490 Multiphase Reactors ‘The reactant A must be transferred from the gas phase into the Fiquid phase in order oreact with B. The rate of mass transfer per unit of area is aa = aah ~ KYCA) where K*is the equilibrium distibution of A between gas and liquid phases, as discussed previously. The area of this interface is 2 R\L. ‘We can now write the mass-balance equations for the phases as ac PAR Ch — KECH) de aR 2nR, -#CKCh Spinach ~ REC Get ECS + \ ) ‘We included the term r# = 0 10 indicate tat there is no reaction inthe gas phase. The mass transfer rates obviously have opposite signs, and we have to multiply the mass transfer flux by (arsa/volumel, where the volume is that occupied by that phase. Note thatthe mass transfer tm afier dividing out becomes proportional 10 R}, Since the reactor volume is proportional to R2 while the surface area for mass transfer is proportional to R, the fal film column obviously becomes less ecient for larger reactor sizes. This i fandamental problem with the falling film reactor in that small tubes give high mass transfer rates but Jow total production of product. ‘The mass transfer coefficient is usually much lower in the liquid phase, and therefore C4 is a function of 2 the distance from the wall to the interface. One would have to solve for tie steady-state profile C,(R), and find its average C2) 10 inser into the PETR ‘mass-balaace equations simultaneously to find C(L) in each phase. Example 12-1 An aqueous solution containing 10 ppm by weight of an organic cont inmyof molecular weight 120 sto be removed by ai oxidation na -on-damete ling filmpenctor at 25°C, The liquid lows at an average velocity of 10 cm/sec and forms a Tn, Tin thick on the wall while the air at 1 atm flows at an average velocity of 2 emisec ‘The reaction in the liquid phase has the stoichiometry A +20; —> products with a rate ak, (a) What ite the compositions when the reaction has gone to completion? ‘We assume that both phases are in nearly plug flow, and we need first to caleulate the flow rates of each reactant, uf = Alu! = 70.5? - 04%) x 10= 2.83 em™see Uf = AME = a x 04? 2 = 1.005 emsee ‘The feed concentrations are 10 : 4, =O = 8.33% leslem® Chg = Hy = 838 « 10-* motesem assuming the density of water is ~ 1 glem® and Po. 02 awe = 8.58 x 1076 molesicm? ‘0 RT ~ 82 x 300 S58 x 10 Hes Falling Film Reactor 491 Therefore, the molar flow rates are Pha = 0 Chg = 2.83 X 8.33 x 10°6 = 2.36 x 10-7 molevsec Fo = UCB, = 1.005 x 8.58 x 10°% = 3.62 x 10° motessee ‘Thus we see that there isan excess of O3; so all A will be consumed at complete conversion. This gives Foyg ~ Fo, = 2Fao (Chere are 2 moles of O3 consumed per mole of A reacted), so that ifthe reaction goes 10 completion, we have =o Cog = 8.14 x 10-* molesem* which we will assume to be a negligible change in Os (b) Write the equations) that must be solved to find the reactor length required fora given organic removal At these flow rates the Os inthe aris no depleted, and we donot need to worry about the mass balance of the ait in the gas phase. We only need to solve the equation forthe organic in the liquid phase, which s act a (©) How many tubes in parallel are required to process 100 liters/min of water? What will be the diameter of the tube bundle if the tubes are packed in a square array and the tube wall thickness is neglected? ‘One tube processes 2.83 cm/sec; soto process 100 iters/min we will nced 100 x 108 283 x 60 these are packed in square configuration with a negligible tube wall thickness, ‘cach tube occupies an area 1 em? in the tube bundle. The cross-sectional area of the tube bundle is 590 cm; so the diameter of the column is p= (222) -an4en ~18 (@) Estimate the reactor length needed to reduce the organic concentration to 1 ppm ifthe reaction rate inthe liquid is infinite and the reaction is limited by the mass transfer of Os in the gas. Assume Do, = 0.1 em? see, = 590 tubes This doesn't seem to be a good approximation because mass transfer in gases is almost always much faster than in liquids. If it were true, the Sherwood number492 Multiphase Reactors ‘would be § for laminar flow ofthe air flowing in the 0.8-cm-diameter tube. Thus we have 5 _ ShoDo Ho, = Mae ‘We have to solve for A in the liquid phase, acy al A Km Con dz : “The interfacial area per volume of reactors AL xDib 4D, ee DL — DF and the equation becomes. ‘The right-hand side is eonstant because Co, does not change significantly, so this ‘equation can be simply integrated to yield ‘This answer is clearly nonsense because We Would need a reactor length of less than I millimeter! {¢) Estimate the reactor length needed to reduce the organic concentration to L ppm if O: ‘mass transfer is sufficiently fat that the liquid solution remains saturated with O> and the rate coefficient kis 1 x 10 literimole sec. The Henry's Law constant for Op in water is 1x 108 aim, [Now mass transfer of O: is assumed to be fast so that the liquid remains saturated with Oo, and the process is assumed to be limited by the reaction in the liquid phase. Therefore, we have to solve the equation so that whic gives Cg = 5.56 x 10-7 molesfiter. Recall that Coy is nearly constant so this equation can be rearranged to yield wt fda so aise astsm = 160 Gh, | Ce * WR SSORT Bubble Column Reactors 493 4 reasonable column height. (f) Estimate the reactor length needed to reduce the organic concentration to 1 ppm if the reaction actually occurs on acatalyst on the wall ofthe reactor tube. Assume thatthe reaction rate onthe walls infinite and the process is limited by the diffusion of On through the liquid, with Dox = 10° em*/sec, and thatthe concentration sofile is Kinear, Now we assume that reaction occurs on the exterior surface of the tube. The ‘equation to be solved is eee Fe AGP" =F zhelCo; ~ Com) = -F halo, ADo.Coy V(R,— R) ~347 x 10°” molester see ‘The area for mass transfer per unit volume of reactor in the liquid is given by A. 4Do Vv" B3- DF ‘We now solve the preceding differential equation, noting that all terms on the right-hand side are constants to obtain the resctor length needed, (Co ~ Ca 347 x 10-1 ‘This is avery tal column, M.len! 2160 em = 22 meters = 70 ft (g) How would the answers to (c),(@), and (e) change ifthe pressure of air were increased from 1 (0 2 atm? Doubling Co, will double the rate ofthe reaction and the rate of O2 mass transfer to the wall of the reactor. Therefore, the reactor length needed willbe half of those calculated in each of the previous situations BUBBLE COLUMN REACTORS We just noted that the falling fil reactor has the problem that the surface area increases us ‘he perimeter between gas and liquid while the volume inerases asthe cross sot wea A R21 Volume ~ gasvohime ~ RPK ~ D In onde to desig a efficient reactor using a falling fim reactor, we would need to have ‘many stall tubes in parallel so thatthe interfacial area cane large. This is dificult to accomplish with flow down tubes, but it is easy f accomplish with rising bubbles o falling drops. The interfacial area is not now the area ofthe eylinder between gas494 Multiphase Reactors, Bubble Column Reactors 495 and liguid but rather the area of the bubbles or drops, whieh can be large in Targ. Fee 210 Sah ecncnenaton diameter tube. afer migrating rm the gas phase no the Inge Consider a liquid flowing downward in a tube with gas bubbles introduced at the hue in bubble column and spray ewer reacts, bottom, The bubbles rise because they are Tess dense than the liquid. At the top the gas is separated from the liquid in the head space, while pure liquid is withdrawn at the boitons, ‘as shown in Figure 12-9. ‘An important example of bubble column reactors isin partial oxidation of organics, ‘such as p-xylene to make terephthalic acid, a monomer for polyester (PET), p xylene 10: > terephthalic acid where p-xylene and terephthalic acid are liquids and O, is @ gas. In partial oxidation such fas these the reaction occurs homogeneously (either with free-radical intermediates or with ‘a homogenzous catalyst inthe liquid phase, and the desired product remains inthe liquid ‘phase, where itis separated from the other organic. Its usually important to have no Os in the product because it ean be explosive; so the reactor must be designed so that all Os in the bubbles has reacted and none reaches the head space, where it could react explosively with the organic products, "Another example of bubble columns is hydrogenation of olefins and other organics, such as reduction of dinitrotoluene 4initrotoluene +H —> diaminotoluene which is an intermediate in production of polyurethanes and in the hydrogenation of fats and ols, Callan + Hy > CyHapa In this case the reaction occurs only in the liquid phase (the oils have negligible vapor pressure), hutreaction requires a solid catalyst such as finely divided Ni, which is suspended inthe liquid. Thus we see that this isin facta three-phase reactor containing Ho gas, organic Fiquid reactants and products, and solid catalyst igure 12-9 Bubble column snd spay ower ree ‘gas Mique ee ‘ors. Large drop ar babble areas increase reactant mss masta th liquid [liquid liquid spray tower bubble drop ‘The concentration profile for a reactant A which must migrate from a drop ot bubble into the continuous phase to react might be as shown in Figuse 12-10. There is 4 concentration drop around the spherical drop or babe because itis migrating outward, but, as with @ planar gas-liquid interface in the falling film reactor, there should be a discontinuity in C, atthe interface due to the solubility of species A and a consequent equilibrium cistrbution between phases. Bubble columns rly on nozzles, mixing plates, and impellers within the reactor to control the bubble size, which determines te interfacial area between gas and liquid phases, Cleary, the interfacial area can be varied over a wide range by suitable design ofthe mixer and flow pater, ‘Consider a bubble phase occupying a fraction én a reactor with volume vesety Suppose all bubbles have radius, so that cach bubble has a volume 4 RE. Af there are [N® bubbles per unit volume of reator,then the Volume occupied by bubbles is aR 3 If the bubbles supply reactant into the liquid phase hen the bubbles are decreasing in size because of reaction; so we need to find Ry(t) oF &s(z) of the bubbles as they rise in the reactor, Thus we have the problem of a sphere that wares in diameter as the reaction proceeds. We considered this in Chapter9 where we were concerned primarily with reaction of solid spheres instead of Tiquid spheres. The bubbles usualy have a distribution of sizes because larger bubbles usually se faster than small ones, and they can coalesce and be redispersed by mixers. However, to keep the problem simple, we will assume that all particles have the same size. For the reactant A supplied from the bubble, we have t solve the equation veane aR, tx Rip Se Aa Re Jjustas we dd for a reacting solid concentration profiles of reactant A and product B reacting around a spherical particle are shown in Figure 12-11 wt R5(Ca ~ Cas)496 ‘Multiphase Reactors igure12-11Skeches of concentatie profiles ofa estat aroun a drop where the reaconis inte surounding continuous hike Arrows indiate decions of reacant mass ow As with reactions of solids, we first assume a steady-state concentration profile of reactant calculate C(x) and then calculate the variation of Ry versus time asthe reaction proceeds. Example 12-2 _Anagueous solution contains 10 ppm by weight ofan organic contaminant of molecular weight 120, which must be removed by air oxidation in a 10-em- products with arate RF CLCS, (4) What are the compositions when the reaction has gone to completion? ‘The volumetric low rates are Vo a WlAl = Loc x 5? = 785 emisec ‘The fed concentrations are 10% fo = 33 x 10° molesem? Cho 120 Po 02 Coo = Rr = Bx 30 ‘The lar eed rats ae therefore 8.58 x 10-* molesfem? Hi, = v'Ch, = 6.5 x 10° motesisee ‘This gives Fr=0 Fo, = Foye ~ 2Fao = 7.8 x 10° molesisee Bubble Column Reactors 497 ‘This means that Co, decreases by only ~3% in the reactor ifthe reaction goes to completion, so we can assume C8, is constant throughout the reactor, (b) Write the equation(s) that must be solved to find the length for a given organic removal Poe baance equation nthe ar pase and oc d courcanes sal fie sine aur ls onan emt The opis bet fonts 7 dz (©) Assuming that mass transfer of O in the Tiguid around the bubbles limits the rate, calculate the reactor length required to reduce the contaminant to ppm. ‘Since mass transfer in the liquid around the bubbles limits the rate, the mass= balance equation on A in the liquid phase becomes {for flow over a sphere we assume Shp = 2.0, so that Shp D5, = 2.x 10 emisee yo, = ‘The right-hand side of the differential equation is constant; soit can be integrated to yield (Cho — Cu (ARV IKfo,Car We next need A/V, the mass transfer area per unit volume of the reactor. The residence time of a bubble is L/ut. The volume of each bubble is © D3, and the surface area ofa bubble is D2. The volumetric flow rate of gas is ‘Therefore, the surface area of bubbles per unit volume of liquid in the reactor is A xDgNy __ 24vt V GAEL ~ Dut? Substituting, we obtain 8.33 x 10 x09 x1 % 38.2% 2% 10 x LIT x 107 8.2 emt L 177 em 177m (@) Estimate the reactor length required to reduce the organic concentration to | ppm if the ‘concentration of O> remains at equilibrium in the solution, [F'the O; remains in equilibrium, the equation to be solved is498 Multiphase Reactors oo Shp-2 unmixed KCKCS, Since Cé, is constant, the differential equation can be integrated to yield mace into = 207 em =2.07m Mixing in drop or bubble phases fan isolated drop or bubble rises or falls inthe reactor, then the low pattern in this phase is clearly unmixed, and this phase should be described as a PETR. However, drops and bubbles may not have simple trajectories because of string in the reactor, and also drops and bubbles can coalesce and breakup as they move through the reactor. ‘These possible flow patterns of a drop or bubble phase are shown in Figure 12-12, At the lef is shown an isolated bubble which rises (turn the drawing over fora falling drop), clearly unmixed situation. If the bubble is in a continuous phase which is being stirred, then the bubble will swirl around the reactor, and its residence time will not be fixed but ‘will be a distributed function. Inthe imit of very rapid stirring, the residence time of drops ‘or bubbles will have a residence time distribution Which is theesidence time distribution in a CSTR, We derived this expression in Chapter 8 ‘where we considered the distribution of residence times of molecules in the reactor, but now we consider the residence time of isolated bubbles or drops. If bubbles flow generally ‘upward, bu: continuously break up and coalesce, the residence time distribution of the species in this pase is narrow or roughly that of a PFTR, po =a, However with stirring and coalescence and breakup, both effects tend to mix the contents of the bubbles or drops, and this situation should be handled using the CSTR mass balance equation. As you might expect, for areal drop or bubble reactor the residence time distribution ight not be given accurately by either ofthese limits, andi might be necessary to measure the RDT to correctly describe the flow pattern inthe discontinuous phase, Figure 12-12. Sieses of st Ho p (Care ne eh ys Ita bbe clan Simoy ef be ota thas case ese te rn Die trofenh nd ntsc sad en Sct ics tn bese se Beak wes etc ete aise nc {cero eben or CSTE eran ape sey twee the saan ml tow ie Soe sob cok breakup and early andiato Mig uml tua es Shp=2 Shgr2 coalescence coalescence unmixed mised unmixed mixed Figure 12-18 A fling i extalstic wall rato in which resto in the gs must aise hough agai i reat ‘a aay which cons the wal of te Falling Fim Catalytic Wall Reactor 499 FALLING FILM CATALYTIC WALL REACTOR, ‘Next we complicate this situation further by allowing reaction, not throughout the liquid, but on a film of porous catalyst that coats the wall. This lm has thickness € and a surface area per volume p, 5, as in Chapter 7, We assume that < Ry, so that the definitions given ‘of volume and r apply, This reactor is sketched in Figure 12-13. ‘Now the reaction occurs by A migrating rom the gas in the center of the tube, through the falling liquid film, and into the porous catalyst, where it reacts with B trom the liquid pphase to form products that must then migrate out ofthe catalyst and into the owing gas ‘or liquid streams to escape the reactor. The reactant cancentiation profile aciuss the rear (C4(R) now is modified because A reacts in the porous catalyst rather than within the liquid film discussed in the previous section, as shown in Figure 12-13. ‘This problem cat be recognized as a variation of the tube wall reactor of Chapter 7, Where the reactants flowing down the tube had to migrate to and into the porous catalyst ‘on the wal to react. The only difference here is that the reactant must frst migrate through the film, which coats the wall before it can enter the eatalyst and react. IFthe second reactant B isin high concentration (liquids have much higher densities than gases even at high pressures) and the reaction is ot limited by its mass transfer, then this becomes a pseudo-frst-order reaction r” = k"C. If all mass transfer steps ate fast ‘compared to the reaction, hen this problem would simplily to be identical to the tube wall catalytic reactor, which gave Cal) = Cao exp (- : ) ‘We can continue to wtite other expressions for different limiting cases, for example, with reaction on a nonporous catalyst film, which coats the wall In the preveding expression we include an effectiveness factor 1) to account for pore diffusion limitations of A, In fact, if the catalyst film thickness on the wall of the reactor is small enough that we can assume it planar, then the effectiveness factor becomes. tanh “FoF, 0 aR, +R,500 Multiphase Reactors ‘where the Thiele modulus = (pe5k"/dp"/, which we also devived in Chapter 7. Its evident, however, that this problem can be much more complicated than either the wetted all column or the catalytic wall reactor, because it combines the complexities, ofboth. Infact, there are numerous addtional complexities with this feactor beyond those simplified cases Mass transfer and pore diffusion Recall than both A and B must diffuse into the catalyst for a bimolecular reaction to ovcur. ‘This cam create fairly complex concentration profiles ofthe two reactants within the catalyst, and the overall effectiveness factor is more complex than withthe assumptions above, Example 12-3 _Anaqueous solution contains 10 ppm by weight ofan osganic contaminant of molecular weight 120, which must be removed by ar oxidation in afspargerreactr]at 25°C. The liquid is admitted at | liter/sec. The air at 1 atm is admitted ROS WIETSES- An peter disperses the ar no bubbles of usiform 1 mm diameter and mixes gas and Tguid ‘ery rapidly. The reaction in dhe liquid phase has the stoichiometry A+ 202 —> products with arate = KICECS, (@) What are the compositions when the reaction has gone to completion? ‘The volumetric flow rates are 10" emYsee 0.5 x 10? em'fsee ‘The feed concentrations are Os 8 2 fo = Fog = 853 x 10° motesfom Po, 02 ss 3.58 x 10® moles/em* 20 RT ~ 82x 300 858% 10 lest ‘The molar feed rates we therefore 8.33 x 107 moles/sec 0.00429 moleshse As bein, the Oo changes ite when the reaction has gone to completion, 0 we may asume that Co, is constant (b) Write the equation(s) that must be solved to ind the reactor volume required for a given ‘organic removal. Since the O» concentration remains constant, we do not need to solve the mass- balance equation in the gas phase, Both phases are mixed, so we must solve the CSTR equation for Ca in the liquid phase, Caot = Cyr = vor Trickle Bed Reactor 501 (©) Assuming mass transfer of Op inthe liquid around the bubbles limits the rate, calculate the reactor volume required to reduce the contaminant to 1 ppm. We assume that Shy = 2 to obtain x = Stow 210 a a ay Kogy = BS w= LA a 2x 10+ emPtce ‘The O; concentration in the liquid atthe bubble surface is Pos 02 8, LL x 107? molesiem? Te Hom, ‘We must solve the equation A aykinn Cae Ca hy, Cby (@) Estimate the reactor volume required to reduce the organi concentration t | ppm if the concentration of O> remains at equiibsum in the solution, Now reaction limit the rate; so the mass-balance equation becomes ve Chg Ch = REC, Ch = HS, Ch with C), assumed constant, Solving this equation for V¢, we obtain yin Mle=ED 9x10 1215 liters TRICKLE BED REACTOR ‘As with the falling film reactor, the rate of mass transfer tothe catalyst goes as R, while the sizeof the reactor goes as R?, 50 this reactor becomes very inefficient except for very small- diameter tubes. However, we can overcome this problem, not by using many small tubes in parallel, but by allowing the gas and liquid to flow (tickle) over porous catalyst pellets ina trickle bed reactor rather than down a vertical wall, as inthe catalytic wall reactor. Inthis multiphase reactor a tube or tank (avery large tube) is filled with catalyst pellets ppacked into a bed and a liquid flows down over the catalyst while a gas lows up or down in ‘countercurrent or cocurrent flow. A cross section of this reactor is shown in Figure 12-14. ‘The petroteum hydrotreating reactor is the most important example of this reactor, [As discussed in Chapter 2, the hydrogenation and cracking of the heavy fraction of erude oil to produce lighter and volatile products occurs in an overall reaction