Bubble-Column Reactors

If the values of local mean bubble diameter and local gas flux are available, a fluid dynamic model can estimate the required influence of mass transfer and reactions on the fluid dynamics of bubble columns. Fortunately, for most reactions, conversion and selectivity do not depend on details of the inherently unsteady fluid dynamics of bubble column reactors. Despite the complex, unsteady fluid dynamics, conversion and selectivity attain sufficiently constant steady state values in most industrial operations of bubble column reactors. Accurate knowledge of fluid dynamics, which controls the local as well as global mixing, is however, essential to predict reactor performance with a sufficient degree of accuracy. Based on this, Bauer and Eigenberger (1999) proposed a multiscale approach, which is shown schematically in Fig. 9.13. 

FIGURE 9.13 Concept of multiscale modeling of bubble column reactors (from Bauer and Eigenberger, 1999). 

---

External and internal loop air-lifts and bubble column reactors containing a range of coalescing and non-Newtonian fluids, have been studied (52,53). It was shown that there are distinct differences in the characteristics of external and internal loop reactors (54). Overall, in this type of equipment... 

Bubble columns in series have been used to establish the same effective mix of plug-flow and back-mixing behavior required for Hquid-phase oxidation of cyclohexane, as obtained with staged reactors in series. WeU-mixed behavior has been established with both Hquid and air recycle. The choice of one bubble column reactor was motivated by the need to minimize sticky by-products that accumulated on the walls (93). Here, high air rate also increased conversion by eliminating reaction water from the reactor, thus illustrating that the choice of a reactor system need not always be based on compromise, and solutions to production and maintenance problems are complementary. Unlike the Hquid in most bubble columns, Hquid in this reactor was intentionally weU mixed. 

Direct Chlorination of Ethylene. Direct chlorination of ethylene is generally conducted in Hquid EDC in a bubble column reactor. Ethylene and chlorine dissolve in the Hquid phase and combine in a homogeneous catalytic reaction to form EDC. Under typical process conditions, the reaction rate is controlled by mass transfer, with absorption of ethylene as the limiting factor (77). Ferric chloride is a highly selective and efficient catalyst for this reaction, and is widely used commercially (78). Ferric chloride and sodium chloride [7647-14-5] mixtures have also been utilized for the catalyst (79), as have tetrachloroferrate compounds, eg, ammonium tetrachloroferrate [24411-12-9] NH FeCl (80). The reaction most likely proceeds through an electrophilic addition mechanism, in which the catalyst first polarizes chlorine, as shown in equation 5. The polarized chlorine molecule then acts as an electrophilic reagent to attack the double bond of ethylene, thereby faciHtating chlorine addition (eq. 6) ... 

Deckwer, W.D., 1992. Bubble column reactors. John Wiley and Sons. 

Shah, Y.T., Kelkar, B.G., Godbole, S.P. and Deckwer, W.D., 1982. Design parameter estimations for bubble column reactors. American Institute of Chemical Engineers Journal, 28, 353. 

This study investigates the hydrodynamic behaviour of an aimular bubble column reactor with continuous liquid and gas flow using an Eulerian-Eulerian computational fluid dynamics approach. The residence time distribution is completed using a numerical scalar technique which compares favourably to the corresponding experimental data. It is shown that liquid mixing performance and residence time are strong functions of flowrate and direction. 

Many industrial processes which employ bubble column reactors (BCRs) operate on a continuous liquid flow basis. As a result these BCR s are a substantially more complicated than stationary flow systems. The design and operation of these systems is largely proprietary and there is, indeed a strong reliance upon scale up strategies [1]. With the implementation of Computational Fluid Dynamics (CFD), the associated complex flow phenomena may be anal)rzed to obtain a more comprehensive basis for reactor analysis and optimization. This study has examined the hydrodynamic characteristics of an annular 2-phase (liquid-gas) bubble column reactor operating co-and coimter-current (with respect to the gas flow) continuous modes. 

An investigation into the applicability of numerical residence time distribution was carried out on a pilot-scale annular bubble column reactor. Validation of the results was determined experimentally with a good degree of correlation. The liquid phase showed to be heavily dependent on the liquid flow, as expected, but also with the direction of travel. Significantly larger man residence times were observed in the cocurrent flow mode, with the counter-current mode exhibiting more chaimeling within the system, which appears to be contributed to by the gas phase. 

Zahradnik, J. and M. Fialova, The effect of bubbling regime on gas and liquid phase mixing in bubble column reactors. Chemical Engineering Science, 1996. 51(10) p. 2491-2500. 

Two basically different reactor technologies are currently in operation low temperature and high temperature. The former operates at -220 °C and 25-45 bar, employing either a multitubular, fixed bed (i.e. trickle bed) reactor or a slurry bubble column reactor with the catalyst suspended in the liquid hydrocarbon wax product. 

Stirred Tank Reactor (STR) Bubble Column Reactor (BCR) Continuous Reactor (CR) Electrochemical (EC). 

In a properly operated bubble-column reactor, the liquid phase can be considered to be perfectly mixed, i.e. concentrations in the liquid are the same everywhere and correspond to those in the effluent. The gas is supposed to flow like a piston, i.e. the reactor is a plug-flow reactor with respect to the gas. These two assumptions are not entirely true, but within a certain flow regime they are not far from the reality. 

Runaway criteria developed for plug-flow tubular reactors, which are mathematically isomorphic with batch reactors with a constant coolant temperature, are also included in the tables. They can be considered conservative criteria for batch reactors, which can be operated safer due to manipulation of the coolant temperature. Balakotaiah et al. (1995) showed that in practice safe and runaway regions overlap for the three types of reactors for homogeneous reactions (1) batch reactor (BR), and, equivalently, plug-flow reactor (PFR), (2) CSTR, and (3) continuously operated bubble column reactor (BCR). 

Figure 4.11 Stripping in solvent-free medium Synthesis of myristyl myristate from myristyric acid and myristyl alcohol applying a bubble column reactor stripping the reaction water...

The slow water removal is obvious within the synthesis of, for example, myristyl myristate determining the total reaction time. In a stirred-tank reactor it takes 24 h to reach a conversion of 99.6% and in a fixed-bed reactor 14 h. Therefore, a new synthesis platform (Figure 4.11) which also enables conversion of highly viscous polyols and fatty acids from renewable resources to ester-based surfactants was designed. It is used by Evonik on a pilot scale, outperforming conventional methods, such as stirred-tank or fixed-bed reactors. In contrast to the setups introduced before, conversion of >99.6% is already obtained after 5.5 h in the bubble column reactor [44-47]. 

The development of three-phase reactor technologies in the 1970 s saw renewed interest in the synthetic fuel area due to the energy crisis of 1973. Several processes were developed for direct coal liquefaction using both slurry bubble column reactors (Exxon Donor Solvent process and Solvent Refined Coal process) and three-phase fluidized bed reactors (H-Coal process). These processes were again shelved in the early 1980 s due to the low price of petroleum crudes. 

Deckwer, W. D., Bubble Column Reactors, John Wiley Sons, Chichester, England (1992)... 

Kwok, K. H., and Doran, P. M., Kinetic and Stoichiometric Analysis of Hairy Roots in a Segmented Bubble Column Reactor, Biotechnol. Prog., 11 429 (1995)... 

Saxena, S. C., Rosen, M., Smith, D. N., and Ruether, J. A., Mathematical Modeling of Fischer-Tropsch Slurry Bubble Column Reactors, Chem. Eng. Comm., 40 97 (1986)... 

Toseland, B. A., Brown, D. M., Zou, B. S., and Dudukovi..M., Flow Patterns in a Slurry-Bubble-Column Reactor Conditions, Trans. Inst. Chem. Engrs., 73 297 (1995)... 

Gruver, V., Young, R., Engman, J., and Robota, H. J. 2005. The role of accumulated carbon in deactivating cobalt catalysts during FT synthesis in a slurry-bubble-column reactor. Prepr. Pap.-Am. Chem. Soc. Div. Pet. Chem. 50 164—66. 

The most difficult problem to solve in the design of a Fischer-Tropsch reactor is its very high exothermicity combined with a high sensitivity of product selectivity to temperature. On an industrial scale, multitubular and bubble column reactors have been widely accepted for this highly exothermic reaction.6 In case of a fixed bed reactor, it is desirable that the catalyst particles are in the millimeter size range to avoid excessive pressure drops. During Fischer-Tropsch synthesis the catalyst pores are filled with liquid FT products (mainly waxes) that may result in a fundamental decrease of the reaction rate caused by pore diffusion processes. Post et al. showed that for catalyst particle diameters in excess of only about 1 mm, the catalyst activity is seriously limited by intraparticle diffusion in both iron and cobalt catalysts.1... 

A continuous cross-flow filtration process has been utilized to investigate the effectiveness in the separation of nano sized (3-5 nm) iron-based catalyst particles from simulated Fischer-Tropsch (FT) catalyst/wax slurry in a pilot-scale slurry bubble column reactor (SBCR). A prototype stainless steel cross-flow filtration module (nominal pore opening of 0.1 pm) was used. A series of cross-flow filtration experiments were initiated to study the effect of mono-olefins and aliphatic alcohol on the filtration flux and membrane performance. 1-hexadecene and 1-dodecanol were doped into activated iron catalyst slurry (with Polywax 500 and 655 as simulated FT wax) to evaluate the effect of their presence on filtration performance. The 1-hexadecene concentrations were varied from 5 to 25 wt% and 1-dodecanol concentrations were varied from 6 to 17 wt% to simulate a range of FT reactor slurries reported in literature. The addition of 1-dodecanol was found to decrease the permeation rate, while the addition of 1-hexadecene was found to have an insignificant or no effect on the permeation rate. 

Oukaci, R., Singleton, A.H., and Goodwin Jr., J.G. 1999. Comparison of patented Co F-T catalysts using fixed-bed and slurry bubble column reactors. Appl. Catal. A 186 129 14. 

AGC-21 A process for converting natural gas to liquid fuels in three stages generation of syngas in a fluidized bed, Fischer-Tropsch synthesis in a slurry bubble column reactor, and hydrocracking. Piloted in 1997 and proposed for installation in Qatar. 

GTSC [Gas to syncrude] A process for converting natural gas to a synthetic crude oil which may be mixed with natural crude oil and used in conventional oil refineries. Based on F-T technology, but using a proprietary slurry bubble column reactor with a promoted cobalt catalyst. Developed by Syncrude Technology, Pittsburgh, PA, in the 1990s. 

Shetty et al. (1992) studied gas-phase backmixing for the air-water system in bubble-column reactors by measuring RTDs of pulse-injected helium tracer. 

---