Experimental procedure for kinetic studies on egg-shell catalysts: The case of liquid-phase hydrogenation of 1,3-butadiene and n-butenes on commercial Pd catalysts

A study of the liquid-phase hydrogenation of 1,3-butadiene on commercial Pd/Al₂O₃ catalysts of the “egg-shell” type has been performed. Experimental conditions (40°C, 4 atm and high conversion of the di-olefin) were selected in accordance to industrial operating conditions employed for selective hydrogenation of 1,3-butadiene. Three experimental schemes were tested: a slurry reactor, a rotating-basket reactor, and a recirculation system with an external fixed-bed reactor. Significant drawbacks shown by the two former devices were mainly derived from the very high activity and the egg-shell structure of the catalysts. Instead, the recirculation system was found to be an excellent alternative.

Although Pd is present only within a very thin external layer (around 50–250 μm), strong diffusion effects impairing selectivity were observed. Plausible kinetic expressions corresponding to nine series–parallel overall reactions are derived from a mechanistic model. To deal with this network of fast reactions, a rather complex set of computational and predictive tools were employed. A worked out example from several replicates demonstrates the capability of both, experimental and data analysis procedures, for inferring kinetic parameters of the proposed model.     

Attrition resistance of cobalt F–T catalysts for slurry bubble column reactor use

There exists much current interest in the use of supported Co catalysts and slurry bubble column reactors (SBCR) for the conversion of natural gas to higher hydrocarbons via the Fischer–Tropsch (F–T) synthesis. Catalyst attrition resistance is extremely important in the operation of slurry-phase reactor systems because of potential problems with plugging of system filters and/or contamination of the liquid products. This paper addresses the effects of different supports, promoters, and preparation methods on the attrition resistance of Co F–T catalysts for SBCR use.

The calcined supports had attrition resistances (inversely related to % fines <11 μm generated during attrition testing) as follows:

−Al₂O₃>TiO₂(rutile)SiO₂

Loading of Co onto the supports improved the attrition resistances of both alumina and silica significantly. It has essentially no effect on titania. The resulting catalysts had attrition resistances in the order

Co/Al₂O₃>Co/SiO₂>Co/TiO₂(rutile)>Co/TiO₂(anatase)

The addition of small amounts of metal (Ru, Cu) and oxide (La, Zr, K, Cr) promoters had mainly small effects on the attrition resistance of the supported Co catalysts. However, it would appear that the addition of Zr to Co/alumina had a negative impact on its attrition resistance. The different preparation methods used in this study (aqueous impregnation, non-aqueous impregnation, and kneading) did not appear to have a significant effect on catalyst attrition resistance.     

Mass and heat transfer enhancement at the wall of cylindrical agitated vessel by turbulence promoters

Rates of liquid–solid mass transfer at a wall of stirred tank reactor lined with an array of vertical tubes turbulence promoter were studied using the dissolution of copper in acidified dichromate technique. Parameters studied are physical properties of the solution, impeller geometry, impeller rotation speed, cylinder diameter, circumferential distance between the vertical cylinders, and the effect of drag reducing polymers. The presence of vertical cylinders at the reactor wall increased the volumetric mass transfer coefficient compared to the presence of the wall without the cylinders by an amount ranging from 12.5% to 214.5%. The presence of Polyox WSR-301 drag reducing polymer decreased the rate of mass transfer by an amount ranging from 3.5% to 32.26% depending on polymer concentration and impeller rotation speed. All data were correlated by dimensionless mass transfer equations. The importance of the present results in building high space time yield catalytic reactors suitable for conducting diffusion controlled reactions was highlighted, also the possible role of the vertical tube array as a secondary built in heat transfer facility which assists external cooling jacket was noted.     

Pattern formation in models of fixed-bed reactors

This work reviews and compares spatiotemporal patterns in three models of adiabatic fixed catalytic beds for reactions with oscillatory kinetics: homogeneous and heterogeneous models, which are studied using generic first-order kinetics, and a detailed model of CO oxidation in the monolithic reactor. These three models describe reactors with one, two or all three phases (fluid-, solid- and adsorbed-phases), respectively. Pattern selection is based on the oscillatory or bistable nature of the kinetics and on the nature of fronts. The heterogenous and detailed models may exhibit local bistability while the homogeneous model does not admit this property: a simple conversion between the parameters of the homogeneous and heterogeneous models is suggested.

The spatiotemporal patterns in the reactor can be predicted from the sequence of phase planes spanned by the reactor. Stationary or oscillatory front solutions, oscillatory states that sweep the whole surface or excitation fronts may be realized in the homogeneous and heterogeneous models. The detailed model of the converter may exhibit oscillatory motion, which may be periodic or chaotic, in which typically a hot domain enters the reactor exit and moves quickly upstream; the following extinction occurs almost simultaneously due to strong coupling by convection.     

A neutronics analysis of long-life, sectored compact reactor concepts for lunar surface power

Neutronics analysis is performed of low temperature (≤900 K) Sectored Compact Reactor (SCoRe-N_x) concepts for operational lives >20 years. They are cooled with circulating liquid Nak-78. The reactor vessel and the UN fuel pins cladding are made of stainless steel. The power systems with the SCoRe-N_x concepts have no moving parts and employ SiGe thermoelectric elements for converting the reactor’s thermal power to electricity at a load voltage >300 VDC. Separate SiGe elements power the electromagnetic pumps that circulate the liquid NaK-78 in the reactor and 6 pairs of primary and secondary loops. Analysis confirmed that the submerged bare reactors in wet sand and flooded with seawater, in the unlikely event of a postulated launch abort accident, are sufficiently subcritical. Results show that the SCoRe-N₅-S concept is capable of operating for 62 full power years at 200 kW_th, while requiring 75% of the control drums to shutdown the reactor at BOL. With only 50% of the control drums required at BOL to shutdown the reactor, its operational life decreases to 39 full power years.     

Relaxation Process of Thermal Non-Equilibrium in Boiling Two-Phase Flow, (I)

The thermo-hydraulics in a thermal non-equilibrium state, which may appear during a postulated loss-of-coolant accident, is one of phenomena which have never been understood enough. In this paper, accelerating boiling two-phase flow is dealt with which realizes thermal non- equilibrium conditions in a steady state in order to clarify the relaxation process of superheated liquid. The following insight is clarified from the results; Jones' model cannot explain the underpressure and relaxation time unless an empirical constant is changed. Therefore, the effect of interfacial area density on the macroscopic relaxation inception is experimentally investigated by adding artificially bubbles in accelerating boiling two-phase flow in order to offer a fundamental data base for modeling the relaxation process of superheated liquid. It is made clear that the macroscopic relaxation inception can be evaluated by a relationship between the integration of liquid superheating by the travelling time and the initial interfacial area density.     

New Uni-Resonance Approximation Technique for Reaction Rate of Higher Resonances in Activation Detectors

As a high efficiency solid sample analysis technique based on resonance ionization spectroscopy (RIS). Resonant Laser Ablation (RLA) is available. RLA combines Laser Ablation (LA) and RIS simultaneously with a single laser device. We have proposed the new dosimetry technique for a solid sample based on RLA.

We have attempted the detection of ²⁶Al (T _1/2: 7.2×10⁵yr) produced in the high purity Al irradiated by 14MeV neutrons at Fusion Neutronics Source (FNS). Japan Atomic Energy Research Institute. Some interference effects are observed in the trace element detection experiments. These interference effects interrupt the detection of ²⁶Al. In conclusion. it is difficult that ²⁶Al is recognized clearly. We have mainly discussed the origins and elimination methods of these interference effects to detect the trace elements produced by nuclear reactions.     

Experimental Investigation of Heat Transfer in BWR LOCA

Some results of the noise diagnostic research, performed at the Department of Reactor Physics of Chalmers University of Technology are presented. This work has been made in co-operation with the Swedish safety authority and the power plants. The subjects discussed in the paper are: (a) Localization of a channel instability in a BWR; (b) Determination of the axial elevation of a control rod with neural networks in a PWR; (c) Diagnostics of core-barrel vibrations in PWRs. New methods were developed or known methods improved in order to handle these cases and the methods were tested through analysis of measurements. This paper gives a review of this work and its results.     

Sodium Fire Code SFIRE1C for Pool Fire Characteristics

Sodium pool fire code, SOFIRE II, written for the constant value of stoichiometric combustion ratio and heat of reaction is used to compute the buildup of pressure and temperature in a containment. In the SOFIRE II model, for the formation of a mixture of Na₂O and Na₂O₂ in the sodium pool, the input stoichiometric combustion ratio and heat of formation values need to be varied to corresponding values admissible for the mixture. In the present work, the SOFIRE II one-cell model is revised and the present version SFIRE1C (Sodium FIRE 1 Cell model) accounts for the formation of Na₂O in an early stage of the fire and shifts to the formation of Na₂O₂ at a later stage. Thus SFIRE1C computes in a more realistic manner the reaction products which are formed in the pool. The model for sodium oxide aerosol release is also modified in this version, by incorporating a more appropriate aerosol release rate equation. The calculated values using the SFIRE1C one-cell model are compared with sodium pool fire experimental results.     

Dynamic Matrix Control of a Bubble‐Column Reactor for Microbial Synthesis Gas Fermentation

A spatiotemporal metabolic model of a representative syngas bubble‐column reactor was applied to design and evaluate dynamic matrix control (DMC) schemes for regulation of the desired by‐product ethanol and the undesired by‐product acetate. This model was used to develop linear step response models for controller design and also served as the process in closed‐loop simulations. A 2 × 2 DMC scheme with manipulation of the liquid and gas feed flows to the column provided a superior performance to proportional integral (PI) control due to slow process dynamics combining the multivariable and constrained nature of the control problem. Ethanol concentration control for large disturbances was further improved by adding the flow of a pure hydrogen stream as a third manipulated variable. The advantages of DMC for syngas bubble‐column reactor control are demonstrated and a design strategy for future industrial applications is provided.