A Study of White‐Spirit Vapor Combustion on Pt/Al2O3 Catalyst

The objective of the work is to investigate the catalytic combustion of white spirit solvent vapors at low concentration in air, typical for depollution applications, on a commercial catalyst, Pt/γ‐Al₂O₃ (0.5 wt‐% Pt). To study the influence of the main variables on the process kinetics, experiments were performed under various operating conditions (temperature domain: 150–350 °C; flow rates: 125–250 mL min^–1; white spirit concentrations: 220–260 ppmv). The stoichiometry and kinetics of the vapor combustion was described globally by using a pseudo‐compound, representing the average molecular weight and the carbon/hydrogen ratio of the mixture. Experimental data were reasonably well correlated by a first order rate expression with respect to the apparent concentration of the lumping pseudo‐component.     

Simplified Free‐Radical Reaction Kinetics for p‐Xylene Oxidation to Terephthalic Acid

The kinetic models based on complex free‐radical mechanisms always involve lots of parameters, which result in model overparameterization. In this work, on the basis of free‐radical reaction mechanisms, a simplified kinetics for liquid‐phase catalytic oxidation of p‐xylene (PX) to terephthalic acid (TPA) was developed. By assuming that different peroxy radicals have equivalent reactivity, all the initiation rate constants are identical, and the differences in the rates of termination between various peroxy radicals are neglected, the kinetic model is simplified to include only six parameters that are to be determined by experiment. The kinetic model established in this paper was shown to have satisfactory precision in predicting the concentration profiles. The kinetic model proposed is even simpler than the first ‐ order kinetic model because the rate constants concerning chain propagation and termination are independent of temperature within the range investigated.     

Hybrid Process for o‐ and p‐Xylene Production in Aromatics Plants

A new hybrid process for the production of o‐ and p‐xylene is proposed to replace the traditional plant of aromatics in refineries. The proposed process comprises a simulated moving bed (SMB) unit and two crystallizers. The SMB technology as the first unit of the suggested process is applied for the separation of xylene isomers and was investigated by simulation of an industrial size unit, using experimentally measured adsorption equilibrium data on MIL‐53(Al)‐shaped material. The separation of p‐xylene from o‐xylene with m‐xylene as desorbent is the key characteristic of this method. An industrial‐scale SMB unit could provide extract and raffinate streams with very high purities.     

Glycerol‐Reforming Kinetics Using a Pt/C Catalyst

Catalytic steam reforming of glycerol, a by‐product in biodiesel production, represents an attractive route to hydrogen. For the first time, the kinetics of the glycerol steam reforming reaction over a Pt/C catalyst was considered. Kinetic data, i.e., glycerol conversion vs. space time, were obtained experimentally by using a fixed‐bed reactor and were analyzed by the integral method of analysis. It was found that in the studied ranges of temperature from 623 to 673 K and space time from 0.39 to 1.56 g h/mol the investigated reaction is of the first‐order with respect to glycerol. The specific reaction rate constant at 673 K was determined to be 1.1·10⁵ cm³/g_cat h. The values of glycerol conversion predicted by the first‐order kinetic model were in good agreement with those obtained experimentally. The increase in temperature, space time, and initial water/glycerol ratio caused the expected increase in hydrogen yield.     

Catalytic combustion of methane over bimetallic Pd–Pt catalysts: The influence of support materials

The effect of support material on the catalytic performance for methane combustion has been studied for bimetallic palladium–platinum catalysts and compared with a monometallic palladium catalyst on alumina. The catalytic activities of the various catalysts were measured in a tubular reactor, in which both the activity and stability of methane conversion were monitored. In addition, all catalysts were analysed by temperature-programmed oxidation and in situ XRD operating at high temperatures in order to study the oxidation/reduction properties.

The activity of the monometallic palladium catalyst decreases under steady-state conditions, even at a temperature as low as 470 °C. In situ XRD results showed that no decomposition of bulk PdO into metallic palladium occurred at temperatures below 800 °C. Hence, the reason for the drop in activity is probably not connected to the bulk PdO decomposition.

All Pd–Pt catalysts, independently of the support, have considerably more stable methane conversion than the monometallic palladium catalyst. However, dissimilarities in activity and ability to reoxidise PdO were observed for the various support materials. Pd–Pt supported on Al₂O₃ was the most active catalyst in the low-temperature region, Pd–Pt supported on ceria-stabilised ZrO₂ was the most active between 620 and 800 °C, whereas Pd–Pt supported on LaMnAl₁₁O₁₉ was superior for temperatures above 800 °C. The ability to reoxidise metallic Pd into PdO was observed to vary between the supports. The alumina sample showed a very slow reoxidation, whereas ceria-stabilised ZrO₂ was clearly faster.     

Catalytic Combustion of Toluene over a Copper‐Manganese‐Silver Mixed‐Oxide Catalyst Supported on a Washcoated Ceramic Monolith

Monolithic catalysts were prepared by washcoating an alumina sol and then impregnating Cu‐Mn‐Ag mixed oxides onto cordierite substrates. The effects of the preparation parameters including the Ag/Cu/Mn ratio, the total amount of active phase and the loading of washcoat, and the reaction conditions, e.g., the space velocity and the oxygen/toluene ratio on the catalytic performance for the combustion of toluene were investigated. It is shown that the Cu‐Mn‐Ag oxides are very active for the combustion of toluene and that the highest catalytic activity is achieved over a monolithic catalyst containing 14.7 wt % of washcoat and 21.2 wt % of active phase with a Ag/Cu/Mn molar ratio of 13.8/43.1/43.1. It is also seen that the optimum catalyst has a good catalytic stability and exhibits an excellent activity not only at a rather high space velocity but also within a wide range of oxygen/toluene ratios.     

Treatment of Volatile Organic Compounds with a Pt/Co3O4‐CeO2 Catalyst

For emission control of volatile organic compounds (VOC), e.g., in the painting and printing industries, conventional Pt/Al₂O₃ and Co₃O₄‐CeO₂ catalysts are used. On the Pt/Al₂O₃ catalyst, aromatic hydrocarbons containing a benzene ring such as toluene can be oxidized at a lower complete oxidation temperature than on Co₃O₄‐CeO₂, under typical treatment conditions. However, ethyl acetate and isopropyl alcohol can be oxidized at a lower complete oxidation temperature on Co₃O₄‐CeO₂ than on Pt/Al₂O₃. In this study, platinum was directly supported on Co₃O₄‐CeO₂. Using chloroplatinic acid, the platinum cohered and the catalytic activity did not improve. But when the platinum was supported using platinum colloid coated with dispersant, high‐dispersion support of the platinum on the Co₃O₄‐CeO₂ surface was achieved, and toluene, ethyl acetate, and isopropyl alcohol could be oxidized at less than 250 °C.     

Anodic Alumina Supported Pt Catalyst for Total Oxidation of Trace Toluene

Featuring an assembly of identical pores, through-pore anodic alumina (AAO) makes an ideal monolith-like cat-alyst support for volatile organic compound (VOC) combustion. This work employs the oxidatio...     

Effect of polymerization conditions on o‐phenylenediamine and o‐phenetidine oxidative copolymers

A series of new o‐phenylenediamine (OPD)/o‐phenetidine (PHT) copolymers with partly phenazine‐like structures has been successfully synthesized at three polymerization temperatures by chemically oxidative polymerization in four different polymerization media. The molecular structures and properties of the resulting OPD/PHT polymers were investigated by IR, UV–vis and high‐resolution ¹H NMR spectroscopies, and DSC, in order to ascertain the effect of reaction temperature, comonomer ratio and acid medium. The copolymerization mechanism of OPD with PHT monomers has been proposed. It is found that the statistical OPD/PHT copolymer obtained at a temperature of 118 °C has a higher degree of polymerization than that obtained at 12–17 °C. The OPD content in the copolymers calculated from NMR spectroscopic analysis is higher than that in the feed OPD content, whereas the OPD content calculated from element analysis is slightly lower than the feed OPD content. It can be predicted that denitrogenation takes place in the OPD units during the polymerization process at OPD/PHT molar ratios of 90/10 and 100/0. These OPD/PHT copolymers exhibit a much better solubility than the OPD homopolymer, hence suggesting an incorporation of PHT units into the phenazine structure of the homopolymer. The thermal behavior of the copolymers was also studied. Copyright © 2004 Society of Chemical Industry     

Combustion of CH4 over a PdO/ZrO2 catalyst: an example of kinetic study under severe conditions

A kinetic study on CH₄ combustion over a very active PdO/ZrO₂ catalyst with high Pd loading (10% w/w of Pd) is presented as an example of a demanding problem which requires both the development of appropriate experimental tools and a theoretical insight on surface chemistry.

The use of an annular catalytic reactor as a tool to collect kinetic data under unusually severe conditions (high temperature and CH₄ concentration) is described in comparison with the use of a conventional packed bed reactor. In particular, problems related to the biasing effects of mass, heat and momentum transfer are addressed.

Kinetic data addressing the effects of CH₄, O₂, H₂O and CO₂ concentration in a temperature range from 400 to 550 °C are analysed by means of a purely empirical power law model and of a formal kinetic model based on literature indication assuming methane dissociative adsorption as the rate controlling step.     

Pt/Pd催化燃烧催化剂处理含苯系物废气技术研究

采用Pt/Pd催化燃烧催化剂对含苯系物的有机废气进行了处理.通过对单组分和多组分关键污染物模拟废气的催化燃烧考察实验表明,Pt/Pd催化剂对含苯系物有机废气中各关键污染组分具有较强的脱除效果.在反应器人口温度250℃,空速20 000 h-1的条件下,污染物去除率达到97％以上.净化后气体符合国家排放标准.     

Reactivation and Reuse of Platinum‐Based Spent Catalysts for Combustion of Exhaust Organic Gases

The optimum pretreatment method for a Pt‐based spent catalyst for the removal of exhaust organic gases was examined. Two different pretreatment procedures with gas and aqueous solution were evaluated. Results obtained from the catalytic combustion of trace CH₄ demonstrate that air pretreatment has a slightly positive effect. NaBH₄ solution treatment leads to the highest initial activity. No pulverization of the granule size and sintering of the Pt nanoparticles happen after NaBH₄ treatment. Results from the catalytic combustion of toluene indicate that the performance of the NaBH₄‐treated catalyst can be further improved by combination with air pretreatment.     

Kinetics of methane combustion over CVD-made cobalt oxide catalysts

The present investigation provides the required kinetic parameters to evaluate and to predict the rate of the catalytic combustion of methane over cobalt oxide. For this purpose, monolithic cordierites with low specific surface area were uniformly coated with cobalt oxide thin films of controlled thickness using the chemical vapor deposition (CVD) process. The obtained catalysts were tested in the catalytic combustion of methane in oxygen-deficient and -rich conditions. Catalysts with loadings above 0.46 wt.% are active starting at a temperature of 250 °C and completely convert methane to CO₂ below 550 °C where the conversion rate reaches 35 μmol (CH₄)/g_cat s. The involvement of the bulk-oxide-ions in the catalytic reaction was supported by the constant value of the normalized reaction rate to the weight of deposited cobalt oxide. The experimental data fit well to the Mars–Van Krevelen redox model and can be approximated with a power rate law in oxygen-rich mixtures. The resulting activation energies and frequency factors allow the identification of the rate-limiting step and accurately reproduce the effect of the temperature and partial pressure of the reactants on the specific reaction rate.     

Kinetics of Catalytic Ozonation of Methyl tert‐Butyl Ether in the Presence of Perfluorooctyl Alumina

In this work, the kinetics of heterogeneous ozonation of methyl tert‐butyl ether (MTBE) in the presence of perfluorooctyl alumina (PFOAL) catalysts is presented. Activity of the PFOAL catalysts in ozonation reactions of MTBE was studied in a batch reactor over the temperature range of 25 to 40 °C. The results show that PFOAL is an effective catalyst for enhancing the molecular mechanism of ozone reactions. For a catalyst concentration of 5 g/L, the contribution of the rate of heterogeneous catalytic reaction in the total reaction rate is about 50 %, 75 %, and 85 % at the reaction temperatures of 25 °C, 30 °C, and 40 °C, respectively. Kinetic studies showed that the chemical reaction of ozone and MTBE is the controlling step in this catalytic system. The quasi‐homogeneous kinetic model proved to be an appropriate approach in modeling the heterogeneous reaction of ozone with MTBE on PFOAL catalysts.     

Catalytic Combustion of the Stoichiometric n-Butane/Air Mixture on Isothermally Heated Platinum Wire

The catalytic combustion of the stoichiometric n-butane–air mixture per se or diluted with N₂, on a platinum wire at different initial pressures (10–70 kPa) and temperatures (690–1,080 K) was studied. The chemical heat flow rate, dQ _r/dt, of the surface reaction was measured in isothermal and isobaric conditions and the overall kinetic parameters were evaluated for both steady state and initial transient catalytic combustion. At low total pressure (10 kPa), the temperature dependence of dQ _r/dt indicated a normal (Arrhenius) behavior for 690 < T < 900 K, while at higher temperatures, over 900 K, an anti-Arrhenius behavior was found. The obtained results are consistent with a diffusion-controlled process, accompanied by reactant depletion around the catalytic surface, at higher temperatures.     

Potassium‐Activated Wire Mesh: A Stable Monolithic Catalyst for Diesel Soot Combustion

Potassium‐modified FeCrAl alloy wire mesh was developed as a catalytic diesel particulate filter to suppress the emission of soot from a diesel engine. Potassium species were deposited on wire mesh by a chemical vapor deposition method, in which a model soot was used to convert KOH into metallic K at high temperatures to subsequently activate the wire mesh. Tests showed that metallic K reacted with the enriched Al₂O₃ component on the surface derived from segregation and successive oxidation during precalcination. The resulting layer of K‐O‐Al species offers remarkable activity and stability for the catalytic oxidation of diesel soot. The K‐activated wire mesh could lower the initial temperature of soot combustion and maintain the activity for several cycles.     

Industrial Xylene/Ethylbenzene Isomerization Unit Using a Radial‐Flow Reactor and EUO‐Type Zeolite

A mathematical model based on 34 days continuous operation of an industrial isomerization unit was developed. The unit involves a radial‐flow reactor with a catalyst capable of converting xylenes and ethylbenzene to mixed xylenes. The catalyst contains EU‐1 zeolite, platinum, and alumina as binder. Two reactions are considered, i.e., ethylbenzene isomerization and xylene isomerization. The rates are based on the Hougen‐Watson model according to the literature. An optimization procedure based on the trust‐region‐reflective algorithm was carried out in order to obtain new kinetic constants that minimize the difference between the actual and the calculated values. The standard error of the parameters estimated was calculated through the deleted‐one Jackknife method.     

Studies on the dielectric properties of poly(o‐toluidine) and poly(o‐toluidine‐aniline) copolymer

Poly(o‐toluidine) (PoT) and poly(o‐toluidine co aniline) were prepared by using ammonium persulfate initiator, in the presence of 1M HCl. It was dried under different conditions: room temperature drying (48 h), oven drying (at 50°C for 12 h), or vacuum drying (under vacuum, at room temperature for 16 h). The dielectric properties, such as dielectric loss, conductivity, dielectric constant, dielectric heating coefficient, loss tangent, etc., were studied at microwave frequencies. A cavity perturbation technique was used for the study. The dielectric properties were found to be related to the frequency and drying conditions. Also, the copolymer showed better properties compared to PoT alone. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 592–598, 2004     

Electrochemical Methoxylation of p‐Xylene Over Modified Kaolin

Electrochemical methoxylation of p‐xylene with methanol over mono‐ and multi‐metal oxide(s) modified kaolin was performed under various conditions and the conversion of p‐xylene was seen to be higher than 80 %. The oxidation states of the metal(s) after modification were found from catalyst characterization by powder X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS). The reaction process was monitored by UV‐Vis spectroscopy and the extent of reaction was evaluated. Investigation of the application of the products by gas chromatography/mass spectrometry (GC‐MS) could lead to an improvement of the octane number of gasoline.     

Revamping an Existing Aromatics Complex with Simulated Moving‐Bed Reactor for p‐Xylene Production

A simulated moving‐bed reactor (SMBR) for the production of p‐xylene is studied as part of a proposal to modify an existing aromatics complex in order to increase the production of benzene and p‐xylene. The proposed complex includes a single‐stage crystallization unit to further purify high p‐xylene streams from a selective toluene disproportionation and said SMBR units. Mass balances for two cases are estimated, namely, the current flow of reformate fed to the complex and a twofold flow. Results show significant increases of benzene and p‐xylene for both cases compared to the current production of the complex.