Air Pollution Control Absorption

Absorption ; Gas absorption ; Gas washing

Gas absorption is a unit operation by which a gas mixture is contacted with a liquid for the purposes of preferentially dissolving one or more components from the gas in the liquid and to provide a solution of these in the liquid. For example: the gas from by-product coke ovens is washed with water to remove ammonia and again with oil to remove benzene and toluene vapours; offensive (objectionable) hydrogen sulphide is removed from such a gas or from natural hydrocarbon gases by washing with various alkaline solutions in which it is absorbed; valuable solvent carried by a gas stream may be recovered for reuse by washing the gas with an appropriate solvent for the vapours. Such operations require mass transfer of a substance from the gas stream to the liquid one. When mass transfer occurs in the opposite direction, i.e. from the liquid to the gas, the operation is called desorption, or stripping. For example, the benzene and toluene are removed from the absorption oil mentioned above by contacting the liquid solution with steam, whereupon the vapours enter the gas stream and are carried away, and the absorption oil may be used again. The principle of both absorption and desorption are basically the same, and we may study both operations at the same time. Ordinarily, these operations are used only for solute recovery and solute removal. Separation of solutes from each other requires the fractional techniques of distillation. The rate at which a gaseous constituent will dissolve in an absorbent liquid depends upon the departure from equilibrium which is maintained, and therefore it is necessary to consider the equilibrium characteristics of gas-liquid systems. A very brief discussion willl be given here. Equilibrium Suppose a fixed closed container partly filled with water and above the water with a gaseous mixture of ammonia and air. The whole system is maintained at constant temperature and pressure. Since ammonia is very soluble in water, some ammonia molecules will instantly transfer from the gas into the liquid, crossing the interfacial surface separating the two phases. A portion of ammonia molecules escapes back into the gas, at a rate proportional to their concentration (number) in the liquid. As more ammonia enters the liquid, its concentration is increasing within the liquid, consequently the rate at which ammonia returns to the gas increases also, until eventually the rate at which it enters the liquid exactly will be equal to that at which it leaves. At the same time, through the mechanism of diffusion, the concentrations throughout each phase become uniform. A dynamic equilibrium now exists, and while ammonia molecules continue to transfer back and forth one phase to the other, the net transfer falls zero. The concentrations within each phase no longer change. To the observer who can not see the individual molecules the diffusion has apparently stopped. If now we inject additional ammonia into the container, increasing the concentration of ammonia in the gas phase, a new set of equilibrium will eventually be established, with higher concentrations in each phase than were earlier. In this manner we can obtain the complete relationship between the equilibrium concentrations in both phases. If the ammonia is designated as substance A, the equilibrium concentrations in the gas and liquid, y*A and xA mole fractions, respectively, give the equilibrium-distribution curve of the type shown in Figure 1. Figure 1.
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This curve does not depend on the amounts of water and air that we start with and is influenced only by the conditions, such as temperature and pressure, imposed upon the threecomponent system. It is important to note that at equilibrium the concentrations of the two phases are not equal (remark: but chemical potential of the ammonia is the same in both phases, consequently it is equality of chemical potentials, not concentrations, which cause the net transfer of solute to stop). The curve of Figure 1 does not show all the equilibrium concentrations existing within the system. For example, the water will partially vaporize into the gas phase, the components of the air will also dissolve to a small extent in the liquid, and equilibrium concentrations for these substances will also be established. We do not consider these equilibria at present, since they have minor importance to the present discussion. Obviously also, other concentration units than mole fractions may be used to describe the equilibria. Generally speaking, whenever a substance is distributed between two insoluble phases, a dynamic equilibrium of this type can be established. Of course, the various equilibria are peculiar to the particular system investigated. For example, replacement of the water in the example considered above with another liquid such as benzene, or with a solid adsorbent such as activated carbon, or replacement of the ammonia with another solute such as e.g. sulphur dioxide will each result in new curves not at all related to the first. Two-component system: If a quantity of single gas and a relatively non-volatile liquid are brought to equilibrium in the manner described earlier, the resulting concentration of dissolved gas in the liquid is said to be the gas solubility (the solubility of the gas) at the prevailing temperature and pressure. At fixed temperature, the solubility concentration will increase with partial pressure of the component in the manner, for example, of curve A in Figure 2 which shows the solubility of ammonia in water at 30 C. Figure 2. Different liquids and gases yield separate solubility curves, which must ordinarily be determined experimentally for each system If the equilibrium partial pressure of a gas at a given liquid concentration is high, as in the case of curve B (sulphur dioxide for 10 C), the gas is said to be relatively insoluble in the liquid, while if it is low, as for curve C (hydrogen chloride for 10 C), the solubility is said to be high. The solubility of any gas is influenced by the temperature and by the total pressure. In most cases, the solubility of a gas decreases with increasing temperature. As an example, curve A for ammonia in water at 10 C lies below the corresponding curve for 30 C. At the boiling point of the solvent, provided that its vapour pressure is less than that of the gas or vapour solute, the gas solubility will be zero. Multicomponent system: If a mixture of gases is brought into contact with a liquid, under certain conditions the equilibrium concentrations of each gas will be independent of the others, provided, however, that the equilibrium is described in terms of the partial pressures in the gas mixture. If all but one of the components of the gas are substantially insoluble, their concentrations in the liquid will be so small that they can not influence the solubility of the relatively soluble component. For example, curve A on Figure 2 will also describe the solubility of ammonia in water when the ammonia is diluted with air, since air is so insoluble in water, provided that the ordinate of the plot is considered as the partial pressure of ammonia in the gas mixture. Ideal and non-ideal liquid solutions: When the liquid phase may be considered ideal, we may compute the equilibrium partial pressure of a gas from the solution without experimental results. In reality there are no ideal solutions, and actual mixtures only approach ideal solutions as a limit. Ideality would require that the molecules of the constituent be similar in size, structure, and chemical nature. Perhaps the isomers of organic compounds
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approach this condition mostly. Practically however, many solutions are so closely ideal that for engineering applications they may be considered ideal. When the gas mixture with an ideal liquid solution also follows the ideal-gas law, the partial pressure p*A of a solute gas A in equilibrium with the liquid is equal to the product of its vapour pressure PA at the same temperature and its mole fraction in the solution xA. This is Raoults law: p* = PA x A A The nature of the solvent liquid does not enter into consideration as it establishes an ideal solution, and it follows that the solubility of a particular gas in ideal solution in any solvent is always the same. For not ideal liquid solutions Raoults law will give highly incorrect results. Line D in Figure 2, for example, is the calculated partial pressure for ammonia in equilibrium with water solutions at 10 C and it clearly does not represent the experimental data. On the other hand, the straight line E is seen to represent the 10 C ammonia-water data very well up to mole fractions of 0.06 in the liquid. The equation of such a line is the Henrys law which relates the partial pressure of the solute A in gas phase and the mole fraction of the dissolved solute A in liquid phase solvent B: p* = H A x A A where HA is the Henrys law coefficient expressed in kPa (or bar) per mole-fraction solute in liquid. For dilute concentrations of many gases and over a fairly wide concentration range for some gases it may be applicable with different values of H for each gas and also applicable for the gases shown in the figure. This equation is quite useful when it can be applied, but it should be checked experimentally to determine the accuracy with which it can be used. If Henrys law holds, the solubility is defined by stating the value of the constant H along with the temperature and the solute partial pressure for which it is employed. Failure to follow Henrys law over wide concentration ranges may be the results of chemical interaction with the liquid or electrolytic dissociation, as is the case with ammonia-water, or non-ideality in the gas phase. For quite a number of gases, Henrys law holds very well when the partial pressure of the solute is less than 100 kPa (1 atm). For partial pressures of the solute gas greater than 100 kPa, H is seldom independent of the partial pressure of the solute gas, and a given value of H can be used over a narrow range of partial pressures. The less soluble gases, such as nitrogen or oxygen in water, can be expected to follow the Henrys law up to equilibrium partial pressure of 1 bar, and gases of the vapour type (which are below their critical temperature) will generally follow the law up to pressures of approximately 50 percent of the saturation value at the prevailing temperature, provided no chemical action occurs in the liquid. There is a strong nonlinear variation of Henrys law coefficient with temperature. Investigation is recommended before considering temperature extrapolations of Henrys-law data. In any case H must be determined experimentally. Additional data and information on the applicability of Henrys-law constants can be found in literature. High values of H indicate very poor solubility of the pollutant in the liquid or, in other words, low absorption capacity of the liquid for the pollutant. On the other hand, a very low value for H indicates very effective solution of the pollutant in the liquid, that is, the absorption capacity of the liquid for the pollutant is very high. To absorb a certain amount of pollutant, a much larger amount of liquid is required with a high value of H than the case of a system with a small value of H (see Figure 2.). The use of Henrys law is illustrated by the following examples. Example 1. It is desired to calculate how much ammonia can be dissolved in water from a gas mixture when the total pressure is 101325 Pa (1 atm), the mole fraction of the ammonia in the gas phase is 0.03, and the temperature is 20 C. The value of the Henrys coefficient is 3105
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Pa (3 bar). To apply the Henrys law the partial pressure of the ammonia should be calculated which by using the Dalton law is as follows: p * = p* 3 = py * = py * 3 = 101325 0.03 = 3040 Pa A NH A NH and according to Henrys law, the mole fraction of ammonia in the liquid phase: p* 3 3040 NH x NH 3 = = = 1.013 10 2 H NH 3 300000 Example 2. It is desired to calculate how much sulphur dioxide can be dissolved in water from a gas mixture when the total pressure is 101325 Pa (1 atm), the mole fraction of the sulphur in the gas phase is 0.03, and the temperature is 20 C. The value of the Henrys coefficient is 3106 Pa (30 bar). The partial pressure of the sulphur dioxide is the same as earlier (since the mole fraction in gas phase and total pressure are the same): p* 2 = py * 2 = 101325 0.03 = 3040 Pa SO SO and according to Henrys law, the mole fraction of sulphur dioxide in the liquid phase: p* 2 3040 SO x SO 2 = = = 1.013 10 3 H SO 2 3000000 To evaluate the results we calculate how much ammonia and sulphur dioxide can be solved in 1 kg of solution (the mass fraction of the pollutant in the liquid). The relation between the two types of the concentrations is shown by the next equation: mk M k nk M k xk k = = = m k + m w M k n k + M w n w M k x k + M w (1 x k ) since x k + x ww = 1 Substituting the mole fractions calculated above the solubility of ammonia and sulphur dioxide is as follows: NH3 = 0.009576

SO 2 = 0.002473 or 9576 as well as 2473 ppm (parts per million weight). To make a comparison we calculate how much oxygen can be solved in water when the partial pressure of the oxygen in the gas mixture is about 21000 Pa (as in the atmospheric air) and the value of the Henrys coefficient is about 39108 Pa (39000 bar). The following result is received: y O2 = 0.21
x O2 = 5.38 10 6

O2 = 0.00000957
which is 9.57 ppm.

Evaluation of the results The results show that the solubility of ammonia and sulphur dioxide is much larger than the solubility of oxygen although the concentration of the first two components is much less than the oxygen concentration in the gas mixture. t is a general situation for most of the pollutants to be removed from waste gases or flue gases before emitted into the atmosphere. Similar results may be calculated for nitrogen. Therefore the natural components of the air (oxygen and nitrogen) have much less solubility than the pollutants and this gives means for solving the air pollution control. Physical absorption was assumed for the calculation but
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chemical absorption may be also used when the reagent concentration in the absorbent determines the absorptive capacity which may be much larger than for physical absorption (see later). Chemical Equilibrium Conditions: In a chemical absorption process the pollutant A is transferred from the gas phase to the liquid phase where a chemical reaction takes place. It means that the pollutant A and reactant B produce a new compound as follows: A + BB PP where k is stoichiometric coefficient for the components and the arrow indicates forward and backward (a reversible) reactions. The rate of the chemical reaction is: r = k 1 c A c BB k 2 c P P where k1 and k2 is the rate constant for the forward and the backward reactions and ck is the mole concentration of the components. The chemical equilibrium constant is defined as follows: k cP K = 1 = P k 2 c A c BB For the chemical absorption process it is of great advantage when the chemical conversion is product oriented, that is: the forward reaction is much faster than the backward. This will be the case for high values of k1 and K. In this case the reaction is very fast and proceeds in the liquid phase very close to the interface. For practical applications this type of chemical absorption is the most advantageous, since for environmental protection the concentrations of the pollutants are generally very low and physical absorption will never be able to reduce the pollutant concentration very close to zero (or to zero), but it is often desirable. Such conditions can be only met by chemical absorption. Hence, chemical absorption is of great importance in the field of air pollution control.

Selection of solvent for absorption If the principal purpose of the absorption operation is to produce a specific solution, as in the manufacture of hydrochloric acid, for example, the solvent is specified by the nature of the product (it is water in hydrochloric acid production). If the principal purpose is to remove some constituent from the gas mixture (as for solving environmental problems that is to remove some pollutant from the air), some choice is frequently possible. When choice is possible, liquids with high solubilities for the solute are preferred as a high solubility reduces the amount of solvent to be circulated. Water is, of course, the cheapest and most plentiful solvent, but the following properties are important for considerations: Gas solubility: The gas solubility should be high, thus increasing the rate of absorption and decreasing the quantity of solvent required. Generally solvents of a chemical nature similar to that of the solute to be absorbed will provide good solubility. Thus hydrocarbon oils, and not water, are used to remove benzene from coke-oven gas. For cases where the solutions formed are ideal, the solubility of the gas is the same in terms of mole fractions for all solvents. But it is greater in terms of weight fractions for solvents of low molecular weight, and smaller weights of such solvents, as measured in kilograms, need to be used. Chemical reaction of solvent with the solute will frequently result in very high gas solubility, but if the solvent is to be recovered for reuse, the reaction must be reversible. For example, hydrogen sulphide may be removed from gas mixture using (mono- or di-) ethanolamine solutions since the sulphide is readily absorbed at low temperatures and easily stripped at high temperatures. Caustic soda (NaOH) absorbs hydrogen sulphide or calcium
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hydroxide (Ca(OH)2) absorbs sulphur dioxide excellently but will not release it in a stripping operation. Volatility: The solvent should have a low vapour pressure since the gas leaving the absorption unit is ordinarily saturated with the solvent and therefore much may be lost by using solvent of high volatility. Solvent loss may be costly and may present environmental contamination problems. If necessary, a second, less volatile liquid may be used to recover the evaporated portion of the first. This is sometimes done, for example, in the case of hydrocarbon absorbers, where a relatively volatile solvent oil is used in the principal portion of the absorber because of the superior solubility characteristics and the volatilised solvent is recovered from the gas by a non-volatile oil. Similarly, hydrogen sulphide may be absorbed by water solution of sodium phenolate, but the desulphurized gas is further washed with water to recover the evaporated phenol. Corrosiveness: The materials of construction required for the equipment should not be unusual (rarely used) or expensive. Cost: The solvent should be inexpensive, so that losses are not costly, and should be readily available. Viscosity: Low viscosity is preferred for reasons of rapid absorption rates, improving flooding characteristics in absorption towers, low pressure drops on pumping, and good heattransfer characteristics (if necessary). Miscellaneous: The solvent if possible should be non-toxic, non-flammable and chemically stable and should have a low freezing point (the equipment are generally operated outside). To sum up: the solvent should have high gas solubility, should be relatively nonvolatile, inexpensive, non-corrosive, chemically stable, non-viscous, non-foaming, and preferably non-flammable. Generally low-cost solvents should be chosen over more expensive ones of higher solubility or lower volatility. Water is generally used for gases fairly soluble in water, oils for light hydrocarbons, and special chemical solvents for acid gases such as carbon dioxide, sulphur dioxide and hydrogen sulphide. Sometimes a reversible chemical reaction will result in a very high solubility and a minimum solvent rate. Data on actual systems are desirable when chemical reactions are involved. Examples of gas-liquid combinations for air pollution control, widely used in industry, are given in Table 1. Table 1.

Material balances
Remark: the concentration-difference driving forces are existing at one position in the equipment used to contact the immiscible phases. In the case of a steady-state process, because of the transfer of the solute from one phase to the other one, the concentration within each phase changes as the phase moves through the equipment. These changes produce changes in the driving forces, which can be followed with the help of material balances.

The basic expressions for material balances and their graphical interpretations will be presented for countercurrent flow (a similar method may be used for cocurrent flow). Figure 3 shows a countercurrent tower which may be either a packed or spray tower, a plate tower (filled with bubble-cap or any other trays), or may have any internal constructions to bring about liquid-gas contact. Figure 3. Steady-state process is assumed. It means that concentrations at any position in the tower remain constant with passing time. This requires continuous, invariable flow of all phases into and out of the apparatus, a continuous and constant flow conditions within the apparatus, constant concentrations of the feed streams, and unchanging conditions of temperatures and pressures. In the figure the apparatus used is represented simply as a rectangular box and the
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two insoluble phases are identified as gas phase G and liquid phase L. It is assumed that only a single substance A diffuses from gas phase G to liquid phase L during their contact in the apparatus. The other constituents of the phases, solvents for the diffusing solutes, are then considered not to diffuse (these are the inert components). The gas stream at any point in the tower consists of G total moles/hr, made up of diffusing solute A of mole fraction yA, partial pressure pA, or mole ratio YA, and nondiffusing, essentially insoluble gas GS moles/hr. The relationships among these are: G GS G GA = yA = A = G GS + G A G
GA yA pA = = GS 1 y A p pA G G S = G (1 y A ) = 1 + YA Similarly the liquid stream consists of L total moles/hr, containing xA mole fraction soluble gas, or mole ratio XA, and essentially non-volatile solvent LS moles/hr. The relationships among them are: xA XA = 1 xA L L S = L(1 x A ) = 1 + XA In the figure the subscripts 1 indicate that end of the tower where the gas phase enters and 2 that end where the gas phase leaves. At the entrance to the tower (device, apparatus) in which the two phases are contacted, phase G contains G1 total moles per unit time, consisting of non-diffusing solvent gas GS moles per unit time and diffusing solute A, whose concentration is y1 mole fraction. As the gas phase G moves through the equipment, A diffuses to the liquid phase L and consequently the total quantity of G decreases to G2 moles per unit time at the exit, although the rate of flow of non-diffusing solvent GS remains is the same as at the entrance. The concentration of A has decreased to y2 mole fraction. Similarly the liquid phase L at the entrance contains L2 total moles per unit time, of which LS moles per unit time is non-diffusing solvent, and an A concentration of x2 mole fraction. Owing to the accumulation of A to a concentration x1, liquid phase L increases in amount to L1 moles per unit time at the exit, although the solvent content LS remained constant. Envelope I, the closed irregular line drawn about the lower part of the equipment, will help to establish a material balance for substance A, since an accounting for substance A must be made wherever the envelope is crossed by an arrow representing a flowing stream. The A content of the entering G phase is G1y1, that of the L phase is Lx. Similarly the A content of the leaving streams is Gy and L1x1, respectively. Thus the material balance (for y and x subscript A is omitted): G 1 y 1 + Lx = Gy + L1 x1 which is rearranged for the gas phase mole fraction of y as: L G y L 1x1 y = x+ 1 1 G G The last equation represents a line with varying slope on x-y coordinates, of local slope L/G, passing through the point whose coordinates are (x1,y1). This line represents the relation between the liquid and gas concentration at any level in the lower part of the tower. A similar material balance can be written on the upper part of the equipment, giving the following rearranged equation: YA =
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L G y L2x2 x+ 2 2 G G which also represents a line with varying slope on x-y coordinates, of local slope L/G, passing through the point whose coordinates are (x2,y2). It is easy to prove that the second parts of the last two equations are equal, by writing a material balance on the whole equipment which can be rearranged as follows: G 1 y 1 L1x1 = G 2 y 2 L 2 x 2 It follows that the lines represented by the last two equations coincide. This line is illustrated on Figure 4 and is called operating line of the equipment. This line represents the relation between the liquid and gas concentration at any level in the tower. Figure 4. The equilibrium-solubility data (the equilibrium curve) for the solute gas in the solvent liquid may also be plotted on the same diagram as shown in the figure. Since the solvent gas and solvent liquid are essentially unchanged in quantity as they pass through the tower, it is convenient to express the material balance in terms of these. A solute balance about the lower part of the tower (envelope 1) is: G S Y1 + L S X = G S Y + L S X1 and after rearranging: L G Y L S X1 Y = S X+ S 1 GS GS This is the equation of a straight line (the operating line) on X,Y coordinates, of slope LS/GS, which passes through the point whose coordinates are (X1,Y1). Substitution of X2 and Y2 for X and Y shows the line passes through the point whose coordinates are (X2, Y2) also. This line represents the relation between the liquid and gas concentration at any level in the tower as at point P on Figure 5. Figure 5. The equilibrium data are also plotted in terms of these concentration units on the same diagram as shown in the figure (as curve MN). Each point on this curve represents the gas concentration in equilibrium with the corresponding liquid at its local concentration and temperature. For an absorber (for mass transfer from gas to liquid) the operating line always lies above the equilibrium curve, while for stripper (for mass transfer from liquid to gas) the operating line is always below. In mass transfer theory it is proved that the overall driving force at any position of the tower is represented by a vertical or a horizontal line between the operating line and the equilibrium curve on Figure 4 or Figure 5. The driving force obviously changes in magnitude from place to place or from one end of the equipment to the other. If the operating line should touch the equilibrium curve anywhere, so that the phases contacted are in equilibrium, the driving force and hence the rate of mass transfer would become zero, and the time required for a finite material transfer would be infinite. It is clearly seen that when the operating line is closer to the equilibrium curve the driving force at any position will be smaller, consequently, larger equipment is required to fulfil the same mass transfer. y=

Minimum liquid-gas ratio for absorption In the design of absorbers, the quantity of gas to be treated G1 or GS, the terminal concentrations Y1 and Y2 (the inlet and the outlet concentrations) and the composition of the entering liquid X2 are ordinarily fixed by process requirements, but the quantity of liquid to be used for the solution of the problem is subject to choice. The operating line must pass through point D and must end at the ordinate Y1 as shown on Figure 6.
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Figure 6. If such a liquid is used to give the operating line DE, the exit liquid concentration will be X1. If less liquid is used, the exit-liquid concentration will be clearly greater, as point F shows, but the driving forces for the mass transfer are less, the absorption becomes more difficult. The contact time between gas and liquid must be greater, and the absorber must be correspondingly taller. The minimum liquid quantity which may be used corresponds to the operating line DM, which has the greatest slope for any line touching or crossing the equilibrium curve and is the tangent to the curve at P. At P the diffusional driving force is zero, the required contact time for the concentration change desired is infinite, and an infinitely tall tower results. This then represents the limiting (the minimum) liquid-gas ratio. The equilibrium curve is frequently concave upward, as is shown in Figure 6 also, and the minimum liquid-gas ratio then corresponds to an exit liquid concentration in equilibrium with the entering gas. The actual liquid-gas ratio normally will be greater than the minimum one by as much as 25 to 100 percent and may be determined by economic considerations as well as by judgement and experience. For example, in some packed-tower applications involving very soluble gases or vacuum operation, the minimum quantity of solvent needed to dissolve the solute may be insufficient to keep the packing surface thoroughly wet, leading to poor distribution of the liquid stream. These principles also apply to strippers, where an operating line which anywhere touches the equilibrium curve represents a maximum ratio of liquid to gas and a maximum exit-gas concentration. Equipment for absorption The purpose of the equipment used for absorption is to provide intimate contact of the two phases in order to permit inter-phase diffusion of the constituents. The mass transfer rate is directly dependent on the interfacial surface exposed between the phases, and the nature and degree of dispersion of one of the phases in the other one are therefore of prime importance. The equipment may be classified according to whether its principal action is to disperse the gas or the liquid, although sometimes both phases become dispersed. The gas is dispersed in agitated vessel (rarely used for absorption) and in tray towers. The liquid is dispersed in Venturi scrubbers, in wetted-wall towers, in spray towers, in baffle towers (or shower trays) and in packed towers. Only a brief discussion of tray towers and packed towers will be given here. Tray (or Plate) towers Tray towers are vertical cylinders in which the liquid and gas are contacted in stepwise fashion on trays or plates. A schematic representation of a bubblecap tray tower is shown on Figure 7. Figure 7. The liquid enters at the top and flows downward by gravity. On the way, it flows across each tray horizontally and through a downcomer to the next tray below. Figure 8 shows different tray arrangements and the direction of liquid flow on the trays. Figure 8. The gas passes upward through the openings in the tray, and then bubbles through the liquid to form froth, and disengaging from the froth passes on to the next tray above. The overall effect is a multiple countercurrent contact of gas and liquid, although each tray is characterized by a cross flow of the two phases. Each tray of the tower is a stage, since on the tray the fluids are brought into intimate contact, interphase mass transfer occurs, and the fluids are separated. The number of theoretical trays (or stages) in a column (or tower) is dependent only upon the difficulty of the separation to be carried out and is determined solely
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from material balances and equilibrium considerations. The stage or tray efficiency, and therefore the number of real trays, is determined by the mechanical design used and the conditions of operation. The diameter of the tower, on the other hand, depends upon the quantities of liquid and gas flowing through the tower per unit time. Once the number of theoretical trays required has been determined the principal problem in the design of the tower is to choose dimensions and arrangements which will represent the best compromise among several opposing tendencies, since it is generally found that conditions leading to a high tray efficiency will ultimately lead to operational difficulties. The most frequently used types of trays are bubble-cap trays, sieve trays and valve trays. Figure 9 shows two typical bubble-cap designs. Figure 9. Plate columns may be economically preferable for large-scale operations and are needed when liquid rates are so low that packing would be inadequately wetted, when the gas velocity is so low (owing to a very high liquid-to-gas ratio) that axial dispersion or pumping of the gas back down the (packed) column can occur, or when intermediate cooling is desired. Also, plate towers may have a better turndown ratio and less subject to fouling by solids than are packed towers. Packed towers Packed towers are vertical cylinders which have been filled with packing or devices of large surface. A schematic representation of a packed tower is shown on Figure 10. Figure 10. The liquid is distributed over, and trickles down through the packed bed, thus exposing a large surface to contact the two phases. The adequate initial liquid distribution is very important. Dry packing is of course completely ineffective for mass transfer between the two phases, and various devices are used for more efficient liquid distribution. Two major types of packing are used, random or regular. Random packing is that which is simply dumped into the tower and allowed to fall at random. Regular packing is carefully stacked in the tower. Both types of packing have advantages and disadvantages from economic standpoint (investment and operational costs). Figure 11 shows several types of packing. Figure 11. Packed columns usually are chosen for very corrosive materials, for liquids that foam badly, for either small- or large-diameter towers involving very low allowable pressure drops, and for small-scale operations requiring diameters of less than 0.6 m (2 ft). The type of packing is selected on the basis of resistance to corrosion, mechanical strength, capacity for handling the required flows, mass-transfer efficiency and cost. Details on the operating characteristics of plate and packed towers are given in special literature.

Absorption plant The general layout of an absorption plant is shown in Figure 12. Figure 12. An absorption plant consists of the absorption unit, the regeneration unit and all necessary auxiliary equipment and machinery. The gas mixture with the gaseous pollutant, namely the solute or the absorptive, enters the absorption unit at the bottom. Within the absorption unit the gas mixture is brought into contact with the liquid (solvent or absorbent). During the contact time the pollutant is at least partly transferred from the gas to the liquid. The purified gas mixture leaves the absorption unit at the top. The liquid normally enters at the top of the absorber and leaves it at the bottom. The liquid leaving the absorption unit and carrying the
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pollutant is directed to some regeneration unit where the absorbent is treated in such a way that it may be recycled to the absorption unit and the pollutant is disposed appropriately. Regeneration may be achieved by various processes such as vaporisation, rectification, steam stripping, desorption, extraction etc. If necessary, regenerative medium is introduced to extract the pollutant. The solubility of the different gases is decreasing with increasing temperature and decreasing pressure (as mentioned earlier). It follows that the absorption process should be carried out at a relatively low temperature and high pressure. However in air pollution control many times the gas mixture to be treated has a higher temperature and lower pressure. Therefore, the waste gas has to pass through a pre-cooler in order to reduce its temperature as low as possible. Another important property which should be observed is the low (sometimes very low) concentration of the pollutant in the gas mixture. In many cases the pollutant concentration is so low that it hardly can be detected in the gas mixture so a very efficient absorption technique is required for the removal of such a tracer component. Taking into account the considerations mentioned above the absorption unit is only one part of the absorption plant which may consists of a generation unit, heat exchangers, as well as fans and pumps for transporting the gas and the liquid, respectively. In many cases, the absorption unit is the smallest part of the plant. Earlier the consideration was focused on the absorption process and the absorption unit which is the heart and the most important part of the whole absorption plant. But it should be emphasized that the absorption unit (or the absorber) should be considered in combination with the auxiliary equipment for the optimisation of the process. In the following an important application will be shown.

Sulphur dioxide removal from stack gases. Sulphur dioxide is an important chemical component of waste gases from power plants when some fossil fuel (coal, crude oil, natural gas) containing sulphur is used as energy source. Before the eighties in Europe (also in the USA) many countries used coal which had high sulphur content (3-4 % m/m). Burning the coal in the boiler the sulphur is also burnt and sulphur dioxide is produced: S + O 2 = SO 2 If the sulphur dioxide is emitted into the atmosphere it causes the acid rain. Strict international regulation has been applied to decrease the emission of the sulphur dioxide below the emission limit since 1985 (signed by most European countries as well as by the USA, Canada and the UN). At the beginning the requirement was fulfilled by changing the fuel (using coal or crude oil with less sulphur content or natural gas which practically has no sulphur content) but when the regulation was tightening up the desulphurization of the waste gas was introduced. The desulphurization of the waste gas can be carried out with several processes classified into three groups as wet processes, dry processes and half-dry (or halfwet) processes but mainly a wet process is used all over the world. In this process the absorbent (the solvent) contains calcium hydroxide which reacts with the sulphur dioxide in the liquid phase creating gypsum. Figure 13 schematically describes the desulphurization of stack gases. Figure 13. The volumetric flow rate of these waste gases is of the order of several million m3/h. The polluted gas containing the sulphur dioxide passes through a dust separator (because of the strict regulation generally the electrostatic precipitators or sometimes bag filters are used). The waste gas leaving the dust separator moves to the absorber that may be operated in one or (rarely) two stages (two absorbers connected into series).
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The sulphur dioxide is absorbed in the absorbent, where reacts with the calcium hydroxide producing calcium sulphite. The problem is that the calcium sulphite is soluble in water and can not be disposed since the rainwater will wash it into the soil and underground water. It means that an oxidation process is required to get calcium sulphate (gypsum). The steps are as follow: absorption in the water, producing sulphuretted (or sulphurous) acid: SO 2 + H 2O = H 2SO 3 , chemical reaction in the liquid phase with the calcium hydroxide, producing calcium sulphite: Ca(OH )2 + H 2SO 3 = CaSO3 + 2H 2O , oxidation of the calcium sulphite producing calcium sulphate (which is practically insoluble in the water and it is the reason that gypsum is used as building material): CaSO3 + 0.5O 2 = CaSO 4 , which contains crystal water (not shown in the chemical reaction), removable only with heating. The flue gas generally contains the oxygen necessary to the oxidation as some excess air is used in the boiler, but more excess air or directly oxygen can be introduced into the lower part of the absorber in order to enhance the efficiency of the oxidation. The desulphurized waste gas from the absorber moves through a mist separator and to a heat exchanger for reheating it to about 110 C or higher and finally to stack. Remark: a quick calculation shows that 1 kg of absorbent containing 0.1 kg calcium hydroxide (10 % by mass) can absorb about 0.086 kg sulphur dioxide which is 86000 ppm (in ideal conditions). It is about 35 times higher than received for physical absorption (it was 2473 ppm).

Advantages and disadvantages of absorption systems (packed and plate columns) Advantages Relatively low pressure drop Capable of achieving relatively high mass-transfer coefficient and high mass transfer rate Increasing the height and/or type of packing or try numbers capable of improving mass transfer without purchasing a new piece of equipment Relatively low capital cost Relatively small space requirements Ability to collect particles as well as gases Collected substances may be recovered by distillation Fiberglass-reinforced plastic construction permits operation in highly corrosive atmospheres. Disadvantages Possibility of creating water (or liquid) disposal problem (remark: IPPC) Product collected wet Particulates deposition possibly causing plugging of the bed or the plates Fibreglass-reinforced plastic is sensitive to temperature Relatively high maintenance cost Must be protected from freezing (if operated in outside) Comparison of packed and plate towers Packed towers Lower pressure drop
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Simpler and cheaper construct Preferable for liquids with high foaming tendencies Plate towers Less susceptible (sensitive) to plugging Less weight Less susceptible (sensitive) to channelling Temperature variation resulting in less damage

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Introduction Definitions Gas absorption is a unit operation in which soluble components of a gas mixture are dissolved in a liquid. The inverse operation, called stripping or desorption, is employed when it is desired to transfer volatile components from a liquid mixture into a gas. Both absorption and desorption (stripping), in common with distillation, make use of special equipment for bringing gas and liquid phases into intimate contact. This section is concerned with the application of absorption and stripping processes as well as with several special questions of their design and operation. Equipment Absorption and stripping (as well as distillation) operations are usually carried out in vertical, cylindrical columns or towers in which devices such as plates or packing elements are placed. The gas and liquid normally flow countercurrently, and the devices provide the contacting interfacial surface through which mass transfer takes place (cocurrent flow is also possible from economic standpoint). Background material on this mass transfer process is given in a different class. General design procedure The designer is ordinary required to determine (1) the best solvent; (2) the vessel diameter; (3) the height of the vessel and its internal members, which is the height and type of pacing or the number of the contacting trays; (4) the optimum solvent circulation through the absorber and stripper; (5) the temperatures of streams entering and leaving the absorber and the quantity of heat to be removed to account for heat of solution and other thermal effects; (6) the pressures at which the absorber and stripper will operate; and (7) mechanical design of the absorption and stripping vessels (normally columns or towers), including flow distributors, packing supports, and so on. The problem presented to the designer of a gas-absorption unit usually specifies the following quantities: (1) gas flow rate; (2) gas composition, at least with respect to the component or components to be removed (to be absorbed); (3) operating pressure and allowable pressure drop across the absorber; (4) minimum degree of recovery of one or more solutes; and, possibly, (5) the solvent to be employed. Items 3, 4, and 5 may be subject to economic considerations and therefore are sometimes left up to the designer. For determining the number of variables that must be specified in order to fix a unique solution for the design of an absorber one can use the same phase-rule approach as for distillation. Recovery of the solvent, sometimes by chemical means but more often by distillation, is almost always required, and the recovery system ordinarily is considered an integral part of the absorption-system process design. A more efficient solvent-stripping operation normally will result in a less costly absorber because of a smaller concentration of residual dissolved solute in the regenerated solvent; however, this may increase the overall cost of solvent recovery. A more detailed discussion of these and other economic considerations is not presented here because of time shortage. Selection of solubility data Solubility values determine the liquid rate necessary for complete or economic solute recovery and so are essential to design. Equilibrium data generally will be found in one of three forms: (1) solubility data expressed either as solubility in weight or mole percent or as Henrys-law coefficients (2) pure-component vapour pressures, or (3) equilibrium distribution coefficients (K values as mentioned in literature). Data for special systems may be found in different references.

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In order to define completely the solubility of a gas in a liquid, it generally is necessary to state the temperature, the equilibrium partial pressure of the solute gas in the gas phase, and the concentration of the solute gas in the liquid phase. Strictly speaking, the total pressure on the system also should be stated, but for low total pressures, less than about 500 kPa (5 atm), the solubility for a particular partial pressure of solute gas normally will be relatively independent of the total pressure of the system. Pure-component vapour pressures can be used for predicting solubilities for systems in which Raoults law is valid. For such systems p A = PA x A where PA is the pure-component vapour pressure of the solute, pA is its partial pressure in the gas phase and xA is its mole-fraction in the liquid phase. Extreme care should be exercised when attempting to use pure-component vapour pressures to predict gas-absorption behaviour. Both liquid-phase and gas-phase nonidealities can cause significant deviations from the behaviour predicted by Raoults law. Vapour-pressure data are available in literature. Whenever data are available for a given system under similar conditions of temperature, pressure, and composition, equilibrium distribution coefficients (K values) provide a much more reliable tool for predicting vapour-liquid distributions. The distribution coefficient gives a direct relation between the mole fraction of A component in the gas phase and the liquid phase as follows: y A = K AxA Detailed discussion of equilibrium K values may be found in references.

Calculation of Liquid-to-Gas Ratio The minimum possible liquid rate is readily calculated from the composition of the entering gas and the solubility of the solute in the exit liquor, saturation being assumed. It may be necessary to estimate the temperature of the exit liquid based on the heat of solution of the solute gas. Values of latent and specific heats and values of heats of solution (at infinite dilution) are given in references. Column Diameter and Pressure Drop Flooding determines the minimum possible diameter of the absorber column, and the usual design is for 60 to 80 percent of the flooding velocity. Maximum allowable pressure drop may be determined by the cost of energy for compression of the feed gas. For systems having a significant tendency to foam, the maximum allowable velocity will be lower than estimated flooding velocity, especially for plate towers. The safe range of operating velocities should include the velocity one would derive from economic considerations. Methods for predicting flooding velocities and pressure drops are given are references. Computation of Tower Height The required height of a gas-absorption or stripping tower depends on (1) the phase equilibria involved, (2) the specified degree of removal of the solute from the gas, and (3) the mass-transfer efficiency of the apparatus. These same considerations apply both to plate towers and to packed towers. Items 1 and 2 dictate the required number of theoretical stages (plate tower) or transfer units (packed tower). Item 3 is derived from the tray efficiency and tray spacing (plate tower) or from the height of one transfer unit (packed tower). Solute-removal specifications normally are derived from economic considerations. For plate towers, the approximate design methods may be used to estimate the number of theoretical stages, and the tray efficiencies and tray spacing for the tower can be specified
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on the basis of the information given later. Considerations involved in the rigorous design of the theoretical stages for plate towers are treated in references. For packed towers, the continuous differential nature of the contact between gas and liquid leads to a design procedure involving the solution of differential equations, described in references.

Selection of Stripper-Operating Conditions Stripping involves the removal of one or more volatile components from a liquid by contacting it with a gas such as steam, nitrogen, or air. The operating conditions chosen for stripping normally results in a low solubility of the solute (i.e. a high value of m), so that the ratio mG/L will be larger than unity. A value of 1.4 may be used for rule-of-thumb calculations involving pure physical desorption. For platetower calculations the stripping factor S=KG/L, where K=y/x, usually is specified for each tray. When the solvent from an absorption operation must be regenerated for recycling back to the absorber, one may employ a pressureswing concept, a temperature-swing concept or a combination of both in specifying stripping conditions. In pressure-swing operation the temperature of the stripper is about the same as that of the absorber, but the stripping pressure is much lower. In temperature-swing operation the pressures are about the same, but the stripping temperature is much higher than the absorption temperature. In pressure-swing operation a portion of the dissolved gas may be sprung from the liquid by the use of a flash dram upstream of the stripping-tower feed point. If the flashing of the feed liquid takes place inside the stripping tower, this effect must be accounted for in the design of the upper section in order to avoid overloading and flooding near the top of the tower. Design of Absorber-Stripper Systems The solute-rich liquor leaving a gas absorber normally is distilled or stripped to regenerate the solvent for recirculation back to the absorber. It is apparent that the conditions selected for the absorption step (e.g., temperature, pressure, L/G) will affect the design of the stripping tower, and, conversely, a selection of stripping conditions will affect the absorber design. The choice of optimum operating conditions for an absorber-stripper system therefore involves a combination of economic factors and practical judgements as to the operability of the system within the context of the overall process flow sheet.

Absorption is the process by which a gas component is dissolved in a liquid. In most cases, absorption is the process of selective removal of a component from a gas mixture. The gas mixture consists of insoluble and soluble components, the first one is called inert component and the second one is the diffusive or solute component. The liquid consists of the solvent and the absorbate selectively removed from the gas mixture. The liquid mixture including the absorbate is called the absorbent. Absorption is one of the most advanced techniques applied to the separation of gas mixtures. Absorption is widely used in industry, and in the areas of air pollution control it has become one of the important processes for the abatement of gaseous pollutants. In Table 1 pollutants are compiled that may be removed from a gas mixture by means of absorption.

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