Enhanced oxidation of the 9%Cr steel P91 in water vapour containing environments

The short term (∼100 h) oxidation behaviour of the 9%Cr steel P91 was studied at 650 °C in N₂-O₂-H₂O gas mixtures containing a relatively low oxygen level of 1%. The oxidation kinetics were measured thermogravimetrically and the oxide scale growth mechanisms were studied using H₂¹⁸O-tracer with subsequent analyses of oxide scale composition and tracer distribution by MCs⁺-SIMS depth profiling. The corrosion products were additionally characterised by light optical microscopy, SEM-EDX and XRD. It was found that the transition from protective, Cr-rich oxide formation into non-protective mixed oxide scales is governed by the ratio H₂O^(g)/O₂ ratio rather than the absolute level of H₂O^(g). The results of the tracer studies in combination with the data obtained from experiments involving in situ gas changes clearly illustrated that under the prevailing conditions the penetration of water vapour molecules triggers the enhanced oxidation and sustains the high growth rates of the poorly protective Fe-rich oxide scale formed in atmospheres with high H₂O^(g)/O₂ ratios. The experimental observations can be explained if one assumes the scale growth to be governed by a competitive adsorption of oxygen and water vapour molecules on external and internal surfaces of the oxide scales in combination with the formation of a volatile Fe-hydroxide during transient oxidation. The formation of the non-protective Fe-rich oxide scales is suppressed in atmospheres with low H₂O^(g)/O₂ -ratios, and the healing of any such scale is promoted.     

催化动力学光度法在贵金属测定中的实际应用

综述了催化动力学光度法在钌、铑、钯、银、锇、铱、铂等贵金属测定中的实际应用新近发展状况。     

THE “UCKRON-1” TEST PROBLEM FOR REACTION ENGINEERING MODELING

Testing kinetic models against a “true” and detailed kinetic expression was the aim of the Workshop on Kinetic Model Development at the Denver AIChE Meeting in August, 1983. For this purpose an artificial reaction mechanism was created, based on the known thermodynamics of the methanol synthesis as a framework. The kinetic rate laws, that were derived from this mechanism, were made thermodynamically consistent by achieving agreement between equilibrium constants calculated at various temperatures from the given, real original thermodynamic relationship and those calculated from the detailed reversible kinetic expressions.

Using the artificial kinetics as the "true" one, CSTR experiments were simulated. The results of a statistically designed set of experiments were published after 5% random error was added to the data. Participation was invited for all interested to correlate the data, develop kinetic models and to calculate the performance of the specified reactor.

The results of 19 submitted entries are summarized with the conclusion that the models had more differences than were expected, but their predictive values were not as different as was anticipated, if the extreme high production rates due to thermal runaways are not considered. This in turn points out the necessity to check models experimentally, in pilot plant, not only for predicted optimum, but also for calculated runaway conditions. Models which did not capture the true character of this reaction failed to predict the onset of runaway reactions.     

KINETIC AND TRACER STUDIES ON METHANOL CONVERSION OVER SUPPORTED PLATINUM CATALYSTS

Hydrogen-deuterium exchange in methanol over Al₂,O₃, platinum black and alumina supported platinum catalysts have been investigated by means of mass spectrometry. The hydrogen-deuterium exchange proceeds faster over Pt/Al₂O₃ than either platinum black or alumina, and the rate (as well as the rate of dimethyl ether formation) increases with platinum dispersion. From the reactions CH₃OH + D₂, CD₃OH + H₂ and CD₃OH + D₂ the different exchange rates of the CH₃ and OH groups (R₁, and R₂, respectively) were determined. For all catalysts studied the exchange in the OH group was two or three orders of magnitude faster than CH₃ group. Exchange in the methyl group needs higher activation energy: R₁/R₂ ratio increases with temperature. Catalyst pretreatment has an important effect: higher activation temperature results in a higher R₁/R₂ ratio.

A methematical method is suggested for the evaluation of exchange rates of a molecule with two different types of hydrogen and a model is given for the interpretation of measured data: methanol is activated mainly on Al₂,O₃, forming surface methoxide groups on the Lewis acidic sites. This methoxide can react with deuterium atoms having been activated over platinum sites. With increasing dispersion the metal-support interface is enhanced which leads to higher rate of exchange.     

Prediction of particle motion in a two-dimensional bubbling fluidized bed using discrete hard-sphere model

The solids motion in a gas-solid fluidized bed was investigated using a discrete hard-sphere model. Detailed collision between particles and a nearest list method are presented. The turbulent viscosity of gas phase was predicted by subgrid scale (SGS) model. The interaction between gas and particles phases was governed by Newton's third law. The distributions of concentration, velocity and granular temperature of particles are obtained. The radial distribution function is calculated from the simulated spatio-temporal particle distribution. The normal and shear stresses of particles are predicted from the simulated instantaneous particle velocity. The pressure and viscosity of particles are obtained from both the kinetic theory of granular flow and the calculated stresses of particles. For elastic particles the individual lateral and vertical particle velocity distribution functions are isotropic and Maxwellian. The observed anisotropy becomes more pronounced with increasing degree of inelasticity of the particles.     

Application of the general rate model with the Maxwell-Stefan equations for the prediction of the band profiles of the 1-indanol enantiomers

The adsorption isotherm data of R- and S-1-indanol and of their racemic mixture on cellulose tribenzoate were measured by frontal analysis. These experimental data were fitted to the single-component and the modified competitive Bilangmuir isotherms. The overloaded elution profiles of bands of the pure enantiomers and of the racemic mixture were calculated for different sample sizes, using the best competitive isotherm model and the General Rate Model of chromatography coupled with the generalized Maxwell-Stefan equation that describes the surface diffusion flux. The calculated and the experimental profiles were found to be in excellent agreement in all cases. The parameters of the model of the mass transfer kinetics were derived from the band profiles obtained for the pure enantiomers. The same values of these parameters give an excellent prediction of the profiles of multicomponent bands. The new model described here allows a satisfactory interpretation of the competitive mass transfer kinetics.     

动力学控制结晶法拆分1,1''''-联二萘酚工艺研究

对外消旋1,1'-联二萘酚(BINOL)的拆分进行了研究.采用动力学控制结晶的方法改进了(S)-2-吡咯烷酮-5-羧酰苯胺拆分BINOL的工艺,得到一种实用有效的获得光学纯BINOL的方法.采用该方法可以同时得到BINOL的R和S两种异构体,它们的ee值均大于99%.采用正交实验的方法研究了反应时间、拆分剂用量、溶剂组成以及溶剂体积在拆分过程中对(R)和(S)-BINOL的产率的影响.在最佳条件下,(R)-BINOL和(S)-BINOL的收率分别为18.0%和35.2%,外消旋BINOL的回收率为58.8%,拆分剂的回收率为68.6%.     

A study on structure and electrochemical properties of (La, Ce, Pr, Nd)2MgNi9 hydrogen storage electrode alloys

(La, Ce, Pr, Nd)₂MgNi₉ hydrogen storage alloys were prepared through induction melting followed by a long annealing treatment. The structure and electrochemical properties of annealed alloys have been investigated by orthogonal design experiments. Both the individual effects of each substituting element and their interaction in alloys were studied systemically. It has been shown that the structure of main phase in alloys belongs to PuNi₃-type with a space group R-3m. Substituting rare-earth elements have a significant effect on both the phase structure of alloys and microstructure. The anisotropic change in the crystal structure of alloys can cause the acceleration of pulverization of alloy particles and result in the deterioration of the cyclic stability of alloy electrodes. Misch metals can raise the plateau pressure of hydrogen absorption/desorption. The discharge capacity of alloy ranges from 342.97 to 380.68 mAh g⁻¹ depending on the sort and content of substituting elements. Both cerium and neodymium can obviously reduce the discharge capacity of alloy electrodes. When compared to the La₂MgNi₉ alloy electrode, mish metals can significantly improve the high rate dischargeability of alloy electrodes. The improvement of the kinetic characteristic of alloy electrodes mainly results from the increase of the hydrogen diffusion rate in alloy bulk.     

An apparent kinetic model for the carbonation of calcium oxide by carbon dioxide

For the apparent kinetics of the carbonation reaction of calcium oxide by carbon dioxide, as a kind of noncatalytic gas–solid reaction, a model equation has been proposed as follows: X=kbt/(b+t), where X is the conversion of CaO; k, a kinetic rate constant (time⁻¹); b, a constant (time) equivalent to the time taken to attain half the ultimate conversion of CaO, and t, the time. As a result of analyses for some literature-reported data of CaO-carbonation conversion, it has been found that the rate of the carbonation can be well represented by dX/dt=k(1−X/X_u)², where X_u is the ultimate conversion of CaO, which is given by the product of two parametric constants, k and b. The constants k and b in the two rate control regimes of CaO-carbonation, chemical reaction control and diffusion control, have been determined as functions of temperature, respectively. The activation energy in the carbonation of surface CaO with CO₂ is estimated to about 72 kJ/mol regardless of the sources of CaO, however, that in the diffusion control regime appears differently as 102.5 (mesoporous CaO) or 189.3 kJ/mol (commercial-available CaO), possibly due to the morphological differences of the two CaO samples. From a practical point of view, the simple model equation proposed in this study deserves attention in that the CaO-carbonation behavior at working temperatures higher than 700 °C could be closely predicted.     

Aromatic gas oil cracking under realistic FCC conditions in a microriser reactor

A paraffinic hydrowax feed spiked with naphthalene, anthracene, and phenanthrene was cracked in a once-through microriser reactor at 575 °C and with a catalyst-to-oil (CTO) ratio of 4.8 g_cat g_oil⁻¹. The conversion by cracking reactions is limited to the paraffinic fraction of the feed and the alkyl groups associated with the benzene ring in aromatic compounds; the aromatic probes did not crack under the applied conditions, and in fact an additional amount of naphthalene was formed by complex dealkylation and hydrogen transfer reactions. The ‘uncrackabilty’ of aromatics was directly demonstrated by processing an aromatic gas oil, containing 33.3 wt% aromatics. Experiments were performed with residence times between 0.05 and 8.2 s, keeping the temperature (525 °C) and CTO ratio (5.5 g_cat g_oil⁻¹) constant. The data was interpreted with a simplified first-order five-lump kinetic model, where approximately 19 wt% of the feed was found to be uncrackable. HCO (feedstock) conversion took mainly place during the first two seconds and coke was only formed during the first 50 ms of catalyst-oil contact. Gasoline was not overcracked to gas. Approximately 50 wt% of the LCO fraction was formed during this 50 ms and did not change thereafter.