Economic background of chemical integration - a case study

In this second paper on chemical integration the author refines the usual relation of total costs equals fixed plus variable costs further by splitting the fixed costs into core, true fixed and capacity related fixed costs. A set of equations for a simplified definition of the returns on investment for an entire chemically integrated complex and individual production units in the manufacturing plant is given, from which the individual contributions of diversification and of chemical integration can be deduced. An example taken from practice is given

The role of pellet thermal stability in reactor design for heterogeneously catalysed chemical reactions

For exothermic fluid-phase reactions, a reactor which is cooled at the wall can exhibit multiplicity or parametric sensitivity. Moreover, for heterogeneously catalysed exothermic fluid-phase reactions, each of the catalytically active pellets in the reactor can exhibit multiplicity. Both forms of multiplicity can lead to thermal instability and as such have to be taken into account in reactor design. Here the effect of both instabilities is quantified. To this end, simple first-order kinetics are assumed, and intraparticle resistances and reactor and particle dynamics are not considered. A one-dimensional model, consisting of microscale mass and heat balances, is chosen to describe the reactor. It is assumed that the fluid inlet temperature equals the coolant temperature. The pellet scale model is a combined mass and heat balance for the pellet and it assumes that the Chilton¿Colburn analogy holds. For its incorporation in the reactor model it is assumed that for every individual pellet heat removal to neighbouring pellets via the mutual contact spots is negligible as compared to the heat transferred to the surrounding fluid. Consequently every pellets is isolated from its neighbours. In the thermally most critical region, i.e. the hot-spot region, reactor stability is determined by three parameter groups: a dimensionless adiabatic temperature rise, an Arrhenius number or dimensionless activation temperature and the ratio of the number of heat transfer units to the number of reaction units. For pellet multiplicity, a fourth parameter group becomes significant in addition: the ratio of the reaction rate to the pellet mass transfer rate. This number depends on the pellet size. A general recipe is given which enables us to determine whether or not pellet thermal instability can become important in reactor operation. For the situation where it is significant, generalized diagrams are presented indicating which pellet sizes problems must be expected due to pellet multiplicity

Safe design and operation of fluidized-bed reactors: Choice between reactor models

For three different catalytic fluidized bed reactor models, two models presented by Werther and a model presented by van Deemter, the region of safe and unique operation for a chosen reaction system was investigated. Three reaction systems were used: the oxidation of benzene to maleic anhydride, the oxidation of naphthalene to phthalic anhydride, and the oxidation of ethylene to ethylene oxide. Predictions of the optimal yield, the operating temperature and the conversion were also subjects of our study. It appeared that for reactions carried out in a fluidized bed operating under conditions of good fluidization all models predicted the same region of safe and unique operation. For a well-designed fluidized bed only the constraint of uniqueness is affected by the reactor model chosen. Predictions of the yield, conversion and operating temperature appeared to fit slightly less well. But still a good indication can be obtained from any of the models since the deviation in the results was less then a few percent for all three reaction systems. The strongest deviations between the models occurs in the region of gas loads only slightly higher than the minimum fluidization velocity. As the heat transfer characteristics are bad at low gas loads this region is unsuitable for highly exothermic reactions where large amounts of heat have to be removed by the coolant. In the region of good heat transfer with gas loads at least several times higher than the minimum the three models predict the same results. For this reason we finally recommed the use of simple models

Safe design of cooled tubular reactors for exothermic multiple reactions: Multiple-reaction networks

The model of the pseudo-homogeneous, one-dimensional cooled tubular reactor is applied to a multiple-reaction network. It is demonstrated for a network which consists of two parallel and two consecutive reactions. Three criteria are developed to obtain an integral yield which does not deviate more than a chosen fraction from the maximum yield that can be obtained in an isothermal reactor. The criteria enable us to choose relevant design and operating conditions for the safe execution of a reaction network in a tubular reactor. The method is illustrated for the production of maleic anhydride by air oxidation of benzene

A model for a countercurrent gas—solid—solid trickle flow reactor for equilibrium reactions. The methanol synthesis

The theoretical background for a novel, countercurrent gas—solid—solid trickle flow reactor for equilibrium gas reactions is presented. A one-dimensional, steady-state reactor model is developed. The influence of the various process parameters on the reactor performance is discussed. The physical and chemical data used apply to the case of low-pressure methanol synthesis from CO and H2 with an amorphous silica—alumina as the product adsorbent. Complete reactant conversion is attainable in a single-pass operation, so that a recycle loop for the non-converted reactants is superfluous.\ud \ud In the following article the installation and experiments for which this theory was developed will be described

The influence of the reactor pressure on the hydrodynamics in a cocurrent gas-liquid trickle-bed reactor

The influence of the reactor pressure on the liquid hold-up in the trickle-flow regime and on the transition between trickle-flow and pulse-flow has been investigated in a trickle-flow column operating up to 6.0 MPa with water, and nitrogen or helium as the gas phase.\ud \ud The effect of the gas velocity and gas density on the hold-up has been explained by means of the modified Galileo number Ga{1+ΔP/(ρlgL)}. At the transition between trickle- and pulse-flow the liquid hold-up is - for a given value of the superficial gas velocity - nearly the same at each gas density. Therefore, at elevated gas densities the transition occurs at higher liquid throughputs. From a comparison of the experiments with water-nitrogen and water-helium it has been concluded that at an equal gas density - for given values of vl and vg - the hydrodynamic behaviour is the same

Safe design of cooled tubular reactors for exothermic, multiple reactions; parallel reactions—II: The design and operation of an ethylene oxide reactor

In part I a model and criteria have been developed for the safe design and operation of cooled tubular reactors for multiple reactions of the parallel type. In this Part II the model is extended to parallel reactions with an arbitrary stoichiometry. The results are applied to the industrial process of the ethylene oxidation with pure oxygen. It is shown that the criteria derived in part I lead to useful guidelines for the design and operation of an ethylene oxide reactor

Safe design of cooled tubular reactors for exothermic, multiple reactions; parallel reactions—I: Development of criteria

Previously reported design criteria for cooled tubular reactors are based on the prevention of reactor temperature run away and were developed for single reactions only. In this paper it is argued that such criteri a should be based on the reactor selectivity, from which eventually a maximum allowable temperature can be derived. To this end and for the pseudo-homogeneous, one dimensional model of a cooled tubular reactor in which two parallel, irreversible first order exothermic reactions are carried out, two criteria are developed for the safe design and operation of the reactor. The criteria enable us to choose tube diameters and operating conditions, which are safe in view of the derived selectivity and of possible runaway as well. The method outlined can be used in the initial design stage and requires kinetic information on both the desired and the undesired reaction

Incorporation of statistical distribution of particle properties in chemical reactor design and operation: the cooled tubular reactor

Pellet heat and mass transfer coefficients inside packed beds do not have definite deterministic values, but are stochastic quantities with a certain distribution. Here, a method is presented to incorporate the stochastic distribution of pellet properties in reactor design and operation models. The theory presented is illustrated with a number of examples. It is shown that pellet-scale statistics have an impact on cooled tubular reactor design and operation. Cooled tubular reactor design is determined to a large extent by the objective that run away inside the reactor tubes be avoided. We obtain the highest conversion if conditions in the tubes are such that the pellet and reactor run-away mechanisms are in balance. This determines an optimum amount of particles on a diameter inside a cooled tubular reactor. This optimum is influenced by the distribution of transport coefficients over the pellets. Because of the pellet-scale statistical behaviour, a certain percentage of the tubes will always suffer run away if we operate close to the run-away region. If we have certain fluctuations in the coolant temperature, reactor pressure or load, any of these can damage a certain amount of tubes. As these fluctuations occur often, the performance of the cooled tubular reactor will deteriorate with time. The effects, as shown in this study, may cause an increase in inherent reactor instability. Therefore, if these effects are taken into account, a more conservative reactor design emerges