Transformation of Thermal Regimes of Exothermic Reaction in the Case of Harmonic Perturbations of the Velocity and Temperature of the Reagent at the Entrance of the Adiabatic Reactor

The stationary-state behaviour of the simple autocatalytic models: quadratic autocatalysis A + B → 2B; rate = k 1 ab ; cubic autocatalysis A + 2B → 3B; rate = k 1 ab 2 , in a well stirred, open system (isothermal c. s. t. r.) is determined via singularity theory methods. These methods allow all of the possible patterns for the dependence of the stationary-state extent of conversion x on the residence time Da (i. e. the x —Da bifurcation diagrams) to be identified and located. The cubic rate law has a cusp singularity, separating diagrams with a unique dependence of x on Da from those which display a simple S-shaped hysterisis loop with multiple stationary states. This behaviour is qualitatively similar to that shown by a simple exothermic reaction in an adiabatic c. s. t. r. (i. e. the two systems are contact equivalent). If the autocatalyst is not infinitely stable but instead undergoes a simple decay B → C; rate = k 2 b , a wider range of bifurcation diagrams is possible, with isolas or mushroom patterns. These arise as the system is ‘unfolded’ from its winged cusp singularity by varying parameters such as the catalyst lifetime and inflow concentration. It is shown that these are also the only patterns possible for a generalized order of autocatalysis, i. e. for a rate proportional to ab m , with m taking any value greater than one, integral or non-integral. The ranges of the above parameters over which the different responses are found are also given analytically for the general m . These parameters cannot, however, give a complete unfolding, so certain additional bifurcation diagrams that are found for the exothermic reaction in a non-isothermal, non-adiabatic reactor (which also has a winged-cusp singularity) are not found in the autocatalytic system.


Author(s):  
D.M. Vanderwalker

There is a fundamental interest in electrochemical fusion of deuterium in palladium and titanium since its supposed discovery by Fleischmann and Pons. Their calorimetric experiments reveal that a large quantity of heat is released by Pd after hours in a cell, suggesting fusion occurs. They cannot explain fusion by force arguments, nor can it be an exothermic reaction on the formation of deuterides because a smaller quantity of heat is released. This study examines reactions of deuterium in titanium.Both iodide titanium and 99% pure titanium samples were encapsulated in vacuum tubes, annealed for 2h at 800 °C. The Ti foils were charged with deuterium in a D2SO4 D2O solution at a potential of .45V with respect to a calomel reference junction. Samples were ion beam thinned for transmission electron microscopy. The TEM was performed on the JEOL 200CX.The structure of D charged titanium is α-Ti with hexagonal and fee deuterides.


1986 ◽  
Vol 51 (6) ◽  
pp. 1259-1267
Author(s):  
Josef Horák ◽  
Petr Beránek

A simulation apparatus for the experimental study of the methods of control of batch reactors is devised. In this apparatus, the production of heat by an exothermic reaction is replaced by electric heating controlled by a computer in a closed loop; the reactor is cooled with an external cooler whose dynamic properties can be varied while keeping the heat exchange area constant. The effect of the cooler geometry on its dynamic properties is investigated and the effect of the cooler inertia on the stability and safety of the on-off temperature control in the unstable pseudostationary state is examined.


1984 ◽  
Vol 49 (11) ◽  
pp. 2566-2578 ◽  
Author(s):  
Josef Horák ◽  
Petr Beránek ◽  
Dagmar Maršálková

An algorithm is set up and tested for the temperature control of a batch reactor consisting in jump changes in the inlet temperature of entering coolant. This temperature is so chosen that its difference from the temperature of the reaction mixture is near the highest difference at which the stable pseudostationary state of the system still exists. For the prediction of the new coolant inlet temperature, a zero-order reaction model is used with an adaptive parameter estimated from the experimentally established value of the maximum of the reaction mixture overheating at the previous coolant temperature.


1982 ◽  
Vol 47 (2) ◽  
pp. 454-464 ◽  
Author(s):  
František Jiráček ◽  
Josef Horák

The effect has been studied of the inertia of the cooling system on the reliability of control of the temperature of the reaction mixture. The study has been made using a mathematical model of the batch reactor with an exothermic reaction. The temperature has been controlled by a two-level controller opening and closing the flow of the coolant. The aim of the control has been to maintain a constant value of the degree of utilization of the cooling capacity of the reactor. The instantaneous value of the degree of utilization has been assessed from the ratio of times for which the cooling system is idle to the time of operation. The reliability of control has been studied for variable activity of the catalyst.


1982 ◽  
Vol 47 (2) ◽  
pp. 446-453
Author(s):  
Josef Horák ◽  
František Jiráček ◽  
Libuše Ježová

A possibility has been tested in the paper of the feed back control of temperature of the reaction mixture in a batch reactor with an exothermic reaction through the variable area of the cooling surface. The measurement were carried out in a laboratory reactor with a retractable cooler which was being immersed into the reaction mixture. The speed of motion of the cooler was sufficiently high permitting the process of immersion to be regarded as practically instantaneous. The aim of the control was to stabilize the set point temperature of the reaction mixture by a two-point controler. In dependence on the rate of response of the system to a change of the section variable either the ideal relay or the relay with hysteresis control algorithmus were used. The results of measurements showed that with the aid of a retractable cooler the temperature could be controlled safely even in those cases, in which the control by the variable flow rate of the coolant was unfeasible. The verification was carried out in the open-loop instable operating point of the reactor.


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