Pressure trickle-bed

M.H. Al-Dahhan and M.P. Dudukovic, Pressure drop and liquid hold-up in high pressure trickle-bed reactors, Chem. Engng. Science, 49 (1994) 5681-5698. 

M.H. Al-Dahhan, F. Larachi, M.P. Dudukovic and A. Laurent, High-pressure trickle-bed reactors a review, Ind. Engng. Chem. Res., 36 (1997) 3292-3314. 

Gas-Liquid Mass Transfer in High Pressure Trickle-Bed Reactors ... 

Abstract—Gas-liquid interfacial areas a and volumetric liquid-side mass-transfer coefficients kLa are experimentally determined in a high pressure trickle-bed reactor up to 3.2 MPa. Fast and slow absorption of carbon dioxide in aqueous and organic diethanolamine solutions are employed as model reactions for the evaluation of a and kLa at high pressure, and various liquid viscosities and packing characteristics. A simple model to estimate a and kLa for the low interaction regime in high pressure trickle-bed reactors is proposed. 

Wartimes et al. [5] by the suggested model are shown in Fig. 2. The experimental conditions and the number of data considered are listed in Table 2. To our knowledge these are all the data available on high pressure trickle-bed reactors and they fall within the 48% error. Statistical tests used to evaluate the goodness of fitting of the correlation are shown inTable 3. 

Gas-liquid interfacial areas, a, and volumetric liquid-side mass transfer coefficients, kLa, are measured in a high pressure trickle-bed reactor. Increase of a and kLa with pressure is explained by the formation of tiny bubbles in the trickling liquid film. By applying Taylor s theory, a model relating the increase in a with the increase in gas hold-up, is developed. The model accounts satisfactorily for the available experimental data. To estimate kLa, contribution due to bubbles in the liquid film has to be added to the corresponding value measured at atmospheric pressure. The mass transfer coefficient from the bubbles to the liquid is calculated as if the bubbles were in a stagnant medium. 

Al-Dahhan, M.H. Highfill, W. Liquid holdup measurement techniques in laboratory high pressure trickle bed reactors. Can. J. Chem. Eng. 1999, 77, 759. 

Al-Dahhan, M.H., Larachi, R, Dudukovic, M.P., and Laurent, A. (1997), High-pressure trickle-bed reactors A review, Industrial Engineering Chemistry Research, 36(8) 3292-3314. 

Al-Dahhan MH, Khadilkar MR, Wu Y, Dudukovic MP. Prediction of pressure drop and liquid holdup in high-pressure trickle-bed reactors. Ind. Eng. Chem. Res. 1998 37 793-798. 

Trickle bed reaction of diol (12) using amine solvents (41) has been found effective for producing PDCHA, and heavy hydrocarbon codistiUation may be used to enhance diamine purification from contaminant monoamines (42). Continuous flow amination of the cycloaUphatic diol in a Hquid ammonia mixed feed gives >90% yields of cycloaUphatic diamine over reduced Co /Ni/Cu catalyst on phosphoric acid-treated alumina at 220°C with to yield a system pressure of 30 MPa (4350 psi) (43). 

Trickle Bed Hydrodesulfurization The first large-scale apph-cation of trickle bed reactors was to the hydrodesulfurization of petroleum oils in 1955. The temperature is elevated to enhance the specific-rate and the pressure is elevated to improve the solubihty of the... 

Downward flow of both fluids imposes no restriction on the gas rate, except that the pressure drop will be high. On the whole, the trickle bed is preferred to the flooded bed. 

Slurry Reactors with Mechanical Agitation The catalyst may be retained in the vessel or it may flow out with the fluid and be separated from the fluid downstream. In comparison with trickle beds, high heat transfer is feasible, and the residence time can be made veiy great. Pressure drop is due to sparger friction and hydrostatic head. Filtering cost is a major item. 

Pressure Drop Some models regard trickle bed flow as analogous to gas/liquia flow in pipe lines. Various flow regimes may exist like those typified in Fig. 23-25/ but in a vertical direction. The two-phase APcl is related to the pressure drops of the individual phases on the assumptions that they are flowing alone. The relation proposed by Larkin et al. (AJChE Journal, 7, 231 [1961]) is APaj 5.0784... 

Several other correlations are cited in the literature, some of which agree with the one quoted here. Pressure drop usually is not a major factor in the design of a trickle bed. 

Trickle-bed operation is the oldest and the most commonly used its development is described in a recent publication (VI). Cobalt-molybdenum catalysts may be used at a temperature of 360°C and a pressure of 57 atm for the hydrogenation of straight-run gas oils. 

Catalytic hydrogenation is typically carried out in slurry reactors, where finely dispersed catalyst particles (<100 (tm) are immersed in a dispersion of gas and liquid. It has, however, been demonstrated that continuous operation is possible, either by using trickle bed [24] or monoHth technologies [37]. Elevated pressures and temperatures are needed to have a high enough reaction rate. On the other hand, too high a temperature impairs the selectivity of the desired product, as has been demonstrated by Kuusisto et al. [23]. An overview of some feasible processes and catalysts is shown in Table 8.1. 

Reactors with a packed bed of catalyst are identical to those for gas-liquid reactions filled with inert packing. Trickle-bed reactors are probably the most commonly used reactors with a fixed bed of catalyst. A draft-tube reactor (loop reactor) can contain a catalytic packing (see Fig. 5.4-9) inside the central tube. Stmctured catalysts similar to structural packings in distillation and absorption columns or in static mixers, which are characterized by a low pressure drop, can also be inserted into the draft tube. Recently, a monolithic reactor (Fig. 5.4-11) has been developed, which is an alternative to the trickle-bed reactor. The monolith catalyst has the shape of a block with straight narrow channels on the walls of which catalytic species are deposited. The already extremely low pressure drop by friction is compensated by gravity forces. Consequently, the pressure in the gas phase is constant over the whole height of the reactor. If needed, the gas can be recirculated internally without the necessity of using an external pump. 

Column reactors are the second most popular reactors in the fine chemistry sector. They are mainly dedicated reactors adjusted for a particular process although in many cases column reactors can easily be adapted for another process. Cocurrently operated bubble (possibly packed) columns with upflow of both phases and trickle-bed reactors with downflow are widely used. The diameter of column reactors varies from tens of centimetres to metres, while their height ranges from two metres up to twenty metres. Larger column reactors also have been designed and operated in bulk chemicals plants. The typical catalyst particle size ranges from 1.5 mm (in trickle-bed reactors) to 10 mm (in countercurrent columns) depending on the particular application. The temperature and pressure are limited only by the material of construction and corrosivity of the reaction mixture. 

In continuous flow experiments, catalyst was packed into a downflow trickle-bed reactor of 30 cc bed volume. Hydrogen was passed slowly over the catalyst at atmospheric pressme and the temperature was slowly raised to the desired reduction/activation temperature and held for at least four hours. After activation, the reactor was cooled to the desired reaction temperature, the pressure was raised, and flow of an aqueous feed of glycerol and sodium hydroxide initiated along with a corresponding amonnt of hydrogen. A large set of reaction conditions was tested. 

A well-substantiated correlation for air-water systems taken from the trickle bed literature (Morsi and Charpentier, 1981) was used for the volumetric mass transfer coefficients in the / , and (Rewap)i terms in the model. The hi term was taken from a correlation of Kirillov et al. (1983), while the liquid hold-up term a, in Eqs. (70), (71), (74), (77), and (79) were estimated from a hold-up model of Specchia and Baldi (1977). All of these correlations require the pressure drop per unit bed length. The correlation of Rao and Drinkenburg (1985) was employed for this purpose. Liquid static hold-up was assumed invariate and a literature value was used. Gas hold-up was obtained by difference using the bed porosity. 

A useful application of the model is to examine the S02 and 02 concentration profiles in the trickle bed. These are shown for the steady-state conditions used by Haure et al. (1989) in Fig. 25. The equilibrium S02 concentration drops through the bed, but the 02 concentration is constant. In Haure s experiments 02 partial pressure is 16 times the S02 partial pressure. At the catalyst particle surface, however, 02 concentration is much smaller and is only about one-third of the S02 concentration. This explains why 02 transport is rate limiting and why experimentally oxidation appears to be zero-order in S02. 

Assuming plug flow of both phases in the trickle bed, a volumetric mass transfer coefficient, kL a, was calculated from the measurements. The same plug flow model was then used to estimate bed depth necessary for 95% S02 removal from the simulated stack gas. Conversion to sulfuric acid was handled in the same way, by calculating an apparent first-order rate constant and then estimating conversion to acid at the bed depth needed for 95% S02 removal. Pressure drop was predicted for this bed depth by multiplying... 

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