Microkinetic modeling as a tool in catalyst discovery

We propose a new approach for catalyst development that combines different scientific disciplines: experimental design, surface science, reaction kinetics and simulations with the objective of accelerating catalyst development. In this paper we present a study of the possibilities of using small data sets in microkinetic modeling, and studies of the required precision of temperature measurement.     

Mechanism and kinetics of the free radical ring-opening polymerization of cyclic allylic sulfide lactones

The polymerization of 7-, 8- and 11-membered lactones, 6-methylene-1,4-oxathiepan-7-one, 3-methylene-1,5-oxathiocan-2-one and 3-methylene-1-oxa-5-thiacycloundecan-2-one in benzene at 70, 40–70 and 40–65 °C, respectively, is presented. All polymerizations proceeded with complete ring-opening up to approximately 25% conversion, where insoluble polymer was formed. Evidence is given attributing polymer double bond loss to crosslinking, although redistribution of the molecular weights via addition to polymer double bonds followed by β-fragmentation also appears to occur for polymerizations of the 8- and 11-membered lactones. Michael adducts of lactones with 2-methyl-2-propanethiol were prepared as models for chain-transfer products of hydrogen abstraction by carbon-centred radicals. Polymerization rates were found to increase marginally with ring size. Arrhenius parameters obtained for the polymerizations of the 8- and 11-membered lactones indicated that the addition step was more important than fragmentation in determining the rate of propagation.     

The Sephadex story

The environment and the circumstances leading to the Sephadex group of products for gel filtration (SEC, size exclusion chromatography) are described. The importance of Porath's and the author's experience from zone electrophoresis is stressed. To be able to get high resolution the technique for packing columns was of decisive importance for electrophoresis. It paved the way for the observation of the separation properties of dextran gels. The synthesis of dextran-based gels at AB Pharmacia and the development of varieties of them for varying applications are described together with the project leading to their marketing in 1959. The work of the author on gel filtration is summarized. The story is based on publication and memory. Aids to the latter have been laboratory notebooks and other documents still in the possession of the author.     

A full-scale experimental set-up for assessing the energy performance of radiant wall and active chilled beam for cooling buildings

Full-scale experiments under both steady-state and dynamic conditions have been performed to compare the energy performance of a radiant wall and an active chilled beam. From these experiments, it has been observed that the radiant wall is a more secure and efficient way of removing heat from the test room than the active chilled beam. The energy saving, which can be estimated to around 10%, is due to increased ventilation losses. The asymmetry between air and radiant temperature, the air temperature gradient and the possible short-circuit between inlet and outlet play an equally important role in decreasing the cooling need of the radiant wall compared to the active chilled beam. It has also been observed that the type and repartition of heat load have an influence on the cooling demand. Regarding the comfort level, both terminals met the general requirements, except at high solar heat gains: overheating has been observed due to the absence of solar shading and the limited cooling capacity of the terminals. No local discomfort has been observed although some segments of the thermal manikin were slightly colder.     

Gravitational drainage of compressible organic materials

A model was developed to simulate drainage of compressible particle suspensions, and study how cake compression and volumetric load influence the process. The input parameters were settling velocity, cake resistance and compressibility. These parameters were found using a new experimental method. Dextran‐MnO₂ particle suspensions were drained as these resemble organic waste slurries with respect to settling and compressibility. It was demonstrated that cake compressibility must be taken into account to obtain adequate simulations. This implies that pressurized filtration resistances cannot be used for drainage simulations. In the filtration step, a distinct increase of dry matter from top to bottom of the cake was observed. During the subsequent consolidation, the cake compressed and a uniform dry matter profile was found. The final dry matter content of the cake increased with feed concentration and volumetric load. The drainage time increased proportionally with feed concentration and, more importantly, proportionally with squared volumetric load. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

Experimental investigation of an industrial scale black liquor gasifier. 1. The effect of reactor operation parameters on product gas composition

A novel technology to mitigate the climate changes and improve energy security is Pressurized Entrained flow High Temperature Black Liquor Gasification (PEHT-BLG) in combination with an efficient fuel synthesis using the resulting syngas. In order to optimise the technology for use in a pulp and paper mill based biorefinery, it is of great importance to understand how the operational parameters of the gasifier affect the product gas composition. The present paper is based on experiments where gas samples were withdrawn from the hot part of a 3 MW entrained flow pressurized black liquor gasifier of semi industrial scale using a high temperature gas sampling system. Specifically, the influence of process conditions on product gas composition (CO₂, CO, H₂, CH₄, H₂S, and COS) were examined by systematically varying the operational parameters: system pressure, oxygen to black liquor equivalence ratio, black liquor flow rate to pressure ratio and black liquor pre-heat temperature. Due to the harsh environment inside the gasification reactor, gas sampling is a challenging task. However, for the purpose of the current study, a specially designed high temperature gas sampling system was successfully developed and used. The results, obtained from two separate experimental campaigns, show that all of the investigated operational parameters have a significant influence on the product gas composition and present valuable information about to the process characteristics.     

Low‐Temperature Superionic Conductivity in Strained Yttria‐Stabilized Zirconia

Very high lateral ionic conductivities in epitaxial cubic yttria‐stabilized zirconia (YSZ) synthesized on single‐crystal SrTiO₃ and MgO substrates by reactive direct current magnetron sputtering are reported. Superionic conductivities (i.e., ionic conductivities of the order ～1 Ω^?1cm^?1) are observed at 500 °C for 58‐nm‐thick films on MgO. The results indicate a superposition of two parallel contributions – one due to bulk conductivity and one attributable to conduction along the film–substrate interface. Interfacial effects dominate the conductivity at low temperatures (<350 °C), showing more than three orders of magnitude enhancement compared to bulk YSZ. At higher temperatures, a more bulk‐like conductivity is observed. The films have a negligible grain‐boundary network, thus ruling out grain boundaries as a pathway for ionic conduction. The observed enhancement in lateral ionic conductivity is caused by a combination of misfit dislocation density and elastic strain in the interface. These very high ionic conductivities in the temperature range 150–500 °C are of great fundamental importance but may also be technologically relevant for low‐temperature applications.     

Two Classes of Cosine-Modulated IIR/IIR and IIR/FIR NPR Filter Banks

This paper introduces two classes of cosine-modulated causal and stable filter banks (FBs) with near perfect reconstruction (NPR) and low implementation complexity. Both classes have the same infinite-length impulse response (IIR) analysis FB but different synthesis FBs utilizing IIR and finite-length impulse response (FIR) filters, respectively. The two classes are preferable for different types of specifications. The IIR/FIR FBs are preferred if small phase errors relative to the magnitude error are desired, and vice versa. The paper provides systematic design procedures so that PR can be approximated as closely as desired. It is demonstrated through several examples that the proposed FB classes, depending on the specification, can have a lower implementation complexity compared to existing FIR and IIR cosine-modulated FBs (CMFBs). The price to pay for the reduced complexity is generally an increased delay. Furthermore, two additional attractive features of the proposed FBs are that they are asymmetric in the sense that one of the analysis and synthesis banks has a lower computational complexity compared to the other, which can be beneficial in some applications, and that the number of distinct coefficients is small, which facilitates the design of FBs with large numbers of channels.