Interpretation of hydrogenation kinetics of spent oil distillate from u.v. spectroscopy

Hydrotreatment of spent oil distillate was carried out on a commercial Ni-Mo-alumina catalyst in the temperature range 260–340 °C, with a liquid hourly space velocity (LHSV) of 0.7–2.0 h^?1, pressure of 4.5 MPa and $\text{H}{}_2\text{oil}$ ratio of 300 NL L^?1 (normal litre of H₂ per litre of feedstock). U.v. spectra of hydrogenated and original spent oil distillates (measured in normal hexane) gave a band with a maximum at 230 nm. The change in absorbance at three selected wavelengths for original oil distillate and hydrotreated oil at different operating conditions was taken as a guide for the determination of hydrogenation reaction rates (including partial saturation of aromatics and sulphur compound hydrogenolysis). The rate constants of hydrogenation reactions (k) using a second-order equation and a model of two parallel first-order reactions (k₁ and k₂) were calculated. Finally, the apparent activation energy (E_a), enthalpy of activation ($\text{ΔH}{}^1$) and entropy ($\text{ΔS}{}^1$) were calculated based on the values of k, k₁, and k₂. The calculated values of E_a based on k, k₁ and k₂ were 81.479, 71.188 and 62.882 kJ mol^?1, respectively. The values of $\text{ΔH}{}^1$ based on the same rate constants were 76.670, 66.564 and 58.433 kJ mol^?1, while the values of $\text{ΔS}{}^1$ were ?117.150, ?133.779 and ?150.823 J mol^?1 K^?1, respectively.     

Castor oil dehydration kinetics

The dehydration reaction kinetics of castor oil was investigated with sodium bisulfate-sodium bisulfite mixture (SB-SB) or p-toluenesulfonic acid as catalyst. Reactions were carried out at 210, 220, and 230°C, and a kinetic model was determined for each case. The reactions with SB-SB catalyst at 210 and 220°C and with p-toluenesulfonic acid at 210°C followed second-order kinetics. A first-order rate equation showed the best fit to the experimental data for the reaction with SB-SB at 230°C. p-Toluenesulfonic acid-catalyzed reactions at 220 and 230°C were also first-order reactions. Additionally, some mathematical equations were derived between iodine value, refractive index, viscosity, and reaction time.     

Kinetics of the Initial Stage of Sintering from Shrinkage Data: Simultaneous Determination of Activation Energy and Kinetic Model from a Single Nonisothermal Experiment

A new method for the kinetic analysis of the initial stage of sintering for constant-heating-rate data has been proposed. Unlike all of the methods previously reported in the literature, this new method proposed here allows the simultaneous determination of the activation energy and the kinetic model from a single dilatometric curve recorded under a linear-heating-rate program. The proposed method has been tested with simulated sintering curves and experimental results have been obtained for the sintering of a rutile sample.     

Determination of Binder Decomposition Kinetics for Specifying Heating Parameters in Binder Burnout Cycles

The decomposition kinetics of poly(vinyl butyral) binder from barium titanate multilayer ceramic capacitors with platinum metal electrodes were analyzed by thermogravimetric analysis as a function of the heating rate. The activation energy and pre-exponential factor for the decomposition kinetics were determined from two types of integral equations, from the Redhead method, and from the variation in heating rate method. The accuracy of the kinetic parameters determined from these methods was then evaluated for describing the observed rate of binder decomposition. Although the individual models yielded very different kinetic parameters, all were capable of describing the experimental data within ±15% accuracy. The kinetic parameters were then used in a coupled transport and kinetic model for describing the buildup of pressure within the ceramic green body as a function of the heating cycle. A methodology based on calculus of variations was also developed to predict the minimum duration for the binder burnout cycle.     

Theoretical Models for Binder Burnout

The kinetics of binder burnout, from a ceramic green body, are considered for the case of an "unzipping" binder which decomposes to produce a volatile monomer. The process is considered to fail if the concentration of monomer in the green body exceeds that in equilibrium with vapor at 1 atm (≅10⁵ Pa), when an internal bubble would be expected to form. Steady-state diffusional calculations and computer simulations explore the size and temperature dependence of the process and are in agreement. The model suggests that it is not feasible to burn out a large flat piece greater than about 3 mm thick, without going to very long times of burnout. The kinetics are significantly improved if porosity develops in the piece during the early stages of decomposition, as opposed to the retreat of the binder into the piece on a uniform front.     

Studies on crystallization behaviors and crystal morphology of polyamide 66/clay nanocomposites

X‐ray diffraction methods, DSC thermal analysis, and polarized light microscopy (PLM) were used to investigate the structural changes of nylon 66/clay nanocomposites. PA 66/clay nanocomposites were prepared by the method of melt intercalation. The results indicate that the addition of the intercalated organo‐montmorillonite (OMMT) can induce generation of the β‐form crystal of PA 66 and substantially affect the arrangement of molecules in the α‐form crystal, although the crystallinity scarcely changes. Also, the DSC results indicate that the addition of OMMT in the PA 66 matrix leads to increases of crystallization temperatures and the full width at half maximum (FWHM) of the exothermic peaks. Moreover, the viscosity factor is the main influence on FWHM of the exothermic peaks of PA 66/clay nanocomposites. The results of nonisothermal crystallization kinetics show that OMMT has the effect of heterogeneous nucleation and leads to the decrease of the size of the spherocrystal. The heterogeneous nucleation effects of OMMTs influence the mechanism of crystallization and the growth mode of PA 66 crystals. PLM photographs verify that the size of spherocrystal is decreased and visually confirm the theory of crystallization kinetics. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 756–763, 2005     

常温脱氯剂与HCl气体反应动力学的研究

在固定床反应器中研究了自制的铁系常温脱氯剂与HCl气体的反应动力学,导出了计算脱氯剂氯容的动力学方程q=0.309[(exp(0.036t))/(exp(0.036t)+exp(61.9Z)-1)]×100%.根据该方程,可以计算各个时刻、床层不同深度处脱氯剂的氯容,从而判断脱氯剂的性能及其使用寿命.     

Hydrosilylation and dehydrocondensation reactions of methylhydridesiloxane to acrylic and methacrylic acids

The hydrosilylation of α,ω‐bis(trimethylsiloxy) methylhydridesiloxane (degree of polymerization ≈ 53) with acrylic and methacrylic acid with various ratios of the initial compounds, in the presence of platinum hydrochloric acid, has been investigated. In the presence of platinum hydrochloric acid, competitive dehydrocondensation reactions take place with the formation of various oligomers with various chemical links. In the later stages of the reaction, three‐dimensional systems have been obtained. During dehydrocondensation, the reaction order, reaction rate constants, and activation energy have been determined. The structures of the synthesized oligomers have been determined with IR and NMR spectroscopy data. Gel permeation chromatography, differential scanning calorimetry, and X‐ray analyses of the synthesized oligomers have been carried out. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3243–3252, 2007     

中药降香对酪氨酸酶激活作用的动力学研究

酪氨酸酶是生物合成黑素的主要酶。降香有促进酪氨酸酶活性的作用。通过对中药降香的水提取液和乙醇提取液促进酪氨酸酶活性作用的观察研究及降香提高酪氨酸酶活性的动力学观察研究，得到Lineweaver-Burk曲线、动力学回归方程及米氏常数Km值。为研究中药有效成分激活黑素细胞的机理奠定了基础。     

Continuous emulsion polymerization of vinyl acetate. II Operation in a single Couette–Taylor vortex flow reactor using sodium lauryl sulfate as emulsifier

Continuous emulsion polymerizations of vinyl acetate were conducted at 50°C in a single continuous Couette–Taylor vortex flow reactor (CCTVFR) using sodium lauryl sulfate as emulsifier and potassium persulfate as initiator. The polymerization can be carried out very smoothly and stably, but the steady‐state monomer conversion attained in a CCTVFR is not as high as that in a plug flow reactor (PFR), but only slightly higher than that in a continuous stirred tank reactor (CSTR), even if the Taylor number is adjusted to an optimum value. Also, the effects of operating variables, such as the emulsifier, initiator, and monomer concentrations in the feed and the mean residence time on the kinetic behaviors were almost the same as those observed in a CSTR. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2755–2762, 2002