Production of n-propyl acetate by reactive distillation : experimental and theoretical study

First steps of the development of a catalytic reactive distillation process for the production of n-propyl acetate based on experiments and simulations are proposed. The kinetics for homogeneously (sulphuric acid) and heterogeneously (Amberlyst 15) catalysed reaction were investigated and the constants for a pseudo-homogeneous model are presented. Pilot plant experiments were performed using a homogeneous strong acid catalyst in a packed column. A top-column decanter is used to withdraw the aqueous phase and to reflux the organic phase. Simulation results are in good agreement with experimental data. Thermodynamics nonidealities are taken into account using VLE and LLE NRTL interaction parameters. Alcohol conversion and n-propyl acetate purity may be dramatically increased just by adding to the pilot plant a stripping section in an additional column: six different configurations are identified to achieve such a production. The startup is studied in order to determine the best strategy to achieve steady-state conditions. The strong influence of the composition of the initial charging in the decanter can be seen and an initial charging of the two-phase top product leads to the fastest startup

Capturing the Competing Influence of Thermal and Mechanical Loads on the Strain of Turbine Blade Coatings via High Energy X-rays

This paper presents findings of synchrotron diffraction measurements on tubular specimens with a thermal barrier coating (TBC) system applied by electron beam physical vapor deposition (EB-PVD), having a thermally grown oxide (TGO) layer due to aging in hot air. The diffraction measurements were in situ while applying a thermal cycle with high temperature holds at 1000 °C and varying internal air cooling mass flow and mechanical load. It was observed that, during high temperature holds at 1000 °C, the TGO strain approached zero if no mechanical load or internal cooling was applied. When applying a mechanical load, the TGO in-plane strain (e22) changed to tensile and the out of plane TGO strain (e11) became compressive. The addition of internal cooling induced a thermal gradient, yielding a competing effect, driving the e22 strain to compressive and e11 strain to tensile. Quantifying TGO strain variations in response to competing factors will provide a path to controlling the TGO strain, and further improving the lifetime assessment and durability design strategies for TBC systems

Evaluating deformation behavior of a TBC-System during thermal gradient mechanical fatigue by means of high energy X-ray diffraction

Applications of TBC-systems involve complex thermal mechanical loading pattern including transient thermal gradients across the coated system, which result in multiaxial stresses and stress gradients affecting the damage behavior. In an ongoing research, starting more than 10 years ago, the authors developed laboratory test facilities for evaluating the damage behavior of TBC-systems for gas turbine blades in aeroengines under realistic thermal mechanical loading conditions [1]. Fatigue tests involving thermal gradients have been conducted and damage behavior in dependence of load pattern and pre heat treatment has been intensively investigated on TBC-systems comprising a partially yttria stabilized zirconia (YSZ) topcoat and a MCrAlY bond coat both applied by electron physical vapor deposition (EB-PVD) onto nickel based super alloys serving as substrate [2]. Numerical analyses by means of FE-calculations did provide hypotheses explaining the observed damage behavior [3], but even though the results are plausible they did depend on reasonable assumptions on materials properties since reliable data on the properties of the thin coating layers are still lacking, especially for high temperatures. High energy X-ray diffraction can provide the requested information since it is possible to achieve information on the local deformation processes in each layer with high spatial resolution, and short acquisition times allow for in situ investigation of time dependent deformation processes. A new test facility based on concepts after [1] for cyclic thermal loading of tubular specimens and applying a controlled thermal gradient across the coated specimen’s wall has been developed for implementation into an electro-mechanical test machine at the advanced photon source (APS) at Argonne National Laboratory. A precision positioning rig allows for exact µm-positioning of the entire test machine with respect to the focused X-ray beam, and X-ray diffraction patterns were taken using a 2D detector, giving accurate 360° lattice parameter data [4]. Tests have been performed with varying thermal and mechanical load schemata intending to determine material properties from the respective strain response. The beam energy was 65 keV, and throughout all experiments the beam scanned through the coating layers with a window and step size of 30 µm. Strain data were acquired in plane parallel to the specimen’s length axis and out of plane. Results of the strain data evaluation will be presented and discussed. Exemplary results are: - Elastic properties of the YSZ showed a gradient across the coating thickness reflecting the microstructure gradient of the YSZ resulting from the EB-PVD process. - The YSZ strain was – below the deposition temperature - in plane compressive and out of plane tensile, which is a consequence of (i) the higher thermal expansion coefficient of YSZ with respect to the substrate and (ii) the cylindrical specimen geometry with the YSZ at the outer surface. [1] M. Bartsch, G. Marci, K. Mull, C. Sick, Adv. Eng. Mater. (1999), 1(2), 127–9 [2] M. Bartsch, B. Baufeld, S. Dalkilic, L. Chernova, M. Heinzelmann, Int. J. Fatigue (2008) 30, 211–8 [3] M. T. Hernandez, A. M. Karlsson, M. Bartsch, Surf. Coat. Technol. (2009) 203, 3549–58 [4] S.F. Siddiqui, K. Knipe, A. Manero, C. Meid, J. Wischek, J. Okasinski, J. Almer, A.M. Karlsson, M. Bartsch, S. Raghavan, Review of Scientific Instruments (2013) 84, 08390

Preliminary Design of Reactive Distillation Columns

A procedure that combines feasibility analysis, synthesis and design of reactive distillation columns is introduced. The main interest of this methodology lies on a progressive introduction of the process complexity. From minimal information concerning the physicochemical properties of the system, three steps lead to the design of the unit and the specification of its operating conditions. Most of the methodology exploits and enriches approaches found in the literature. Each step is described and our contribution is underlined. Its application is currently limited to equilibrium reactive systems where degree of freedom is equal to 2 or less than 2. This methodology which provides a reliable initialization point for the optimization of the process has been applied with success to different synthesis. The production of methyl-tert-butyl-ether (MTBE) and methyl acetate are presented as examples

Anisotropic lattice expansion determined during flash sintering of BiFeO3 by in-situ energy-dispersive X-ray diffraction

BiFeO3 has a Curie temperature (TC) of 825 °C, making it difficult to sinter using conventional methods while maintaining the purity of the material, as unavoidably secondary phases appear at temperatures above Tc. Flash sintering is a relatively new technique that saves time and energy compared to other sintering methods. BiFeO3 was flash sintered at 500 °C to achieve 90% densification. In-situ energy dispersive X-ray diffraction (EDXRD) revealed that the material did not undergo any phase transformation, having been sintered well below the TC. Interestingly, anisotropic lattice expansion in the material was observed when the sample was exposed to the electric field.U.S. Office of Naval Research (ONR) N00014-10-1- 042, N00014-17-1-2087, Sub 4104-78982U.S. Department of Energy DE-AC02-06CH1135

Strain response of thermal barrier coatings captured under extreme engine environments through synchrotron X-ray diffraction

The mechanical behaviour of thermal barrier coatings in operation holds the key to under-standing durability of jet engine turbine blades. Here we report the results from experiments that monitor strains in the layers of a coating subjected to thermal gradients and mechanical loads representing extreme engine environments. Hollow cylindrical specimens, with electron beam physical vapour deposited coatings, were tested with internal cooling and external heating under various controlled conditions. High-energy synchrotron X-ray measurements captured the in situ strain response through the depth of each layer, revealing the link between these conditions and the evolution of local strains. Results of this study demonstrate that variations in these conditions create corresponding trends in depth-resolved strains with the largest effects displayed at or near the interface with the bond coat. With larger temperature drops across the coating, significant strain gradients are seen, which can contribute to failure modes occurring within the layer adjacent to the interface