Gas-Liquid-Particle Processes

The area of interest covered by this paper is limited to processes in which chemical conversion occurs, as in the processes noted above. Gas-liquid-particle processes in which a gaseous phase is created by the chemical reaction between a liquid and a solid (for example, the production of acetylene by the reaction between water and carbide) are excluded from the review. Also excluded are physical separation processes, such as flotation by gas-liquid-particle operation. Gas absorption in packed beds, another gas-liquid-particle operation, is not treated explicitly, although certain results for this operation must necessarily be referred to. 

The gas-liquid-particle processes considered in this paper may be grouped into two major classes. In the first, components of all three phases participate in the chemical reaction. In the second, components of only the gaseous and the solid phases participate in the chemical reaction, the liquid phase functioning as a chemically inactive medium for the transfer of momentum, heat, and mass. Important examples of these two types of processes are described, respectively, in Sections II,A and II,B. 

Processes with Chemical Reaction between Gas, Liquid, 

A number of industrially important processes are carried out by gas-liquid-particle operation, as illustrated by the following four examples. 

Because of the high pyrolysis temperature, the C4-fraction contains quantities of vinyl acetylene and ethyl acetylene, the removal of which prior to the recovery of butadiene is necessary in certain cases, particularly if butadiene of low acetylene content is desired. Similar considerations apply to effractions obtained by the dehydrogenation of n-butane and n-butenes. 

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The catalytic hydrogenation of fatty oils, the desulfurization of liquid petroleum fractions by catalytic hydrogenation, Fischer-Tropsch-type synthesis in slurry reactors, and the manufacture of calcium bisulfite acid are familiar examples of this type of process, for which the term gas-liquid-particle process will be used in the following. 

A gas-liquid-particle process termed cold hydrogenation has been developed for this purpose. The hydrogenation is carried out in fixed-bed operation, the liquefied hydrocarbon feed trickling downwards in a hydrogen atmosphere over the solid catalyst, which may be a noble metal catalyst on an inert carrier. Typical process conditions are a temperature of 10°-20°C and a pressure of 2.5-7 atm gauge. The hourly throughput is as high as 20-kg hydrocarbon feed per liter of catalyst volume. 

Sorbitol is produced by a gas-liquid-particle process in which a solution of glucose is hydrogenated in the presence of a solid catalyst consisting of nickel on diatomaceous earth carrier (B6). 

A number of important gas-liquid-particle processes fall outside the categories of Sections II,A and II,B. The review of gas-liquid-particle operations in the following sections is written with particular regard to applications in processes of the types already referred to, but may also be of some significance with regard to other types. A few examples of such processes will be briefly mentioned below. 

Gas absorption in packed beds may be described as a gas-liquid-particle process involving reacting gas and liquid phases and an inert particle phase, the latter functioning mainly as a momentum-transfer medium. 

Processes in which two phases react and result in the formation of a third form an important group of gas-liquid-particle processes. In the production of acetylene, a gaseous phase is formed by reaction between a liquid and a particle phase water and carbide. In the production of gas hydrates in desalination processes, a particle phase is formed by reaction between a liquid and a gaseous phase sea water and, for example, propane. In the melting of gas-hydrate or ice crystals a liquid phase is formed when gaseous and particle phases are brought in contact. 

Trickle-flow operation is widely used for large-scale gas-liquid-particle processes, as noted in Section II. 

In this section, a number of important elementary process steps into which a gas-liquid-particle process can be subdivided will be mentioned. Several theoretical models proposed in the literature will be discussed, and a slightly more comprehensive model will be described. 

The most complex type of gas-liquid-particle process is one in which gaseous components participate in a heterogeneous catalytic reaction, with the formation of gaseous products. The following elementary steps must occur in a process of this type ... 

The process steps mentioned are not of importance in all gas-liquid-particle processes. In particular, the last step does not occur in processes in which a liquid product is formed by reaction between gaseous and liquid reactants, as may be the case, for example, in the catalytic hydrogenation of liquid petroleum fractions. 

A more general model of gas-liquid-particle processes than those that have so far appeared in the literature would, it seems, be of considerable interest as a basis for comparing the reaction-engineering properties of the several types of gas-liquid-particle operations, and as a means for analyzing operations with finite liquid flow (for example, trickle-flow operation and gas-liquid fluidization). 

Trickle-flow operation is probably the most widely used operation for large-scale industrial gas-liquid-particle processes. It has been the subject of a large number of investigations, and is, as a result, relatively well described. 

Further work regarding the axial dispersion of gas in irrigated packed beds seems needed, and it may be noted, with particular regard to gas-liquid-particle processes, that no results have been reported for beds of cylindrically or spherically shaped packing materials. 

Hydrogenation of unsaturated fats and fatty oils is one of the oldest heterogeneous catalytic processes of industrial significance, and is carried out exclusively by gas-liquid-particle operation, the vaporization of the fats being impracticable. Stirred-slurry operation is the normal mode of operation, the suspended catalyst being finely divided by Raney nickel (B2). 

The production of alcohols by the catalytic hydrogenation of carboxylic acids in gas-liquid-particle operation has been described. The process may be based on fixed-bed or on slurry-bed operation. It may be used, for example, for the production of hexane-1,6-diol by the reduction of an aqueous solution of adipic acid, and for the production of a mixture of hexane-1,6-diol, pentane-1,5-diol, and butane-1,4-diol by the reduction of a reaction mixture resulting from cyclohexane oxidation (CIO). 

Epoxides such as ethylene oxide and higher olefin oxides may be produced by the catalytic oxidation of olefins in gas-liquid-particle operations of the slurry type (S7). The finely divided catalyst (for example, silver oxide on silica gel carrier) is suspended in a chemically inactive liquid, such as dibutyl-phthalate. The liquid functions as a heat sink and a heat-transfer medium, as in the three-phase Fischer-Tropsch processes. It is claimed that the process, because of the superior heat-transfer properties of the slurry reactor, may be operated at high olefin concentrations in the gaseous process stream without loss with respect to yield and selectivity, and that propylene oxide and higher... 

As a final example of the application of gas-liquid-particle operation to a process involving a gaseous reactant and a solid catalyst, the possibility of polymerizing ethylene in, for example, a slurry operation employing a metal or metal oxide catalyst can be cited. It has been suggested that the good control of reaction conditions obtained in a slurry-type operation may be of importance in the production of certain types of polyethylene (Rl). 

It may finally be pointed out that certain separation processes in addition to packed-bed gas absorption are gas-liquid-particle operations. Examples are flotation and a special type of fluidized crystallization process (Z2). 

Gas-liquid-particle operations are of a comparatively complicated physical nature Three phases are present, the flow patterns are extremely complex, and the number of elementary process steps may be quite large. Exact mathematical models of the fluid flow and the mass and heat transport in these operations probably cannot be developed at the present time. Descriptions of these systems will be based upon simplified concepts. 

It seems probable that a fruitful approach to a simplified, general description of gas-liquid-particle operation can be based upon the film (or boundary-resistance) theory of transport processes in combination with theories of backmixing or axial diffusion. Most previously described models of gas-liquid-particle operation are of this type, and practically all experimental data reported in the literature are correlated in terms of such conventional chemical engineering concepts. In view of the so far rather limited success of more advanced concepts (such as those based on turbulence theory) for even the description of single-phase and two-phase chemical engineering systems, it appears unlikely that they should, in the near future, become of great practical importance in the description of the considerably more complex three-phase systems that are the subject of the present review. 

The two models commonly used for the analysis of processes in which axial mixing is of importance are (1) the series of perfectly mixed stages and (2) the axial-dispersion model. The latter, which will be used in the following, is based on the assumption that a diffusion process in the flow direction is superimposed upon the net flow. This model has been widely used for the analysis of single-phase flow systems, and its use for a continuous phase in a two-phase system appears justified. For a dispersed phase (for example, a bubble phase) in a two-phase system, as discussed by Miyauchi and Vermeulen, the model is applicable if all of the dispersed phase at a given level in a column is at the same concentration. Such will be the case if the bubbles coalesce and break up rapidly. However, the model is probably a useful approximation even if this condition is not fulfilled. It is assumed in the following that the model is applicable for a continuous as well as for a dispersed phase in gas-liquid-particle operations. 

Discussed in the following section will be such data and other information regarding the elementary process steps in gas-liquid-particle operations as have appeared in the chemical engineering literature. 

The use of even the very simple models for isothermal operation described in Section IV,B requires a substantial amount of information regarding the elementary iate processes occurring in a gas-liquid-particle operation, as discussed in Section IV,A. While a considerable amount of information of this kind is available in the chemical engineering literature, it is widely scattered. It will be attempted in this section to present a comprehensive review of this information in order to facilitate its use. It is hoped that this review will be of value not only to those chemical engineers directly interested in the practical applications of gas-liquid-particle operations, but also, by pointing to the several areas characterized by very limited information, to those interested in research in this field. 

The absorption of reactants (or desorption of products) in trickle-bed operation is a process step identical to that occurring in a packed-bed absorption process unaccompanied by chemical reaction in the liquid phase. The information on mass-transfer rates in such systems that is available in standard texts (N2, S6) is applicable to calculations regarding trickle beds. This information will not be reviewed in this paper, but it should be noted that it has been obtained almost exclusively for the more efficient types of packing material usually employed in absorption columns, such as rings, saddles, and spirals, and that there is an apparent lack of similar information for the particles of the shapes normally used in gas-liquid-particle operations, such as spheres and cylinders. 

Practical separation techniques for hquid particles in gases are discussed. Since gas-borne particulates include both hquid and sohd particles, many devices used for dry-dust collection (discussed in Sec. 17 under Gas-Sohds Separation ) can be adapted to liquid-particle separation. Also, the basic subject of particle mechanics is covered in Sec. 6. Separation of liquid particulates is frequently desirable in chemical processes such as in countercurrent-stage contacting because hquid entrainment with the gas partially reduces true countercurrency. Separation before entering another process step may be needed to prevent corrosion, to prevent yield loss, or to prevent equipment damage or malfunc tion. Separation before the atmospheric release of gases may be necessaiy to prevent environmental problems and for regula-toiy compliance. 

The secondary source of fine particles in the atmosphere is gas-to-particle conversion processes, considered to be the more important source of particles contributing to atmospheric haze. In gas-to-particle conversion, gaseous molecules become transformed to liquid or solid particles. This phase transformation can occur by three processes absortion, nucleation, and condensation. Absorption is the process by which a gas goes into solution in a liquid phase. Absorption of a specific gas is dependent on the solubility of the gas in a particular liquid, e.g., SO2 in liquid H2O droplets. Nucleation and condensation are terms associated with aerosol dynamics. 

The effect of physical processes on reactor performance is more complex than for two-phase systems because both gas-liquid and liquid-solid interphase transport effects may be coupled with the intrinsic rate. The most common types of three-phase reactors are the slurry and trickle-bed reactors. These have found wide applications in the petroleum industry. A slurry reactor is a multi-phase flow reactor in which the reactant gas is bubbled through a solution containing solid catalyst particles. The reactor may operate continuously as a steady flow system with respect to both gas and liquid phases. Alternatively, a fixed charge of liquid is initially added to the stirred vessel, and the gas is continuously added such that the reactor is batch with respect to the liquid phase. This method is used in some hydrogenation reactions such as hydrogenation of oils in a slurry of nickel catalyst particles. Figure 4-15 shows a slurry-type reactor used for polymerization of ethylene in a sluiTy of solid catalyst particles in a solvent of cyclohexane. 

A very important parr of the gas-deatimg process is the removal of the collected particles from the cleaning system. This should be as controlled as possible in order to avoid particle reenrrainmenr to the gas flow. This can be accomplished in the case of liquid particles such as acid fume or tar or oil smoke. olid particles are normally removed by periodic rapping of discharge and collection electrodes. Solid particles can also be removed with the aid of water, as is done in wet electrostatic precipitators. 

Each stage of particle formation is controlled variously by the type of reactor, i.e. gas-liquid contacting apparatus. Gas-liquid mass transfer phenomena determine the level of solute supersaturation and its spatial distribution in the liquid phase the counterpart role in liquid-liquid reaction systems may be played by micromixing phenomena. The agglomeration and subsequent ageing processes are likely to be affected by the flow dynamics such as motion of the suspension of solids and the fluid shear stress distribution. Thus, the choice of reactor is of substantial importance for the tailoring of product quality as well as for production efficiency. 

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