MTBE by H₂O₂.     

Kinetics of CO and H2 oxidation over CuO-CeO2 catalyst in H2 mixtures with CO2 and H2O

The kinetics of CO and H₂ oxidation over a CuO-CeO₂ catalyst were simultaneously investigated under reaction conditions of preferential CO oxidation (PROX) in hydrogen-rich mixtures with CO₂ and H₂O. An integral packed-bed tubular reactor was used to produce kinetic data for power-law kinetics for both CO and H₂ oxidations. The experimental results showed that the CO oxidation rate was essentially independent of H₂ and O₂ concentrations, while the H₂ oxidation rate was practically independent of CO and O₂ concentrations. In the CO oxidation, the reaction orders were 0.91, −0.37 and −0.62 with respect to the partial pressure of CO, CO₂ and H₂O, respectively. In the H₂ oxidation, the orders were 1.0, −0.48 and −0.69 with respect to the partial pressure of H₂, CO₂ and H₂O, respectively. The activation energies of the CO oxidation and the H₂ oxidation were 94.4 and 142 kJ/mol, respectively. The rate expressions of both oxidations were able to predict the performance of the PROX reactor with accuracy. The independence between the CO and the H₂ oxidation suggested different sites for CO and H₂ adsorption on the CuO-CeO₂ catalyst. Based on the results, we proposed a new reaction model for the preferential CO oxidation. The model assumes that CO adsorbs selectively on the Cu⁺ sites; H₂ dissociates and adsorbs on the Cu⁰ sites; the adsorbed species migrates to the interface between the copper components and the ceria support, and reacts there with the oxygen supplied by the ceria support; and the oxygen deficiency on the support is replenished by the oxygen in the reaction mixture.     

Reduction and oxidation kinetics of Mn3O4/Mg-ZrO2 oxygen carrier particles for chemical-looping combustion

The kinetics of reduction with methane and oxidation with oxygen of Mn₃O₄ supported on Mg-ZrO₂ prepared by freeze granulation has been investigated. The reactivity experiments were performed in a thermogravimetric analyzer (TGA) using different reacting gas concentrations and temperatures in the range of 1073-1223 K. The oxygen carrier particles showed high reactivity during both reduction and oxidation at all investigated temperatures. An empirical reaction model, which assumes a linear relation between time and conversion, was used to determine the kinetic parameters for reduction and oxidation, with chemical reaction being the main resistance to the reaction. The order of reaction found was 1 with respect to CH₄ and 0.65 with respect to O₂. The activation energy for the reduction reaction was 119 and for the oxidation reaction. The reactivity data and kinetic parameters were used to estimate the solid inventory in the air and fuel reactor of a CLC system. The optimum solid inventory obtained was at a value of ΔX_s=0.4. At these conditions, the recirculation rate of oxygen carrier between air and fuel reactor was per MW of fuel, which could be accomplished in an industrial reactor. The high reactivity of the Mn₃O₄/Mg-ZrO₂ with both methane and oxygen showed that this is a very promising oxygen carrier for CLC.     

Tetralin hydrogenation catalyzed by Mo2C/Al2O3 and WC/Al2O3 in the presence of H2S

Supported molybdenum and tungsten carbides were synthesized by temperature-programmed reactions. These materials were characterized by XRD, EDS analysis, HRTEM and CO chemisorption. Hydrogenation of tetralin was carried out at a total pressure of 4 MPa (3.06 MPa of H₂), at 573 K, without or with sulfur (200 ppm of sulfur as DMDS). The resulting activities were compared with those of MoS₂/Al₂O₃ and Pt (1% (w/w) metal loading) supported on Al₂O₃ or SiO₂. In the absence of sulfur, WC/Al₂O₃ showed an initial activity similar to that of Pt/SiO₂, higher than that of MoS₂/Al₂O₃ but lower than that of Pt/Al₂O₃. In the presence of H₂S, WC/Al₂O₃ showed a steady-state activity similar to that of Pt/Al₂O₃ (which suffered a marked deactivation). Post-reaction characterization did not show any sulfur poisoning of the supported carbides. Therefore the supported carbides are sulfur-tolerant and promising catalysts for the hydrogenation of aromatics in diesel fuels in the presence of small amounts of S-containing compounds.     

Development of a kinetic model for the oxidation of methane over Pd/Al2O3 at dry and wet conditions

The kinetics of the oxidation of methane over a commercial 0.5% Pd on γ-Al₂O₃ catalyst has been studied in a lab-scale fixed-bed reactor, the effect of temperature, and methane, oxygen and water partial pressures being investigated, in a range of interest for environmental applications. Different Eley–Rideal, Langmuir–Hinshelwood and Mars–van Krevelen models were fitted to the experimental results, the best fitting being obtained for a Mars–van Krevelen model that considers slow desorption of the reaction products. The model parameters obtained both from differential and integral treatment of the experimental data are in good agreement with each other. A modification of the proposed model, taking into account that water is adsorbed over oxidised sites, is also able to model the inhibition produced by steam.     

助剂Ba对Pd/Al_2O_3和Pt/Al_2O_3催化剂的C1-C3烷烃催化燃烧性能的影响

通过浸渍法制备了Al_2O_3负载的Pd和Pt催化剂,考察催化剂的甲烷、乙烷和丙烷催化燃烧活性,以及助剂Ba对催化性能的影响。对于Pd/Al_2O_3催化剂,加入Ba使活性物种PdO颗粒变大和还原温度升高,形成更稳定的PdO活性物种,是Pd-Ba/Al_2O_3催化剂活性提升的主要原因。对于Pt/Al_2O_3催化剂,加入Ba助剂使活性物种Pt0含量降低,PtO_x与Al_2O_3载体相互作用增强,使PtO_x物种更难被还原为Pt~0,导致Pt-Ba/Al_2O_3催化剂活性降低。Pd和Pt催化剂催化烷烃氧化反应活性规律一致:丙烷乙烷甲烷。Pd/Al_2O_3催化剂有利于C—H键活化,Pt/Al_2O_3催化剂有利于C—C键活化。Pt/Al_2O_3催化剂对C1-C3烷烃氧化活性的差别明显大于Pd/Al_2O_3催化剂。Pt/Al_2O_3催化剂对碳比例高的烷烃活性更高。     

Structure sensitivity of dimethylamine deep oxidation over Pt/Al2O3 catalysts

The deep oxidation of dimethylamine (DMA) was studied over Pt/Al₂O₃ catalysts with small (1 nm) and large (7.8–15.5 nm) Pt crystallite sizes. The turnover frequency (TOF) was higher for the large than for the small Pt crystallites, indicating that the reaction is structure sensitive. Two kinetic models were used to interpret the obtained results, i.e., the Mars van Krevelen and a mechanism based on the adsorption of oxygen and adsorption of dimethylamine on different active sites were employed. Both models showed that the activation energy for the oxygen chemisorption rate constant (k_o) decreased with increasing of Pt crystallite size and that the activation energy for the surface reaction rate constant (k_i) was independent of the Pt crystallite size. The structure sensitivity may be explained by differences in the reactivity of the oxygen adsorbed on these Pt crystallites.The Mars van Krevelen model fits the TOF values very well at concentrations of DMA higher than 1500 ppm, while in the lower concentrations region, the model under predicts the experimental data. The model based on the adsorption of oxygen and DMA on different active sites fits the experimental data quite well over the whole temperature and concentration range. The fitted values of the Henry adsorption constant are independent of the Pt crystallite size.     

Kinetic studies of CH4 oxidation over Pt–NiO/δ-Al2O3 in a fluidised bed reactor

The oxidation of CH₄ over Pt–NiO/δ-Al₂O₃ has been studied in a fluidised bed reactor as part of a major project on an autothermal (combined oxidation–steam reforming) system for CH₄ conversion. The kinetic data were collected between 773 and 893 K and 101 kPa total pressure using CH₄ and O₂ compositions of 10–35% and 8–30%, respectively. Rate–temperature data were also obtained over alumina-supported monometallic catalysts, Pt and NiO. The bimetallic Pt–NiO system has a lower activation energy (80.8 kJ mol⁻¹) than either Pt (86.45 kJ mol⁻¹) and NiO (103.73 kJ mol⁻¹). The superior performance of the bimetallic catalyst was attributed to chemical synergy. The reaction rate over the Pt–NiO catalyst increased monotonically with CH₄ partial pressure but was inhibited by O₂. At low partial pressures (<30 kPa), H₂O has a detrimental effect on CH₄ conversion, whilst above 30 kPa, the rate increased dramatically with water content.     

Preferential oxidation of CO over CuO/CeO2 and Pt-Co/Al2O3 catalysts in micro-channel reactors

Micro-channel plates with dimension of 1 mm × 0.3 mm × 48 mm were prepared by chemical etching of stainless steel plates followed by wash coating of CeO₂ and Al₂O₃ on the channels. After coating the support on the plate, Pt, Co, and Cu were added to the plate by incipient wetness method. Reaction experiments of a single reactor showed that the micro-channel reactor coated with CuO/CeO₂ catalyst was highly selective for CO oxidation while the one coated with Pt-Co/Al₂O₃ catalyst was highly active for CO oxidation. The 7-layered reactors coated with two different catalysts were prepared by laser welding and the performances of each reactor were tested in large scale of PROX conditions. The multi-layered reactor coated with Pt-Co/Al₂O₃ catalyst was highly active for PROX and the outlet concentration of CO gradually increased with the O₂/CO ratio due to the oxidation of H₂ which maintained the reactor temperature. The multi-layered reactor coated with CuO/CeO₂ showed lower catalytic activity than that coated with Pt catalyst, but its selectivity was not changed with the increase of O₂/CO ratios due to the high selectivity. In order to combine advantages (high activity and high selectivity) of the two individual catalysts (Pt-Co/Al₂O₃, CuO/CeO₂), a serial reactor was prepared by connecting the two multi-layered micro-channel reactors with different catalysts. The prepared serial reactor exhibited excellent performance for PROX.     

Photocatalytic reactions of imazamox at TiO2, H2O2 and TiO2/H2O2 in water interfaces: Kinetic and photoproducts study

The photocatalytic transformation of imazamox, a herbicide of imidazolinone family, is investigated in aqueous solution containing titanium dioxide, hydrogen peroxide or the combination of TiO₂/H₂O₂ under simulated sunlight irradiation. The effect of parameters such as the amount of catalysts, the concentration of herbicide, and the pH were investigated by measurement of the rate constant of degradation. Experimental data obtained under different conditions describe the dependency of degradation rate on the above mentioned parameters. Consequently, kinetic parameters were experimentally determined and a pseudo-first-order kinetic was observed. Mulliken charge distributions calculated by the DFT method B3LYP/6–31+G(d) level of theory for key cationic, anionic and neutral structures of imazamox give interpretation for the dependency of photodegradation rate constant on pH. The degradation rate constants were always higher for the heterogeneous catalysis in reactions (TiO₂/UV, TiO₂/UV/H₂O₂) compared to the homogeneous systems (UV alone, H₂O₂/UV). In parallel, five photoproducts could be tentatively identified using Electrospray ionization Fourier transform ion cyclotron resonance mass spectroscopy based on precise chemical formula assignments.     

Lean NOx reduction with CO + H2 mixtures over Pt/Al2O3 and Pd/Al2O3 catalysts

The reduction of NO_x by hydrogen under lean burn conditions over Pt/Al₂O₃ is strongly poisoned by carbon monoxide. This is due to the strong adsorption and subsequent high coverage of CO, which significantly increases the temperature required to initiate the reaction. Even relatively small concentrations of CO dramatically reduce the maximum NO_x conversions achievable. In contrast, the presence of CO has a pronounced promoting influence in the case of Pd/Al₂O₃. In this case, although pure H₂ and pure CO are ineffective for NO_x reduction under lean burn conditions, H₂/CO mixtures are very effective. With a realistic (1:3) H₂:CO ratio, typical of actual exhaust gas, Pd/Al₂O₃ is significantly more active than Pt/Al₂O₃, delivering 45% NO_x conversion at 160 °C, compared to >15% for Pt/Al₂O₃ under identical conditions. The nature of the support is also critically important, with Pd/Al₂O₃ being much more active than Pd/SiO₂. Possible mechanisms for the improved performance of Pd/Al₂O₃ in the presence of H₂+CO are discussed.     

Kinetics of methane oxidation on Pt catalysts in the presence of H2S and SO2

The kinetic parameters of the lean oxidation of CH₄ over alumina and ceria-alumina supported platinum catalysts in the presence of H₂S and SO₂ were derived in a stagnation point flow reactor at atmospheric pressure and at temperatures up to . A novel methodology similar to that of plug-flow reactors was devised to calculate the best-fit values for frequency factors and activation energies for the proposed heterogeneous gas-solid reactions of oxidation. Doping the N₂-diluted CH₄/air reactant flow with H₂S or SO₂ concentrations between 30 and had a significant promotional effect on the methane combustion rate. Al₂O₃ and CeO₂/Al₂O₃ were shown to be inert with respect to the oxidation of CH₄ to CO₂, and also in the oxidation of SO₂ to SO₃ in air. Pt catalysed the oxidation of CH₄, SO₂ and that of H₂S. A temperature window of conversion of SO₂ to SO₃ on the Pt-supported catalysts was found experimentally, and could be of practical use in combustion exhaust clean-up techniques. The repeated use of the foil resulted in a slight ageing effect for Pt/Al₂O₃. The presence of ceria in the washcoat helped prevent the loss of activity in CH₄ oxidation by mitigating the extent of sintering of the Pt particles upon ageing. One-step and two-step chemical reaction mechanisms are proposed for the CH₄ and the SO₂ lean oxidations, respectively.     

Cu/γ-Al2O3 catalyst for the combustion of methane in a fluidized bed reactor

The applicability of a catalyst based on copper dispersed on γ-Al₂O₃ spheres (1 mm diameter) for fluidized bed catalytic combustion of methane has been assessed. Catalyst properties have been determined by physico-chemical characterization techniques and fixed bed activity tests revealing the presence of a surface CuAl₂O₄ spinel phase, still active and stable in methane combustion after repeated thermal ageing treatments at 800 °C. Methane catalytic combustion experiments have been performed in a 100 mm premixed fluidized bed reactor under lean conditions (0.15–3% inlet methane concentration), showing that complete CH₄ conversion can be attained below 700 °C in a fluidized bed of 1 mm solids with a gas superficial velocity about twice the incipient fluidization velocity.