工业原料铁制备浆态床FT合成用的Fe-Cu-K-Si催化剂的探索

费托合成技术是公认的将煤基合成气转化为液体燃料和化工原料的重要技术途径。虽然固定床费托合成技术从五十年代起已经工业运转，但是浆态床费托合成技术由于其传热性能好，可直接使用第二代气化炉生产的富CO合成气，反应器结构简单，单台反应器生产能力大，开工率高，产品结构合理，     

Importance of the Debye interaction in organic solutions: Henry's law constants for polar liquids in nonpolar solvents and vice versa

Henry's law constants have been determined for -butyrolactone (BL), ethyl acetate (EA), and 2-methyl-3-pentanol (MEP) in mixtures of iso-octane (ISO) and toluene (TOL), for BL, EA, TOL, and ISO in cinnamaldehyde (CIN) and for TOL and ISO in each other and in BL. From these data and published vapor pressures, the activity coefficients at infinite dilution and the standard molar Gibbs free energy of transfer, G ₂ ⁰ of the solutes from dilute solution in ISO to dilute solution in each solvent medium have been calculated. The different behavior patterns of BL and EA are attributed to differences in their abilities to exist in different conformations possessing different dipole moments. For polar solutes, G ₂ ⁰ decreases with increasing polarizability of the solvent and with increasing dipole moment of the solute, suggesting increased contributions from dipole-induced dipole (Debye) interactions. The sigmoidal plot of G ₂ ⁰ against the change in pair potential energy calculated from the classical expressions suggests that G ₂ ⁰ seriously underestimates the strength of the Debye interactions in comparison with the London interactions.     

Hydrodynamic equations for attractive particle systems on ℤ

Hydrodynamic properties for a class of nondiffusive particle systems are investigated. The method allows one to study local equilibria for a class of asymmetric zero-range processes, and applies as well to other models, such as asymmetric simple exclusion and misanthropes. Attractiveness is an essential ingredient. The hydrodynamic equations present shock wave phenomena. Preservation of local equilibrium is proven to hold away from the shocks. The problem of breakdown of local ergodicity at the shocks, which was investigated by D. Wick in a particular model, remains open in this more general setup.     

New generalized computations of quasi-planar waveguides characteristics

An efficient hybrid field solution to the general multilayer substrates transmission line problems with full shielded and half open cross-sectional geometry is presented by using the waveguide modes coupling and decoupling procedure in the spectral domain. Modal transverse transmission lines corresponding to the LSE and LSM modes are taken into account so that the Green's elements for the edge conditions can be derived by a simple iterative method. In this paper, we analyze not only the propagation constants and characteristic impedances but also the available transmission power capacity and power distribution of most commonly used structures. Normalized eigenmode power levels characterizing the propagation features are computed.     

Hygrometric Determination of Water Activities and Osmotic and Activity Coefficients of NH4Cl–LiCl–H2O at 25°C

The mixed aqueous electrolyte system of ammonium and lithium chlorides has been studied by the hygrometric method at 25°C. The relative humidities of this system are measured at total molalities from 0.3 to 6 mol-kg^{– 1} for different ionic-strength fractions y of NH₄Cl with y = 0.33, 0.50, and 0.67. The data obtained allow the deduction of new water activities and osmotic coefficients. The experimental results are compared with the predictions of the ECA (extended composed additivity) law proposed in our previous work. The Zdanovskii–Stokes–Robinson (ZSR), the Robinson–Stokes (RS), Reilly–Wood–Robinson (RWR), the Pitzer, and the Lietzke–Stoughton (LS II) models are also compared with our results. Predictions made using these models are, in general, consistent with our results. From these measurements, new Pitzer mixing ionic parameters are determined and used to predict the solute activity coefficients in the mixture for different ionic-strength fractions.     

Mechanism and control of molecular energy flow: a modeling perspective

 Vibrational energy flow in organic molecules occurs by a multiple-time-scale mechanism that can be modeled by a single exponential only in its initial stages. The mechanism is a consequence of the hierarchical structure of the vibrational Hamiltonian, which leads to diffusion of vibrational wavepackets on a manifold with far fewer than the 3N−6 dimensions of the full vibrational state space. The dynamics are controlled by a local density of states, which does not keep increasing with molecular size. In addition, the number of vibrational coordinates severely perturbed during chemical reaction is small, leading to preservation of the hierarchical structure at chemically interesting energies. This regularity opens up the possibility of controlling chemical reactions by controlling the vibrational energy flow. Computationally, laser control of intramolecular vibrational energy redistribution can be modeled by quantum-classical, or by purely quantum-mechanical models of the molecule and control field. Received: 26 July 2002 / Accepted: 30 September 2002 / Published online: 2 December 2002 Electronic Supplementary Material to this paper can be obtained by using the Springer Link server located at http://dx.doi.org/10.1007/s00214-002-0394-2. Acknowledgements. This work was supported by NSF grant CHE 9986670. Correspondence to: M. Gruebele e-mail: gruebele@scs.uiuc.edu     

Determination of mercury in soils and sediments by graphite furnace atomic absorption spectrometry with slurry sampling

A graphite furnace atomic absorption spectrometric procedure for the determination of mercury is presented, in which the samples are suspended in a solution containing hydrofluoric and nitric acids. Silver nitrate (4% m/v) and potassium permanganate (3%) are incorporated, in the order specified, and aliquots are directly introduced into the graphite furnace. A fast heating programme with no conventional pyrolysis step is used. The detection limit for mercury in a 125 mg ml⁻¹ suspension is 0.1 μg g⁻¹. Calibration is performed by using aqueous standards. The reliability of the procedure is proved by analysing certified reference materials.     

Gas–liquid partition coefficients and Henry's law constants of methyl mercaptan in aqueous solutions of Fe(II)–CDTA chelate complex

Utilization of ferric chelate complex of trans-1,2-cyclohexanediaminetetraacetic acid (CDTA) for the oxidative scrubbing of H₂S and CH₃SH in Kraft mill streams can be beneficial from the standpoints of iron protection against precipitation and oxygen-mediated regenerative oxidation of the ferrous chelate CDTA. The physical solubility of methyl mercaptan in CDTA–Fe(III) complex cannot be measured directly because of oxidation of the sulfur-bearing gaseous species with the ferric chelate. Therefore, this investigation was carried out to determine the gas–liquid partition coefficients and Henry's law constants of methyl mercaptan in aqueous iron-free CDTA solutions and non-reacting ferrous chelate solutions (CDTA–Fe(II) complex), using the static headspace method with an estimated accuracy of about 2%. Experiments with aqueous solutions of chelate concentrations varying between 38 and 300 mol m⁻³ were carried out at temperatures between 298 and 333 K and atmospheric pressure. It was shown that the methyl mercaptan solubility decreases with increasing temperature for all systems but was not much influenced, in the studied conditions, by the chelate concentration especially at larger temperatures.     

Analysis of RNA sequence structure maps by exhaustive enumeration I. Neutral networks

Summary Global relations between RNA sequences and secondary structures are understood as mappings from sequence space into shape space. These mappings are investigated by exhaustive folding of allGC andAU sequences with chain lengths up to 30. The computed structural data are evaluated through exhaustive enumeration and used as an exact reference for testing analytical results derived from mathematical models and sampling based on statistical methods. Several new concepts of RNA sequence to secondary structure mappings are investigated, among them that ofneutral networks (being sets of sequences folding into the same structure). Exhaustive enumeration allows to test several previously suggested relations: the number of (minimum free energy) secondary structures as a function of the chain length as well as the frequency distribution of structures at constant chain length (commonly resulting in generalized forms ofZipf's law).

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Analyse der Beziehungen zwischen RNA-Sequenzen und Sekundärstrukturen durch vollständige Faltung, 1. Mitt. Faltung, Neutrale Netzwerke

Zusammenfassung Die globalen Benziehungen zwischen RNA-Sequenzen und Sekundärstrukturen werden als Abbildungen aus einem Raum aller Sequenzen in einen Raum aller Strukturen aufgefaßt. Diese Abbildungen werden durch Falten aller binären Sequenzen desGC-undAU-Alphabets mit Kettenlängen bis zun=30 untersucht. Die berechneten Strukturdaten werden durch vollständiges Abzählen ausgewertet und als eine exakte Referenz zum Überprüfen analytischer Resultate aus mathematischen Modellen sowie zum Testen statistisch erhobener Proben verwendet. Einige neuartige Konzepte zur Beschreibung der Beziehungen zwischen Sequenzen und Strukturen werden eingehend untersucht, unter ihnen der Begriff derneutralen Netzwerke. Ein neutrales Netzwerk besteht aus allen Sequenzen, die eine bestimmte Struktur ausbilden. Vollständiges Abzählen ermöglicht beispielsweise die Bestimmung aller Strukturen minimaler freier Energie in Abhängigkeit von der Kettenlänge ebenso wie die Bestimmung der Häufigkeitsverteilungen der Strukturen bei konstanten Kettenlängen. Die letzteren folgen einer verallgemeinerten FormZipfschen Gesetzes.

     

高温下淀粉的凝胶化作用

凝胶化作用是淀粉及改性产品生产过程中存在的一种现象。淀粉凝胶化作用的结果导致了在其产品中产生了只溶胀但不溶解的颗粒,从而影响了淀粉产品的整体性能。文章初步探讨了淀粉在高温成型过程中凝胶化作用的方式和起因。结果表明,淀粉浆料在高温成型过程中所产生的凝胶团粒是淀粉不完整的凝胶化作用的结果,足量的水分和高温是形成较多的凝胶化淀粉颗粒的原因。