The chain conformation of solution-crystallized polyethylene has previously been confirmed by infra-red spectroscopy, using the CD2 bending bandshape for samples with a minority of the deuterated species1–3. The method of calculating the i.r. band profile from molecular conformational models is now developed to give a more accurate representation of doublet splittings and to include the singlet component. The CH2 bending profile is calculated for samples with a deuterated matrix, and the good agreement with experimental data indicates that the same molecular model is applicable for samples with the deuterated polymer as either guest or matrix, for identical crystallization conditions. This result implies that isotopic fractionation is unimportant under these conditions. 相似文献
A stochastic search technique, simulated annealing (SA), is used to optimize the operation of multiple reservoirs. Seminal application of annealing technique in general to multi-period, multiple-reservoir systems, along with problem representation and selection of different parameter values used in the annealing algorithm for specific cases is discussed. The search technique is improved with the help of heuristic rules, problem-specific information and concepts from the field of evolutionary algorithms. The technique is tested for application to a benchmark problem of four-reservoir system previously solved using a linear programming formulation and its ability to replicate the global optimum solution is examined. The technique is also applied to a system of four hydropower generating reservoirs in Manitoba, Canada, to derive optimal operating rules. A limited version of this problem is solved using a mixed integer nonlinear programming and results are compared with those obtained using SA. A better objective function value is obtained using simulated annealing than the value from a mixed integer non-linear programming model developed for the same problem. Results obtained from these applications suggest that simulated annealing can be used for obtaining near-optimal solutions for multi-period reservoir operation problems that are computationally intractable. 相似文献
A promising catalytic system for the low temperature oxidation of methane to a methanol derivative has been investigated under both batch and semi-continuous operation in two different reactor types. The system comprises of a bimetallic palladium and copper(II) chloride catalyst contained in a trifluoroacetic acid (TFA) and an aqueous phase. Methane, oxygen and a co-reductant carbon monoxide constitute the gas phase. Typical operating conditions were a temperature of 85 °C and a pressure of 83 bar.
The yields of the methyl trifluoroacetate product observed in this present work were less than those obtained in other batch autoclave works, which employed only 4 ml of liquid phase, compared with 50 ml in this study. Furthermore, an encouraging initial product formation rate of ca. 40 mol/m3 h, quickly decreased after the first hour, and came to an apparent end after only 2 h. This observation had not been reported previously.
Work performed in a semi-continuous porous tube reactor (300 ml of re-circulating liquid phase) also showed the same reaction characteristics as in the batch reactor. Thus, the deteriorating product formation rate cannot be attributed to gaseous reactant depletion (batch operation). The results suggest problems associated with catalyst instabilities, e.g. with the previously elucidated Wacker chemistry. 相似文献