On the determination of kinetic parameters for the regeneration of cracking catalyst

In the study of the regeneration of cracking catalyst, two approaches may be taken when determining the kinetic rate constant for the coke combustion reaction. A global coke burning rate equation may be considered, based on the observed oxygen concentration and carbon dioxide to carbon monoxide molar product ratio. This reaction may also be represented by an intrinsic coke burning equation which is a function of the oxygen concentration and the carbon dioxide to carbon monoxide molar ratio at the reaction site, combined with a carbon monoxide postcombustion equation. It is proposed in this paper that the rate constant for intrinsic coke burning, k^c, is essentially equal to the global coke burning rate constant, k_c, and that its value is independent of the rate equation chosen for the carbon monoxide post-combustion reaction.     

Catalytic hydrogenation of CO over the doped perovskite oxide YBa2Cu3O7-x catalysts

Perovskite oxide structured YBa₂Cu₃O₇-x(YBCO) has been first prepared by carbonate precipitation and then modified with palladium or ruthenium by impregnation on the perovskite oxide, while cobalt was co-precipitated simultaneously in the same pH range with perovskite oxide. After characterization the catalysts were used in the temperature range 300–450°C, in the pressure range 1–9 atmospheres and for H₂/CO ratios in the range 1–4 in a differential plug flow reactor for the hydrogenation of carbon monoxide to give hydrocarbons. The perovskite oxide (YBCO) 20% (w/w) and doped 2% (w/w) cobalt oxide catalyst were prepared by the wet chemical method from their nitrate solutions and oxidized at 950°C. Perovskite oxide (Dursun, G. & Winterbottom, J. M., J. Chem. Technol Biotechnol. 63 (1995) 113–16) was also doped with palladium and ruthenium metal by impregnation followed by oxidation at 250°C. The catalysts prepared were characterized by using TemperatureProgrammed Reduction (TPR) to observe the reduction temperature and also to measure total and metal surface area. The modified perovskite oxide on alumina, ruthenium- and cobalt-doped catalysts, has been shown to give a better conversion and also selectivity towards saturated hydrocarbons compared with palladium-doped catalyst. The temperature effect of these catalysts is more consistent, giving a steady increase of conversion with increasing temperature. Although increase of pressure increases the conversion, it causes very little change in product distribution. The activation energy of palladium- and ruthenium-doped, and cobalt co-precipitated catalysts for the reaction has been measured to be 55 kJ mol⁻¹, 75 kJ mol⁻¹ and 50 kJ mol⁻¹ respectively. A general rate equation of the form r=k[H₂]^m[CO]ⁿ has been observed and found to be applicable at the pressures and temperatures used for the catalytic system studied and found to be m≌1·0 for palladium-doped, m≌1·2 for ruthenium-doped and m≌0·95 for cobalt co-precipitated catalysts as n becomes zero or negligibly less than zero. The mechanism of reaction to produce hydrocarbons from syngas has been deduced from the results. It appeared that the carbon monoxide insertion mechanism has been more evident for palladium-doped catalysts whereas the carbide mechanism plays the main role for the ruthenium-doped and cobalt co-precipitated catalysts. © 1998 Society of Chemical Industry     

Ambient temperature oxidation of carbon monoxide using a Cu2Ag2O3 catalyst

The mixed copper–silver oxide, Cu₂Ag₂O₃, has been prepared by co-precipitation and tested for ambient temperature carbon monoxide oxidation. The catalyst demonstrated appreciable low temperature oxidation activity and the catalyst aged for 4 h was the most active. Carbon monoxide conversion increased with time-on-stream, reaching steady state after ca. 1000 min. Acomparison of the catalytic activity has been made with a representative sample of a high activity hopcalite, mixed copper/manganese oxide catalyst. On the basis of CO oxidation rate data corrected for the effect of catalyst surface area the Cu₂Ag₂O₃, aged for 4 h was at least as active as the hopcalite.     

Mechanism of low-temperature CO oxidation on a model Pd/Fe2O3 catalyst

A model Pd/Fe₂O₃ catalyst prepared by the vacuum technique has been studied in the carbon monoxide oxidation in the temperature range of 300–550 K at reagent pressures P(CO)=16 Torr, P(O₂)= 4 Torr. It has been shown that the activity of the fresh catalysts is determined by palladium. According to the XPS data, the reduction with carbon monoxide results in the formation of Fe²⁺ (formally Fe₃O₄) and appearance of the catalytic activity in this reaction at low temperatures (350 K). High low-temperature activity of the catalyst is supposed to be connected with the reaction between oxygen adsorbed on the reduced sites of the support (Fe²⁺) and CO adsorbed on palladium (CO_ads) at the metal–oxide interface.     

High-temperature oxidation of aluminium in various gases

The oxidation of high-purity aluminium sheet in dry oxygen, moist oxygen, carbon dioxide and carbon monoxide (at total pressure 1.333 × 10³ Nm^?2) was studied in the range 673–923°K, using a vacuum microbalance to follow weight gains. ¹⁴CO₂ and ¹⁴CO were used to elucidate the mechanism of the oxidation in these gases and to estimate the extent of carbon deposition in the oxide layer. The rate of oxidation in moist oxygen was similar to that in dry oxygen, the principle reaction being 2Al + 3H₂O ← Al₂O₃ + 3H₂. It is suggested that there are three steps in the reaction in CO₂, viz. 2Al+3CO₂ ← Al₂O₃ + 3CO, followed by 2Al + 3CO ← Al₂O₃ + 3C, and about 10% of the deposited carbon reacting further by 4Al + 3C ← Al₄C₃. Only the last two reactions are operative in carbon monoxide. The Arrhenius plots show a distinct break in the region 773–823°K for both carbon monoxide and carbon dioxide, but not for dry or moist oxygen. This is tentatively explained by a change in the rate-determining process from diffusion via grain boundaries or cracks in the oxide, to lattice diffusion. It is suggested that carbon may become mobile in the oxide film between 773 and 823°K and may tend to congregate in the grain boundaries and cracks. The oxide film remained protective throughout the duration of the experiments in all the gases.     

Promotional effect of H2 on CO oxidation over Au/TiO2 studied by operando infrared spectroscopy

The oxidation of carbon monoxide in the presence of various concentrations of molecular hydrogen has been studied over a Au/TiO₂ reference catalyst by combining diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and mass spectrometry. It is shown for the first time that H₂ enhances the CO oxidation rate on Au/TiO₂ without leading to any major loss of selectivity. Increasing the H₂ pressure induces higher CO and H₂ oxidation rates. Under H₂-free conditions, the surface species detected are Au^δ+–CO, Ti⁴⁺–CO, carbon dioxide and carbonates. Upon the addition of H₂, Au⁰–CO, water and hydroxyl groups become the main surface species. The occurrence of a preferential CO oxidation mechanism involving H_xO_y species under the present experimental conditions is proposed.     

Reaction between Hydrosulfide and Iron/cerium (hydr)oxide: Hydrosulfide Oxidation and Iron Dissolution Kinetics

Hydrosulfide oxidation and iron dissolution kinetics were studied at normal pressure, under inert (N₂) atmosphere, in a liquid–solid mechanically-stirred slurry reactor. The kinetic variables undergoing variations were: hydrosulfide initial concentration (0.90–3.30 mmol/L), oxide initial surface area (16–143 m²/L) and pH (8.0–11.0). The hydrosulfide consumption and products (thiosulfate and polysulfide) formation were quantified by means of capillary electrophoresis, while iron dissolution was monitored through atomic absorption spectroscopy. Most of Fe(II) produced at pH = 9.5 remained associated with the oxide surface in the time-scale of the experiments. The hydrosulfide oxidation by the iron/cerium (hydr)oxide was found to be surface-controlled, with rates (R_i) of both sulfide oxidation and Fe(II) dissolution expressed in terms of an empirical rate equation: R_i = k_i[HS⁻]_t=0^−0.5[A]_t=0[H⁺]_t=0^−0.5 , where k_i represents the apparent rate constants for the oxidation of HS⁻ (k_HS) or the dissolution of Fe(II) (k_Fe), [HS⁻]_{t = 0} is the initial hydrosulfide concentration, [A]_{t = 0} is the initial Fe/Ce (hydr)oxide surface area and [H⁺]_{t = 0} is the initial proton concentration. The rate constant, k_HS, for the oxidation of hydrosulfide at pH = 9.5 was (3.4219 ± 0.65) × 10⁻⁴ mol² L⁻¹ m⁻² min⁻¹, with the rate of hydrosulfide oxidation being ca. 10 times faster than the rate of Fe(II) dissolution (assuming a 1:2 stoichiometric ratio between HS⁻ oxidized and Fe(II) produced; k_Fe = (3.9116 ± 0.41) × 10⁻⁵ mol² L⁻¹ m⁻² min⁻¹).     

Peroxyacetic Acid Oxidation of Olefins and Alkanes Catalyzed by a Dinuclear Manganese(IV) Complex with 1,4,7-trimethyl-1,4,7-triazacyclononane

Natural terpenes, (−)-limonene and (+)-carvone, can be epoxidized by peroxyacetic acid (PAA) at room temperature if a dinuclear manganese(IV) complex with 1,4,7-trimethyl-1,4,7-triazacyclononane (L), [Mn₂L₂O₃] [PF₆]₂, is used as a catalyst. The total yield of the epoxides based on the consumed olefins are 97 and 95%, respectively. A kinetic study of the dec-1-ene and cyclohexane oxygenations including the investigation of their simultaneous competitive oxidation was carried out. The olefin epoxidation rate does not depend on dec-1-ene concentration and the dec-1-ene concentration does not affect the rate of cyclohexane oxidation. The cyclohexane oxidation rate is proportional to the alkane concentration. The kinetic analysis led to the conclusion that two species X ₁ and X ₂ are generated in the system, and there is no their mutual interconversion. The rate equation for the dec-1-ene epoxidation was proposed: W = k ₊₁[cat][PAA], where cat is the initial manganese complex or its derivative, and the constant was determined: k ₊₁ = 3.5 mol⁻¹ dm³ s⁻¹. Species X ₁ is apparently an effectively epoxidizing manganese peroxo derivative whereas species X ₂ is an alkane hydroxylating manganese oxo complex.     

Kinetic modeling of CO oxidation on Pt/CeO2 in a gradientless reactor

Cerium oxide is a major additive in three-way catalysts used in emission control of automobile exhaust. Pt/CeO₂ was studied in order to better understand the role of ceria in promoting CO oxidation reaction. The kinetics of carbon monoxide oxidation on Pt/cerium oxide catalyst, was studied over the temperature range 100–170°C. Steady state kinetic measurements of CO oxidation were obtained in a computer controlled micro-CSTR reactor. Activation energies were reported to vary between 39·5 and 51·2 kJ mol⁻¹. At low concentrations of either reactant (CO, O₂) and total conversion, the catalyst exhibited multiple steady states, similar to the multiplicity behavior of Pt/Al₂O₃. The total conversion was reached at 120°C. In comparison, the total conversion at low reactant concentrations was reached at a temperature of 148°C for the alumina-supported catalyst. Langmuir–Hinshelwood mechanisms gave a good fit to the data. However, no single rate expression could effectively describe the CO oxidation data over the whole concentration in the product of the CSTR reactor. The facts gathered indicate that oxygen adsorbed on interfacial Pt/Ce sites and ceria lattice oxygen provides oxygen for CO oxidation. Cerium oxide has been found to lower CO oxidation activation energy, enhance reaction activity and tends to suppress the usual CO inhibition effect.     

Transient rate tracer studies in heterogeneous catalysis: Oxidation of carbon monoxide

Establishment of the mechanism of a catalytic reaction is important from the viewpoints of both catalyst development and construction of suitable rate equations for design purposes. The use of transient tracing employing isotopes is a useful tool for this purpose. In this paper, a new method is described in which the transfer of isotopic species is superposed on a heterogeneous catalytic reaction conducted under steady-state conditions. An efficient method of modeling the system of first-order differential equations describing tracer transfer is presented. The method is applied to the oxidation of carbon monoxide over hopcalite catalyst. A relatively simple model with one type of site for adsorbed carbon oxide species correlates the data well for both ¹³CO₂ and ¹³CO marking. The final step, CO₂ adsorption and desorption, is fast and reversible.     

Analysis of Steady‐State Temperature Profiles from a Laboratory Reactor by Means of a Process Simulator

A process simulator was used for the analysis of steady‐state results from a laboratory‐scale tubular reactor for the oxidation of carbon monoxide over a platinum catalyst. From a set of 14 steady‐state experiments, temperature profiles were simulated with two adjustable parameters recovered by optimizing the fit: k°, the pre‐exponential portion of the rate constant, and h_out, the outer wall heat transfer coefficient for the reactor tube. Simulation showed that despite elaborate insulation the reactor did not behave adiabatically. Simulation also predicted fairly well the magnitude of phenomena such as ignition, extinction, and rate hysteresis (caused by changes in feed temperatures or concentrations) but at temperatures below the experimental values.     

Effect of catalyst loading on gasliquid mass transfer in a slurry reactor: A statistical experimental approach

A statistical experimental design was employed to study the effects of pressure, temperature, catalyst loading, and mixing speed on the solubilities (C*) and volumetric gas/liquid mass transfer coefficients (k_L^a) for H₂, N₂, CO, CH₄ and C₂H₄ in a liquid mixture of hexanes containing iron oxide catalyst in a 4-litre agitated autoclave. Statistical correlations for k_L^a values for the gases used were developed. Mixing speed and solid concentration showed the strongest effects on k_L^a. At low catalyst concentrations, a maximum in k_L^a was observed and at concentrations > 37 mass%, k_L^a decreased by more than one order of magnitude.     

Kinetics of hydrogen peroxide oxidation of alkyl dimethyl amines

We measured the absolute rate constants for the hydrogen peroxide oxidation of two different octyl dimethyl amines in isopropanol/water mixtures at 23°C. The amines were 1-octyl dimethyl amine (1) and 2-ethylhexyl dimethyl amine (2); their structures were analogous to those most often encountered in commercial alkyl dimethyl amine oxide production. The observed first-order rate constants for the disappearance of amine across a range of H₂O₂ concentrations (0.5–8 M) indicated that the overall rate was first-order in amine and 3/2-order in H₂O₂. Calculations showed k ₁=0.16 M⁻¹h⁻¹, k ₂=0.046 M⁻¹h⁻¹, and k ₁/k ₂=3.5. The rates appeared to decrease with increasing steric hindrance around the nitrogen atom. We also investigated the effect of water on the reaction rates. When [H₂O]<∼4.5 M in isopropanol, the rates increased with increasing [H₂O]; for [H₂O]>∼4.5 M, the rates were insensitive to [H₂O].     

在工业催化剂上水煤气变换反应宏观动力学

用内循环式无梯度反应器,在不同的反应条件下,测定了B106及B109两种型号的原粒度工业变换催化剂的宏观反应速率.根据实验数据关联出两种催化剂都适用的宏观动力学方程,求定了相应的模型参数.该式可用以模拟工业变换反应器.此外,并由实验数据计算了各种情况下的有效因子.整个实验及计算结果表明,这两种催化剂对气体的内扩散阻力都是相当大的.     

Kinetics and mechanism of the vapour phase nitroxidation of toluene over nickel oxide-aluminium oxide catalyst

The kinetics of the oxidation of toluene by nitric oxide over nickel oxide-aluminium oxide catalyst has been studied in the temperature range 280-380°C. A rate equation R_n= k_tp_tk_nP_n I (k₁P₁ + k_nP_n) was deduced, assuming a steady state involving a two-stage irreversible oxidation-reduction process. The model represented the data satisfactorily for the conversion of toluene to benzonitrile.     

Comparative energy barriers for hydrogen activation by homogeneous and heterogeneous metal oxide catalysts

Triethylene glycol solutions of alkali and alkaline earth metal hydroxide complexes are well-defined soluble oxide water-gas shift catalysts which equilibrate the reaction of carbon monoxide and water to yield hydrogen and carbon dioxide at temperatures ranging from 150 ° to 250 °C and carbon monoxide pressures of 1 to 300 atm. Significantly, catalysis proceeds cleanly, even in the complete absence of a metal center in the soluble oxide system. Thus, the rate of hydroxide ion catalyzed hydrogen evolution is highest in the presence of a noncoordinating organic cation: Bu_ΔN⁺>Cs⁺>Na⁺>H⁺>Ca⁺². Furthermore, the activation energy for the homogeneous sodium hydroxide catalyst in triethylene glycol solution, 26±1 kcal, is comparable to that exhibited by a commercially used heterogeneous iron oxide catalyst, 27±0.2 kcal. The alkali metal hydroxide system may be modified for metal cocatalysis. Thus, lead (II) oxide dissolves in the triethylene glycol solutions to yield a new species which exhibits a²⁰⁷Pb NMR resonance shifted 3350 ppm downfield from lead perchlorate. The activity of this lead modified system is improved by three orders of magnitude. Yet, the activation energy is unchanged, 26±1 kcal, suggesting that entropic factors may be important in these homogeneous metal oxide hydrogen evolution/activation systems.     

Oxidation kinetics of linoleic acid in the presence of saturated acyl <Emphasis Type="SmallCaps">l</Emphasis>-ascorbate

The oxidation processes of linoleic acid (LA) in the presence of l-ascorbic acid or saturated acyl l-ascorbate additives were measured at various temperatures and molar ratios of the additive to LA. Higher oxidative stability of LA was observed at higher additive levels for all additives. The addition of the ascorbates lengthened the induction period for the oxidation of LA. An autocatalytic kinetic rate equation was used to model the oxidation processes of LA mixed with the ascorbates, and the dependence of the rate constant, k, on acyl-chain carbon number was determined. At any temperature, the use of ascorbate additives decreased the k value for LA, and there was a slight tendency for k values to decrease with increasing acyl-chain length. The apparent activation energy, E _a, and the frequency factor, k ₀, for the rate constant were determined from Arrhenius plots. The calculated E _a and k ₀ values also decreased with increasing ascorbate acyl-chain length.     

Reaction models for simulation of the oxidation of carbon monoxide in turbulent diffusion flames

The oxidation of carbon monoxide by air in a turbulent flow was investigated under experimental conditions where the rates of turbulent mixing and of chemical reaction are comparable. For this purpose, carbon monoxide was admixed into the completely burnt gas of a natural gas flame operated with excess of air. Measurements of mean values of axial velocity, temperature and volume fractions of carbon monoxide and oxygen were compared with computational simulations involving the k – ? turbulence model and several turbulent reaction models for the oxidation of carbon monoxide. The comparison of measurements and numerical calculations demonstrated that the k – ? turbulence model is suitable for prediction of the turbulent flow field in the flow system investigated. Furthermore, it could be shown that one-variable turbulent reaction models, such as the flamesheet or the eddy-break-up model, cannot explain the measured carbon monoxide volume fraction profiles. Two-variable turbulent reaction models with a probability density function closure of the source term of the transport equation for the mass fraction of the chemical species result in a better agreement between the measured and simulated volume fraction profiles, particularly in predicting the clear influence of the initial temperature on carbon monoxide volume fractions. Weighting of the kinetic rate expression for the oxidation of carbon monoxide with different presumed probability density functions yields slightly different predictions of the carbon monoxide volume fractions, reflecting the assumed different character of turbulent fluctuations.     

Polymerizations of α-olefins and styrene with MgCl2-supported titanium catalyst system: MgCl2/TiCl4/PhCO2Et with AlEt3PhCO2Et

Summary Kinetic analysis was performed in a short time polymerizations of 1-butene,4-methyl-1-pentene and styrene by using a catalyst system composed of MgCl₂/TiCl₄/PhCO₂Et with AlEt₃/PhCO₂Et which is known as a highly active and highly stereospecific catalyst system in olefin polymerization. The concentration of the active centers, [C ^*], the propagation rate constant, k _p, and the chain transfer rate, r _tr, were determined for each monomer. It was found that the values of [C ^*] were almost same for every monomer, but the values of k _p changes widely in the following order: propylene>1-butene>4-methyl-1-pentene>styrene.     

Electrochemical oxidation of acidic Alberta coal slurries

The electrochemical oxidation of four different types of Alberta coals of bituminous and subbituminous rank have been studied in 1 M H₂SO₄ slurries at 90°C under potentiostatic conditions at an applied potential of 1.0 V with respect to RHE. Two particle sizes (>200 and <60 mesh) were used to determine the rate constant for the electrochemical oxidation of coal mediated by Fe³⁺. Two rate constants,k _c.1, andk _c.2, representing initial (0-6 h) and subsequent (6–24 h) stages of electrochemical oxidation of coal, respectively, were observed. A correlation between the rate constants and the fixed carbon content (rank) of the coals was drawn. Gas chromatographic analysis of the gaseous oxidation products indicated the production of carbon dioxide. The rate and current efficiency for this production was determined as a function of electrolysis time with the rate of production reaching a steady-state level after a few hours of electrolysis. Possible mechanisms, for the oxidation of coal are discussed, based on structural and functional group models.