CHAPTER 13 Membrane Separation Proces IAL INTRODUCTION AND TYPES OF MEMBRANE SEPARATION PROCESSES IBAA Introduction ‘Separations by the use of membranes are becoming increasingly important in the process in dusties. In ths relatively now separation process the membrane aets as @semiperme: harrier and separation occurs by the membrane controling the rate of movement of various molecules hetwven to Tiguid phases, wo gas phases, or aliquid and a gas phase. The two Mid phases ae usually miscible and the membrane barrier prevents actual, ordinary hydro dynamic How, A clasitieatio of the main types of membrane separation follows. ne Processes IRL Clasifcation of Memb 1. Gas diffusion in porous sold. In this type a gas phase is present on both sides of the ‘membrane, whch isa microporous solid, The rates of molecular diffusion of the various as ‘molecules depend on the pore sizes and the molecular weights. This type of difusion inthe ‘olecular rasition, and Knudsen regions was discussed in detail in Section 7.6 2. Liguid permeation or dialvsis,_ {this eae, the small solutes in one fiquid phase diffuse reauliy because of concentration diflerences through a porous membrane 1 the second iquid {or vapor) phase, Passage of large molecules through the membrane is more diticult. This membrane process has buen applied in chemical processing separations such as separation of H.SO, from nskel and copper sulfates in aqueous solutions, food processing, and artificial kidneys. and wl be covered in detail in Section 132. In leetrialyss separation of ions ve ‘curs hy imposing an emf difference seress the membrane. 5. Gias permeation in membrane, The membrane inthis process is usualy a polymer sich asrubber, polyamide, and soon, and isnot a porous solid. The solute rembrane and then diffuses in the solid tothe other gas phase. 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Note that the permeance py in Eg. (132-4) is itferent from the meability Py defined in Eq, (6:9, Also, the vale of py is inversely proportional to the thickness. Instead of determining D y and K" in 160 separate experiments. its more con- venient to determine py in one separate difusion experiment. Solving each of the parts of Eq, (132.3) fr the concentration diference, Na - 41328) Pw Aduing the equations, the internal concentrations ¢, ane op out, and the final equation is "TRF Tew - (326) In some cases the resistances in the two liquid films are quite small compared to the mem bane resstane, which controls the permeation rate EXAMPLE 13.2-1. Membrane Diffsion and Liquid Film Resistances A liquid containing dilute solute A ata concentration ¢, = 3% 10? ke mlm is Mowing rasidly pasta membvane of thickness £ = 30° 1 Sin, The distribution Chapter IF Memiave Separation ProesesFive 1822. Conerrions or Pvampte 22 veflicient A” [Sand Dy = 700% 10 "asin the membrane. ‘The solute di fuses through the membrane, and its concentration on the other side i ¢> = (0,30 % 10 7kg mali’, The mass-ranster coefficient, islarge and ean be com sidered as ininte, and,» = 242 % 10-* ms {a) Derive she equation to caloulate the steady-state flux sketch, () Calculate the flux and the concentrations atthe membrane interfaces J, and make a Note that the concen The derivation isthe Soluion: For fue (a)the sketch is shown in Fig. ‘ration profile on the left side fs at (= 00) and, same as for Ey, (13246), but Vi, = Oo give Tow ks (327) For part bh toatl the fx sing Fes. (1324) and (182) Dank _ 7010-8) 1 xox ace | wx lipy 1k; * Was 10 Pw 35% 10% mis osx Fia0e 488.10 "kg mols Tcateulte Ng TAB IOS © ales =) = 2210 Mey = BS 10) Solving, c © O89 * 10 °kgmolim’, Ako. wsing Eq. (132-1). OSG 10 Solving, és. L504 10°" ke mol 1R2B Dialysis Proceses Dialysis uses a semipermeable membrane to separate species by virtue of thei different git fusion rates inthe membrane. The feed solution or dalyzate, which contains the solutes tobe separated, fows on oneside of the membrane and the solvent or difusite stream on the other Pant Separation Proves Principles wassie. Some sovnt may also illuse across the membrane in the opposite diretion, which re duces performance by diluting the dialyzate: Tn practice dialysis is used to separate spevies which ilfer appreciably in size and thus have seasomahly large dtference in diffasion rates, Solute Mes depend on the concentra thon pragiont inthe membrane, Hence. dialysis is characterized by lw fu rates in compari aiteation whieh depend Son to ather membrane processes, uch as reverse osmosis and ul ‘on applied pressre Th poneraldralysis is used with aqueous solutions on hoth ses ofthe membrane, The Jim resistances can be appreciable compared to the membrane resistance, Applications in hue recovery cf sodium hydroxide in cellulose processing, recovery of aids rom metal heal gure, semoval of produets trom culture solution in fermentation, desaling of cheese ee solide andreduetion of aleohol content of heer. Many small-scale applietions occur in the pharmaceut eal industry. 132€ Types of Equipment for Dialysis ‘Various geometrical configurations are used in liquid membrane pracesses. common one J imi toa iter press. where the membrane is a Hat plate, Vertical solid membranes are placed inbetween alternating figuor and solvent feed frames. with the liquor tobe dialyzed paeing fed tothe bottom and the solsent tothe top ofthese frames, The dilyzate andthe di fate are remeved through channels located at the top and bottom of the frames, respec- lively The ment important type consists of many smal tubes or very fine hollow fibers at tinged ina bundle, ike heat exchanger, This type of unit has a very high ato of membrane grea 10 volume ofthe unit. 1X2 Hemodialysis in Artificial Kidney An important example of the liquid permeation proces is alysis with an actifiial kidney in the bismedival eld, In this application for purifying human blood, the principal solutes re- lowed ave the small solutes urea, uri acid. creatinine, Phosphates, and excess amounts of Chloride, A typical membrane used is cellphane about 0.25 mm thick, whieh allows small otutes to diffe but retains the large proteins inthe bload. During the hemostasis, blood is pase on one side ofthe membrane while an aqucous dilyzing uid ows on the other vide. Solutes such as urea, urie acid, NaCl. and soo which have elevated concentrations in the blood, dffxe etoss the membeane 1 the dalyzing aqueous solution, which contains cer tun concentrations of solutes such as potassium salts, and so on, to ensure that concentra tions in the bland de not drop helow certain levels. In one configuration the membranes are tacked in the form ofa multilayered sandwich with blood flowing past one sie ofthe mem Franc and dalyzing Nuid past the other sk. The hollow fiber type is use quite often. EXAMPLE 13.2-2. Dialysis o Remove Urea from Blood CCafculate the flux and the rate of removal of urea at steady state in g/h trom blood ina euprophane (cellophane) membrane dalyzerat 37°C. The membrane 30025 num thick and has an area of 2.0 my. The masytransfer coefficient onthe blood sie fs estimated as ky = 125. 1D? mis and that om the aqueous side is 343% 1) md. The permeance of the membrane 68.73 10°? ms (B2), The “Concentration of Ure inthe bod is 42 ureatO0 mL-and that in the dalying uid wil be assumed a0. lupe 1S Membrane Separation PresesSolution: The concentration ¢ = 02/100 = 200 10 glmk. = 200 gin" and 6-0. Substituting imo Fg. (132-4), Nem Gein Tihs ¥ Vipw + Wh m0 Wias <1 + URI Wa TARR I = 891 10pm? For atime of | hand an area of 20% rateof removal = 891 x 10 43600)(20) = 6.42 urealh 133 GAS PERMEATION MEMBRANE PROCESSES ABBA. Series Resistances in Membrane Processes In membrane processes with two gas phases anda solid membrane. similar equations can he ‘written forthe case strated in Fig. 132-1b, The equilibrium relation between the solid and as phases i given hy 331) Where Sis the solubility of A nm" (STP)/atm +m" sold, as shown in Ey. (65-5). and £1 the equilibrium relation ir ke moln'-aum. ‘This similar to Henry's le The Aus equations in each phase are as foes: ky Nay plea ~ Pan) = les ~ ean) assay DanS = Tatra av ~ Pa «1333, ‘ = pits > Pad 334) ‘The permeability Py given previously is n ~ pags BUSTP)m Pa Pawo CS. atm (65-9) ‘The permeability Py given in ke mol units by dividing Ey, (65-9) by 22.814 mYke mal ke mol-m 1a (STP = 10 Sa CS aim ~ 22474 Som, -atm Ce “Then the fs through he memibane gten by Fy, (1833) becomes Py Na= FP Pas) C86) Pur? Separation Procos Pimples wsEliminating the interfacial concentrations a betore (= Poh vn L WieIRTY + IP VIL (133) 7 Inthe ease whete pure 4 (pi) ion the fll side of the membrane, there i no ditusional re sistance in the zi phase, aid can be considered tobe infinite, Note that ky = & RT. "An example of as permeation ina membrane isthe use ofa polymere membrane 3s ‘oxygenator for a heart-lung machine to oxygenate blood, In this biomedical application, pure O.gosison one side of «thin membrane and biowd ison the other side. Oxygen dtluses the manbrane into the Blot and COs dilluses ina reverse direetion into the as "hr 1AA6 Types of Membranes and Permeabiliis fr Separation of Gases 1. Types of deme-phase smmenic membranes. Early membranes were limited in thelr use Ihecause of low selectivities im separating (0 gmses and quite Tow permeation Nuxes. This low-fly problem was due to the fact thatthe membranes had to he relatively thick (Lil or V1 ofa inch oF greater} in onder to avoid tiny hoes. which reduced the separation by al. lowing viscous oF Knudsen flow ofthe feed. Development of silicone polymers (L mil thiek- hess} increased the permeability by faetors of L0-20 or so. These are called dense-phase symmetcie membranes ys include a very thin but 2. Tipes of assinmeric membranes. Newer asymmetric meme {dense skin on one side ofthe membrane supported bya porous substructure (RL). The dense ‘skim as thickness of about LOIN) A and the porous support thickness is about 25100 am, Te tay increase ofthese membranes is thousands of time higher than the T-mi-thik orig hal membranes. Some typical materials currently used for asymmettie membranes are a lose acetate and modiied cellulose and silicone polycarbonate copoly ‘composite of polysulfone coated with silicone uber, acetates, aromatic polyamides or aromatic polyimide met on & porous support 5. Permeability of membranes. The permeability Py in Eqs. (65-9) and (13.3.6) is defined {8 D Sin av (STP)'s-an'C'S, amin, Sine mixtures of gases ate often presen. Por gas ‘A anid Pi for gis B willbe used instead of Py. The diferent sets of units used and thelr con ‘version factors ae given in Table 13.31, Sometimes unis are given in terms of Batters. as also defined in Table 13.3 The acute prediction of permeabilities of gases in membranes is generally not pos sible, and experimental values are needed, Experimental dats for common gases in some typical dense: pase membranes are given in Table 13.2. Note that there are wie difer- ences among the permesbilies of various gases in a given membrane. Silizone rubber ex hibits very high permeabilities forthe gases in the table For the eifict of temperature Tin K.ln #,jsapproximately linear function of V/s Increases with T. Howeser, operation at high temperatures ean often degrade the mem boanes. When 4 mixture of gases is present, reduetions of permeshibityof sm individual com ponent of up to 10% orsocan often accu In few eases, much larger reduetions have heen Sobserved (RI), Hence. when using. mitre of gases, experimental data should he obtained to determine ifthere i any interaction between the gases. The presence of water vapor ean have similar elects onthe permeablities and ean also possibly damage the membranes‘Tym 133-1. Comervion Factors for Permeability Pc and Permeance Pit Pereabtn, Py 00 en (STP) cm m Linen (St) mst i = 7501 <8 MST) son xy 0 ST svoméom He z seemsem Bg 81 ig oporrer = o wit (STPI em onparerem ~ yor (STP) 10 Bate ae La Baton = 10 9 Loven (STP) cm w (STH omen? (ST) TP) met) -e rate (STP) gas x yop STE ‘omen Hip yA ps Seeman Hi days Lem (STP) sem HT STP) th Lopem (STP) RISTP) Sc a) Taaue 133-2._Permebiltesof Various Gares in Dense-Phase Symmetric Membranes em iSTP) cm Peay, ig PT Maria Top CO) He sO) NRL Silicone rubber 25305508) (2) Nauralrubber 25 BL 4930. (2) Polyearbonate 5-30-1812 S610 14 (2) (Lexane) Nylon 66 2310 017 ost 0.008 (82) Polyester - 16s 0038031 ost any (Permasep) Silicone 2 210 97% 107 qwa) polyearbonate copolymer (37% silicone) ‘Teflon FEP wo 8 Ma 2s si) Ethyleellulose 30387492747 2329, ¢w3) Polystyrene W408 Sou 2.72 747285 (W3) 4 Permeance of membranes. In many cases, especially in asymmetric membranes, the Uhickness snot measured and only experimental values of permeance Pt are given. Con- version factors are als given in Table 13.31 133C Types of Equipment for Gas Permeation Membrane Processey 1. Flar membranes, Flat membranes ate mainly used in experiments to characterize the Permeability of the membrane. The modules are eas to fabricate and use and the areas of ‘the membranes are well defined. In some cases modules are stacked together lke a mult Pant Separation Prasess Prncpespermeate perforated ‘ollecting tube for permeate permeate channel membrane Flaunt 31. Spiraevun lente and asenbly. [Prom RL Bers Chem Eg. neds 008) Wh pein) the very layer sandwich or plateanse-frame filter press, The major drawhack of this type small membrane area per unit separator volume, Smal commercial Nat membranes are used {or praducing onygen-enriched air fr individual medical pplication, 2, Spiratswound membranes. This configuration retains the simpli ‘membranes while increasing markedly the membrane area per unit separator volume Up to 100 i (828 mi) and decreasing pressure drops (RI). The assembly consists ofa sand “wich of four shevts wrapped around a central core of a perforated collecting tube. ‘The four sheets consist ofa top sheet of an open separator arid for the feed channel. membrane, a porous felt hcking forthe permente channel, and smother membrane. as shown in Fig. 33. ‘The spral-mound elements 1M 40200 mm in diameter and s about Ito 1-5 m long in the ox- ial direction. ‘The Rat sheets before rolling are about 1-15 m by about 2-2.5 m. The space hetween the membranes (open aid for feed) is about I mm and the thickness of the porous Inicking (for permeate) is about 0.2 ram. The whole spral-wound clement i lacoted inside 9 metal shell, The feed yas enters at the let en of tae shell, enters the fee channel, and flows through this channel in the axial tirection of the spiral to the right end of the assembly (Fig. 133-1). Then the ent residue gas leaves the shell at this point, The feed stream, which i in he feed channel permeates pe penicularly through the membrane. This permeate then flows through the permeate chan rel in a direction perpendicular to the (ged stream toward the perforated collecting tube. ‘wher it leaves the apparatus atone end. ‘hiss illustrated in Fig. 13.32, where the local gas ‘ow paths are skown for a small element ofthe assembly 4 Hollow-fiber membnines. The membranes are inthe shape of very-smatl-iameter hol low hers. Theinside diameter of the fibers sin the range of 100-S00 jm and the outside 2O-U1HA a, withthe kong up to 3-5 m, The module resembles a shell-and-tube heat Chaps 8 Membrane Separation Pressmembrane SE fa permeate channel SESE ae SE eK, | EY b iB i i 1 a permeate 0 perforated collecting tube at center feed entrance FIGURe 133-2, Love flops fr spend separa temo scl end it | | permeate el | [AISI ser tant H tht feed —= i i Nie SW emese changer. ‘Thousands offine tubes are bound together a each end into a tube sheet thats sue rounded by a metal shel having a diameter of 1-012 m, so thatthe membrane area pet unit volume is up to 1100 mm asin Fig 13.33. A typical age industrial permeator fs hers 10200 jm ID and 400 gy OD in shel ini 110 1 Fong (7), ‘one end and leaves atthe other as inside “Typically. the high-pressure feed enters the s tend. The hollow fibers are closed at one end of the tube bundles. The pe the thers flows countercurrent othe shell side Now: and is cullected in a chamber where the ‘open ends ofthe fkersterminate, Then the permeate exits the device Pont Separation Process PrinciplesIn some lower- pressure operations such a fr separation of ae to rauce nitrogen, the fea enters inside the tubes (7). 13.3D Introduction to Types of Flow in Gas Permeation 1 Types uf flsr and diffusion gradient. tn a membrane proses high pressure fee £85 5 supplied to one side of the membrane and permeates normal to the membrane. The perme. ate lees indirection normal tothe membane, accumulating on the low-pressure side. Be. [Huse ofthe very high difusion coeTcient in sases, concentration prions a the gas phase jn the ditection normal tothe surlace ofthe membrane are quite small Hence, gi re sistaneos competed to the membrane resistance canbe neglected, This means that the con ‘entration inthe gas phase in a direction perpendicular to the membrane is essentially Un form, whether the go steam i lowing parallel 10 the surface or isnot Howing. If the gas streams flowing parallel t the membrane in essentially plug low. concen. tration gradient occurs inthis direction. Hence, several eases can aecur in the operation of 4 membrane madule. The permeate side of the memibrane ean be operated so thatthe phase 's completely mixed (uniform concentration) or so thatthe phase is in plug ow. ‘The high pressure feed side can also be completly mixed or in plug ow. Countercurrent or cocurrent Flow can he used when both sides are in plug flow: Hence. separate theoretical models must be derived for these ullferent types of operation, as given im Sections 131-138, Js for gas separa 2 Assumptions used an ideal flow panerns. In deriving theoretical mo tion by membranes, isothermal conditions and negligible pressure drop in the feed st and permeate steam are generally assumed, [cis also assumed that the elects of total pres sure andior composition of the gas are negligible and that the permeability of each compo: ent is constant (eno interactions hetween different component). Since thereate a numberof idealized How patterns, the important types are summarized in Fig, 133-4, [1 Fig. 133-40, complete mixing is assumed forthe Teed chamber and the per permeate permeate reject ied Tet Teed @ ) permeate permeate teed reer reject © @ Ficune 13.34, eal sow persia membrane span for gases: (a complete mising (by erse fn cl tuneruerent of ocr ove CChaper 11 Membrane Sepuraion Procoes‘mate chamber, Simibr toa continuous-stirred tank, the reject or residue and the product or [permeate compositions are equal to their Fespectve uniform compositions in the chambers. ‘An ideal cros-lee patter is gen in Fig. 13 3b, where the feed stream sin plug flow andthe permeate fowsin a normal direction avay from the membrane without mining. Since the feed compesition varies along is low path, the local permeate concentration also Varies along the membrane path In Fig. [3.-4c, both the feed stream and permeate stream are in plug flow countercur ‘ent to each other. The composition ofeach sream varies along its Now path, Coeurrent Now ‘of the feed and permeate streams is shown in Fig 133-44 14 Com -TE-MIXING MODEL FOR GAS SEPARATION BY MEMBRANES IB4A. Basie Equations Used In Fig, 134-1, detailed process low diagram s shown for complete mixing, When a separ tor element is operated allow recovery (ic, where the permeate flaw rate isa smal faction ‘of the entering fed rte), there isa minimal change in compesition. Then the results derived sing the complete-mixing model provide reasonable estimates of permeate purity: This case ‘was derived by Weller and Steiner (4). Using nomenclature similar to that for distillation (P7) using the feed and nonper meate flow rate 8 L nd composition x mole fraction and the permeate flow rate as Vand compesition y “The overall material balance (Fig. 134-1) ivas follows Ly = Ly + Vy 34a where Lis total feed fow rate in em? (STP), isoutlet reject low rate, em’ (STP) ‘and V, ‘scoutlet permeate Now rae, em (STPY/s. The ctor fraction of feed permeated. 0s given as ia L 342) “The rate of diffusion er permeation of species A (ina bina ‘equation similar to Eg, (133-6) but using em! (STPYS 35 inkg mols-om’ of A and B) isgiven below by an feof permeation rater than Mux (B)ina-nra sy omy low-pressure side iy bys ly LL high-pressure side }——> (cede a noss_jron Foun (341, Process flow for completing case Part 2 Separation Provess Principles stas where P is permeability of inthe membrane, cm! (STP) -emi(s-em* em HB): VI tow fate of A in petrieate, em? (STP): A, is membrane acca, emis membrane thickness. em ‘pis total pressire in the high-pressure (eed) side, 108m) tion Pros Pipes aCase 2 In ths case 8a and pypy are given and y,.X,. and Ay are t be determined, Equation (13.47) eannot be solved for, since x, is unknown. Hence, from Eq. (1349) i substituted into Eq. (13:47) and the reselting equation solved for using the quadrati ‘equation, lo ave assy where a 2 Pe dye an a a ae tO ah atl satay Da Mm After solving fry, the value of x, iscaleulated from Eg. (134-9) and Ay ftom Eg. (13410) EXAMPLE 134-2. Membrane Design for Separation of Sir Ie is desired to determine the membrane area needs! to separate an airstream using a membrane I mi thick with an oxygen permeability of "y= 500 x 10"" em’ (STP) -emi(s-em'-cm Hg). Ana? = 10 for oxygen permeability divided by nitrogen permeability (S6) will be used. ‘The feed rate is Ly = 1% 10" em* (STP) andthe fraction cut # = 0.20. The pressure selected for use are p, = 190 ‘em Hg and p;= 19 em Hg, Again, assuming the complete-mixing model, cle late the permeate composition, the reject composition, and the area. Solution: Using Eq, (13:11) fora feed composition of x, = 0208, PL Ply Po Pw Ps gallo Pe = 9 at 2) ~ 102) ~ wo! « (2 Joa) = -282 (02) 902) 08! « w( 22 Joa) = -2se bee tay a a ares ale = aa ay a nos 2-020 - 2 4 Beary s = 02-020 - 2+ aay « 102) i ») of 2 so) = ' + 10 22) - (#202) + 020) =n y= sate, = =190209) = -209 | + VEE as i a | : [gan TR, } _-sa01+ VB S229) i ws Chap) Monae Spnion reeseSubstituting ino Eq (1349), “oO Finals using Eg (13.410) 10 find the area, 0.200 — 02405060) a = oats PL TPAD = Pate) 0.1 100.5067), © [00% 10 M254 x 10 )(190 x 0.1345 — 19 0.5067) = 3298 > lem 184C Minimum Concentration of Reject Stream all ofthe feed is permeated, then = | andl the feed compositions; = yp. For all values of © 1. the permeate composition y, > (HI). Substituting the value ,~ 5, into Eq. (134-7) ue fs obtained as nye eS aay wna ine mene rao competed em T rp bn i tn tanedbs died or pf Soul aka ed EXAMPLI 14-3. Effect of Feed Composition on Minimum Reject Concentration Caleulate the ninimum reject concentration for Example 134-1 where the feed concentration 1 = WS, Also, what isthe effect of rising the feed purity to x)= 088? Solucion: Substicuing x oft ver n2a- sa] ACen S0into Eq, (134-12), a wa) tay ox{t can-n(2)-00] ay 0% Fors, = 068, +0 n(2)a 00s) a 00 Tq) 068) + OE ° Pant Separation Process Pilesa6 125 COMPLETE-MIXING MODEL FOR MULTICOMPONENT MIXTURES ISA. Derivation of Equations |When multicomponent mitures are present. the iteration metho! of Stern eta. (SI) quite sel, This method will be derived for ternary misture of components A.B. and ©. The process fw diagram isthe same as Fig, 13461, sshere the Feed composition «is. 89 amd fhe The knosen valves ace pact Sys E85 Ps Pr Pe Ps Pa “The unknown values tobe determined are pe Bye Bye Bote Sam ues Wyo LM Ay ing set of eight simultaneous equations i to Ey, (13-43) areas “These cight unknowns can be vbtained by so Using an iteration method. Three rate-of permeation equations simi follows for eomfonents AB. and C Yorn = Pasar ~ Pvpad (13s) P Aad Dyson ~ PaNgn) «13s.2) Vode = B Vose ® PAalatie ~ Pissed assay The throe mitera-balance equations Similar to Eq, (134-9) are written for components A, Band C was was ee et «13s Aa = ae _—_____ (BS) Aw “ 7 (13.5-10) Pi OO ain ~ Ov) ~ Pipa | Charter 13 Membrane Separation Proce | | | i |Rearranging Eq, (13-10) and solving fr sail — 0) 8 Tag) + opal => Be Ina similar manner Eq (135-12) is derived for 3 et) 2” TPEAR) + @palll ~ 8) 13SB_ Meration Soluion Procedure for Multicomponent Mixtures “The following iteration or trikand-ertor procedure ean be used to solve the equations above: 1. A value of yi assumed where J > 2. Using Eg, (13:42) and the known value of 0, Vis calculated. 3. The membrane ares is calculated from Eq. (1359) 4. Values of yor and 3, are calculated from Egs. (13.511) and (135-12) 5. The sum 3 ye ivealculated from Eg. (135-7). If this sum is not equal to 1.0, steps | hough S are repeated until the sum is 1.0, 6, Final Su and yc ate calelated from Eqs. (135-4). (135-8), and (13.56). EXAMPLE 135-1. Design of Membrane Unit for Multicomponent Mixture 'A multicomponent gaseous mixture having a composition of 4 = 025,74 = (0.55, and xjc = 20's to be separated by membrane with a thickness of 2.54 10- em using the complete-mixing model. The feed Mow rate i 1.0 x 10¥ cm (STP)isand the permeabilities are P= 200 > 10-em" (STP) -em(s cm sem Hi), Pj = 30 % 10-", and Pe = 25 % 10", The pressure on the fed side is 300, ‘em Hand 30 cm Hg on the permeate side. ‘The traction permeated will be 0.25, Calculate the permeate composition, reject composition. and membrane area us ing the complete-mixing model Solutton: Follywing the iteration procedure vale of yy Substituting into Eq, (134-2) for step 2 10s assumed. Vp = Oy = 028 % 1.0 % 10! = 025 x 10% ent (STP Ys Using Eq, (13.59), the membrane area for step (3) is Ph ey ] pi peels eon ~ res] 025 x 1oHos0j2.54 x10) / 20x10 (025 028 x 050) ~ 39080)] [= 4.536 > 108 ent? Pad Separation Press Picples astFollowing step 4. the values yyy and yp. are ealeulated using Eqs. (135-11) and (35-25 Pest) 500 158i = 928) Wa = We 456% WF) © ad (0 436% 10) PO Substitating into Bg. (13. Dine = Yo t Yon + Yow 128 1.5000 + 05366 + 0.1159 For the second iteration, assuming that yj, caleuatet 45. the following values are S840 % Wem? yg = 04410 De = 09882 The finaliteration values ae Ay = 336% IP em? ypg © OASSS. yup = O4SN2, and ve = 0.0943, Substituting ito Eqs. (135-1), (13.53), and (13.55), ® roa nom Liga p52) (0.855) = 0.1815 sen hg gon gOS we = ate Tag) 025 pean | da, [volume cles Tow Froune 1361, Process flow dig for roeow mode (On the low-pressure side the permeate stream is lmost pulled into vacuum, so thatthe flow is essentially perpendicular to the membrane. “This model assumes no mixing in the permeate side as well as no mixing on the high pressure side. Henee, the permeate composition at any point along the membrane is deter tmined by the relative rates of permeation of the feed components a that point. This cross flow paltctn approximates that nan actual spiral-wound membrane separator (Fig. 131) with »high-flux asymmetric membrane resting ona porous felt support (P2. Rt) Referring to Fig. 1341, the local permeation rate over a dillerential membrane area 4A,c at any point inthe stage is vav = "ips pyldy (1361) Pi (1 yyav = “Bp = 2) ~ pill ~ 9) dy «1362 Where d= dV and is the total flow rate permeating through the area dA. Dividing Fg, (136-1) by (1362) gives y etfs (mindy ay" 1 =8)= Grip 9) ey “This equation relates the permeate composition yt the reject composition x ata point along the path Teis similar to Fq, (13446) for complete mixing. Hwang and Kammermeyer (H1) sive a computer program forthe solution of the above system of differential equations by hnumerical methods Weller and Steiner (W3, W) used some ingenious t tain an analytic! soltion tothe three equations as follows: erin SERS (Lp aan osformations and were able to ob Pani Separcon Process Princeswhere “ap7 aD =F Go-Tea- Fh 1 "per ‘The term wis the value of wat = J, = ny ~ 4). The value of 0s the fraction permeated ‘up othe value of vin Fig. 136-1. At the outlet where x =x, the value of @* is equal 108 the total fraction permeated. The composition ofthe exit permeate stream sy, ands calculated {om the overall material balance, Eq. (13:49) ‘The total rembrane area was obtained by Weller and Steiner (W3, W4) using some ad- tional transformations of Eqs. (1361)-(136-3) to give a5) i+ PS (1365) where fi Values of "in the integral can be obtained from Ea, (136-4), The integral can be calolated numerically. The term is the value of atthe feed tan the Value of at the outlet ‘shortcut approximation ofthe area without using a numerical integration, available from Weller and Steiver(W3), has a maximum error of about 20% 1368 Procedure for Design of Cross-Flow Case Inthe design fos the complete-mixing model thete are seven variables, and two of the mot, ‘common eases were discussed in Section 13.41, Similarly for the eros-flow model these Caper Membrane Separation PressesCase "The values of 4.45.0 and ppg ae given and yj. and Ay are to be determined The value of # orf ean he calculated directly fom Eq, (186-4) since all other values this equation are known. Then y,calelated from Eq, (13.49). Tocafeulate the atea Ago Se resof values «lessthan the feed s;and greater than the reject outlet, are Substituted inte Eq, (13 6-4) togive a series of #* vales, These values are then used o numerically o eraph ically integrate Eq, (11455) t0 obtain the area Ay Cave 2 Inthiscase the values of 0.4 and ppg ae given and vx, and Ayre to ede termined, “This is rial and error, where values of, are substituted nto Eq, (13,6) t0 sve the equation, The membrane arca i calculated as in Case 1 EXAMPLE 1346-1, Design ofa Membrane Unit Using Cross-Flow ‘The same conditions for the separation of an ai steam ay given in Example 1342 for complete mixing are to he used i this example. The process flow ams will ein cron The given vlles a x, = 0209.8 = 0.20, 0 = W. 190 em Hg py ~ 19cm Hig. Ly = 1 Wem (STP), By = SO 10" em {81P) emits e-em Hg). and e™= 284% 10-¥em, Do as follows: (a) Caketste ff. ad Ay 1) Compare the resus with Example 134-2 Solution: Since his isthe same as Case 2, value of x, = 0.1642 wil he used for the tst ral for art (a). Substituting ito Eg. (13.64) Un Pe J [cio i = 05| SBP + 10} = 4550 p=o5{ (ean, reo ” often aD 1 eF @b- He? Thane — 09%) Pant Separation Proves Pracples wotot ans = 4580 — agT7sio9s ~ “VME = bi + (DYE + 2H + FNS = (4S50)(02612) + (Cass) 02602)" + 2406775) (0.2612) + (980)"]"° os (4550) (0.1965) + [(4.350)°(0.1965)° + 0.6775)(0.1965) + (0950)! 008s (=o) =) _ d= eey(t - ot682) or) i= 0209) = (bez swamzstasany 0.3089 067954.550, (ga? = 100980 0" 0.5089 = 10+ 0950, (2asr=aesay * osm 0950 Solving. 8" = 010392. This value of 0.992 does not agiee withthe given value of @ = 0.200. However. these values can be used later to solve Eq, (13653) For the second iteration, value of , = 0.142 isassumed and is used again to solve lor @* in Eq. (13.644. which esulls in @® = 1482. For the final iteration, x= 011% and 2000. Several more values are caleuated for later use and are: for x, = 0.187, = 0.04876, and for x, = 0209, 0" 0, These values are tabulated in Table 13641 Using the material-balance equation (13.4.9) to calculate y, i= NLL =#) _ 0209 — 0.119001 ~ 0.2000) . 2000 560 TaMLe 1361. Calenated Values for Example 120-1 ” * % F ° 0209016550 a64o4 0187 0.18% 6S FIV 0.099262 OBIS 08246 01482 01420 O90 asH0 1.2000 0.1190 ses) Chaper 1S Membrane Separation ProcesesTi calculate jy at #* = 0. Egy (1863) and (13.417) must be used. giving ) = M550, “Tso fr the area, Eq (80S) can be writen as [___a-ea-» iL [cml 2G] tale 11366) ‘where the funstion is defined as above. Values of F will be calculated for di erent values of in order to integrate the equation. For 8* = 0.200.x, = 0.19, and from Eg. (13.64), ons _ = 013s (I=) (= 0.119) oust From Ey. (1365). f= (DEF) + (DP +2 + PS = (SS x 0.1351 ~ 0950) + (455)(01351) + 20.6775 01381) + (095)°P° = osmis sng the detnition of F; from Eq. (1366), wenn “ “lr RG i] (= 0201 - 0119) oma -onstfrtae -2(— TY ow onss0l ar ~ (rar) | = 11820 ‘Other values of Fare caleulated forthe remaining values of #* and are tabulated in Table 13641. The intepral of Eg, (13.66) is obtained by using the values from ‘Table 136-1 and numerically intcurating F, versus J to give an area of 0.1082. Finally substituting into Eg. (13.65. ay M4 101 AF) 4 i wo Ph 9030 10 "YAW (0.1082) = 2803 « 10m For part (from Example 13.42. 5, = 0.5067 and Ay, = 3228 % 1" en Hence the coseflow mode! yields a higher ¥, of 0.5690, compared to 0.567 for the completemising model, Also, the are for the rosso models 10% less than forthe complete-mixing mode! Pa Separation Process Principles se137 DERIVATION OF EQUATIONS FOR COUNTERCURRENT AND COCURRENT FLOW FOR GAS SEPARATION FOR MEMBRANES IATA. Concentration Gradients in Membranes 1. Donvephase membrane. In gas separation sing a dense-phase symmetrical polymer ‘ntembrane. the solute dlfuses through the high-pressute-side gs film to the membre sur face. Them it dissolves inthe membrane, At the interface equilibrium occurs. The solute then difuses through the sof membrane, and finally difuses through the gas film. The gas i resistances are quite smal and can be newleted (NI). tn Fig. [\7-Ja the concentration profiles are shown, The concentration yin the Nowing bulk: gos phase is the same as atthe imterface of the dense polymer and depends on the flow pattern o the permeate phase 2. Axymmetric membrane. 8 Shown in Fig. 13.7-1b, the membrane ineldes a very thin, Lense polymer membrane which is about 0. 101 jm thick (MS, P7) anda very thick porous layer 0-200 pm thick, A typical hollow-siber memirane for air separation has a 1D of 95 am and sn OD of 13S jm. with wal thickness of 2 jm ‘The concentration gradient inthe thin dense polymer phase similar to that for the symmetrical membrane. However. the concentration y of component in the bulk permeste ls phase snot the same as atthe surface of the thin dense polymer layer. The concent tion y of the balk gas permeate stream depends on the flow paticen and material balances Aso. the value of y can be greater of less than ‘The porous layer isso open that there is assumed to be litle oF no resistance 10 the How sand ys constant along this path. Hence. iti assumed that there is no penetration or mixing ‘ofthe bulk gas phase y inside the porous layer 1L7B Derivation of Equ Symmetric Membranes for Countercurtent Flow in Dense-Phase A flow diagram for this countercurrentlow mode! is given in Fig. 47-2, where both stecans are in plug low. The derivation follows that given by others (BI. NI, P& WS), sense phase ‘ polymer wy FrovRe 137-1, Concontnaun prope in membranes (a denecphee symmetrical mene Chapter 13 Membrane Sepa Process | | |il Ledinay po] ow A any as jai Daa ib Pn _! rset gut i athe Te)ly x tw ° Lay fa aera 1a, fow me ‘volume element se 137-2, Plow dug fr the counercrvem sto model ih dems phase Making total material balance. Lot, «stay ‘where Lis total feed Now rate, con (STP) L, i outlet nonpermeate (eject) flow rate.em (STP) and V, is outk permeate Now rate, em’ (STP)S. The rates of permeation of A and in Bin a binary mixture are similar to Eqs. (13.43) and (13.44: Vlg = VIA = (PHO (OX ~ Bry) «1372 VplAy = VU ~ 9g (PHL =) = p= 99) «1373 ‘where is permeability of A. em’ (STP) -enys-em!-em He): Vis low rate of A in per meate, env (STPYs. A, i membrane ares mp Goal pressure in the high-pressure side. ‘om He: aa pis toral pressure in low-pressure side. em He, ‘The lux ofA outof the element with area dA, is dL y= yd. = (PUP ~ PrN] dy ast) The fax of Bis dh y= (1 ~ yal = (PaiD|pAl ~ x) ~ pl ~ WI) day «1378, Making total halance on the reject stream for area dA L=L dl + dla + dby 1376) Thiseines dL = hg + dby ast Making a balaneeon A for area dA, Ly = (LAL y(n = dv) dla re) Rearranging. dL y= Ldx+ sdb Substituting Eg, (1377) into (13.7. Las Ha a)dl y= vdly Pan 2 Sepa Proves Pricples mesMaking otal balance on petmeste steam for atea dA. VeV-W tty edly «azn This ives AW = aly + dy «37.12 Making balance on A for atea dy Vy = WV —aVyty dy) + dl ata, Rearransing. dla = Vay + av «319 Substituting Eq (137-12) into 137-14), Vay =(1~ y)dby~ydby 1374s) “To eliminate the variables L and V. an overall bance is made forthe area dy sd the reject outlet stream: nLty (3.746) Lee Lis t¥y ass ‘To climate V. VS Eq, (137-16) substituted ino (137-17) and solved for L Lm Lis, y¥t~ y) (37.48) Tocliminate £1 fom Eq, (137-16 stituted ino (13.717) and sls for V = balay — aie = 9) 319) Substituing Eq (13.718) into (137-10), MeN ayy dy as7.20 Substituting Eqs (13.74) and (13.75) nt (13720), Lass = 9) ds aay MPU = DUI) Ag = PHNLEL =O) pl *)ddy BT Rearranging a Gin ta = (SE )te atte ot) = =n) «sry where = pipy and at = (PAIN Pit In a similar eranner, substituting Eq, (13.719) into (137-15). Labs, — sy Ter gy Tn db = vay «137.2 Chaps B. Membrane Separation Proveses‘Again, substituting Eg. (13.74) and (18.7.5) into (137-25) and rearranging. te A (22) yen) == 9) A= hin &a To (729 Dividing Eq, (13724) y 137.20. ay vlat(x~ ry) — x= a) tt 9) Ne " 137.28) a d= = a9) RH Inserting Eq (13722 dy =b sails = 8) a ee ee) Pam, f= “D IC Solution of Countercurrent Flow Equations in Dense-Phane nmetric Membranes {At the outlet of he residue steam of compositions, the permeate » and x, ane related by Eq, (13-46), epeared here as Eq (13,727). where y y ete (pipe! - 37 Ty" Gs) ini 99) «saan The solution to this quadratic equation is given as Eg. (1347). In order to salve Eqs. (137-25) and (137-26), the following procedure ean be wsed, where s, is known a st 1. Using Eg, (13.727). the value of 'isealeulated for 2. Tointegrate Eq (137-25). the vale of (dyidt) ax =x, must be caleulated, However this value is indeterminate sine the denominator i evo, Using L’Hapital’s tule (NI, PA. RI) the numerator idifferentited with respect to xand the denominator with respect to and the valle of yisct 38 to Be GO. ar «37.28 Starting at the residual end at x. Eq (187-25) is inwegrated numerically W give the severstisr relationship and s, (PS. RI) 4. The relationship of y versus is substituted into Eq. (187-26) whichis integrate feos to, toobtain the aren A, §, Substituting intethe material-balance Eqs (13.48) and (13.42). the cut or faction of feed permeated, @ iscaculated (NI. RU. WS), 6. We ie set and i unknown, the solution is trial and error. ‘The vale of s, is assumed andthe inegrat on of Eg, (137-25) is performed to oblainy,. Then 4, is eleulated trom Eq, (13449). Thisis repeated until the assumed and ealelated values x, agree Pan 2 Separation Process Proscipes1870 Derivation of Equations for Countercurrent Flow in Asymmetric Membranes the flow diagram for this countercurrent low model is shown in Fig. 137-3, where both ‘streams are in plug Nose. The permeate y' leaving the membrane differs from the symmet ‘membrane ease and isnot the same as the bulk phase concentration y at this point. This also shown in Fig. 137-Ib The Mux of ut ofthe clement with area dA is Ly = yl = (Patt DAN PV day 4137.29) where vi given by Eq, (137-3), which is similar to Eqs, (137-27) and (13.46) y atte —(epsiy') = — 137-8 (nies 99 (ero, The fx of is Ly = (1 sdb = (Py PLL= 8) pL "V)ddy RABY Equations (137-29) and (137-3) difer from Eqs. (13.74) and (13-5) forthe symmetric "membrane in that ys sed instead of y in the terms for concentration diference ‘The rest ofthe derivation is identical to that for the dense-phase symmetric membrane (NI.R1). The Hina equations are Ly de _-(x-y) Prin da. 8) H(L = matte 199) = al == r= yp assay wu rt = y' Nh shatic ry’) = aft =x) =r yp ame Inverting E47 ts 137-34), de (Pale KL «ns semen Wa) Powe a tow ISM lug ow 1 aby’ fas dense membrane a FIGURE 137-3. Rove digeam for coumirernt fae with asymmetric membrane Cope 13 Membrane Separation Poceses coEquations (13.727) for and (13.728) for (dada) at C= 4, for symmmetsic membranes ae ako applicable here lor asymmetric membranes, The method of solution for the above “equations simi t tha for symmeteic membranes ISTE Derivation of Equations for Cocurrent Flow in Asymmetric Membranes For cocurrent fly the eveurrent madet is shown in Fig. 7-4. The derivation uses Es (137-25) (037-31) asbefore. Proceeding in a manner similar 1 the countercurrent case the final equations are (M1. P4. RI) dy (= 4) [= wate = ry) = MU = == YD ae OTe MET) al = TS 7 ae oC ds Pulm Wee 15) = a1 ID) ‘The method of solution is similar to that for countercurrent flow. Integration of Eq, (137-35) is started at the feed inlet, where i determined by using x instead of x, in Eq, (137.27). Then, using Eq. (13.728) with x, instead of x, (ids) atx = is calculated, “This then used fo integrate Eq. (137-35) staring at the Teed end, where x = sy. Finally, Eg, (137-36) i integrated to obtain 4137.36) IAP Effects of Processing Varlables on Gas Separation 1. Effects of presoue rao and sepanaion factor on recovers: Using the Weller-Steiner Eq, (1346) for the complete-mixing model, the effects of pressure ratio, pp. and separation factor. *, on permite purity can be determined for a fixed feed composition. Figure 13.75 isa plot of this equation for feed concentration of 30% (7). For symmetric and asymmet re membranes, this equation ean be expected to provide estinates of product purity and trends for condition: of low to modest recovery inal types of models, including complete ‘ising cross-flow, and countercurrent Figure 1375 shows that abowe an a of 20, the product purity is not greatly affected. Also. aboue a pressure ratio of about 6, this ratio has diminishing effect on product purity. Vea etme yotae toy og R Te ee oe eal plug toe SSSMy aden WIS fecdin hat Vase | reject ut Te] | | reaeeamae ‘ i | phew —| Proves IST Ploed sam for cosnie ss with ast mob Pant? Separaion Prosess Prcipes70 Permeate purity. ¥, 0 20 0 o 0 Separation factor, a Fico 137-5. Efet of vepanation factor and pressure rato om porte pis (teed = 030) [from "Membre Separate Canes Steves, eB. Stookey, C1 Paton und GL Malcolie Chem. Eng Progen §2(11 36/1990 Reproduced by peroitinof te Aaer ‘im Ins of hema Engineers liquids are present in the gas separation process. liquid flm can inerease the mem. brane resistance markedly. Liquids can also damage the membrane by chemical action or by swelling oF softening. IC water vapor is present in the gas streams. the dew point may be Feached in the residue product and liquid may condense. Condensation of hydrocarbons rust also be avoided. 2, Effects of proces low patterns on separation in symmetric membranes. Detailed para ‘metre studies hve been done by various investigator (Pd, PS, W5) for binary systems. They ‘compared the four flow patterns of complete mixing, cross-flow, cocurrent, ad countercur ‘ent low. In Fig. 137-6 (WS) the permeate concentrations shown plotted versus stage cu, 8 fora feed of airy ~ 0.209 for oxygen) with a” = Hand pip, = 5. Is shown tha, a8 x pected, the countercurrent flow pattern gives the best separation. The other patterns—-cros. flow, cocurrent, and complete mixing—give lower separations in desoending order. Note that when the stage eit @ = 0, all fow patterns are equivalent wo the complete mixing model and ive the same permeate composition. Also, at # = Lal patteras again give the same value ‘of yy = 0.209, which is also the feed composition "The requited membrane areas forthe same process conlitions and air feed versus tage cut were also detrmined (WS). The areas fo all four types of low pattern wete shown to be within about 10% of each other, The countercurrent and cross-flow patterns give the lowest area required, 3, Efects of proces flow patterns om separation is asymmetric membranes. Caleulations us- ing the mathematical models for asymmetsic membranes give virally identical perform ances for eocurrent and countercurrent Row (G1, P2 PS) The porous support prevents mix: ‘ing of the bulk permeate concentration and the skin surface concentration y” as shown in Fig. 137-1b, Hence, the direction of the bulk flow permeate stream has no effect, Exper: Chapter 18 Membrane Separation Proveses 1Permeate punt. yp 02 L 4 o 02 os 06 Stage eut, 0 FraUne 1374. ere om:patern i ssnetrc membranes. Operating con tora olin sy 200 0 HP ‘um dhe som Bie 8 P= sim?» 1 Sen ISTP ena Hg (Peonteraten fos 2) emf 3 nf 4 compte ming WS. Reprinted ro WP Wun and 4 Sten Sop Sei Te88# 059) Be sent Manel Beker imental tests using helium recovery from natural gas (P2. Po). nitrogen recovery fom sit {GI} and helium flom nitrogen (G1) show that the experimental data and the model predic tions agree quite wll 4 Effect of pres drops on separations in asymmetric menbranes. In hllow-Fiher mens francs (Ni). an appreciable pressure drop ean occur for low inside Tons. tuhes oF for thes ‘wth very small ingle diameters, In the shell side the pressure drop i generally very small tnd isneglevted. Pressure drop in the tubes isalvays detrimental fo the separation, For feed inside the tubes. the actual average feed pressute will he less than the inlet feed pressure. I the permeate flow is inside the tubes, then the aetual averag higher than the permeate outlet pressure, In both ofthese eases the driving force fr perme ation is reduced ales separation occurs Ti reduce these presire eflecs, where the Stage cut Mis soll. giving a low permeate ‘ow rate. it is prerable to have the large fee low ate in the shel. where the pressure drop tthe feed shouldbe inside the tubes. where mont of the fed pet 1: permeate pressure will be issmall. Fora high tage meates int the shal {Using the model equations the pressure drop ins using the Hagen Poise equation 2102) fo liar Now 3p Raw @=5) 7b he tubes can be accounted For by (2102) ~ z:istwual length, Writing this fra differential Length d= em and a dp, in Pascal aaszany Prat 2 Separation Prins PriComerting he ed Now fate Lem sat Tan (STP) tthe atv ea Fan py, oy Daf, Tp a a ) way where Vis the number of tubes in parallel. ‘The average viscosity seca he approximated by using the averuge mole traction ofthe feed and the residual outlet. The average jis then the ‘um of the mele fractions of each component times the viscosity af the pore zases. The final equation is (GI, NI, P2) (37.39) The atea Ay ca be related 10: by ay = DN dz. This then rettes de to dps. In inte rating the medel equations. a constant (uniform ps Hes assumed (GI, P2, PP) This gives the relation between yand.cand ly, Then using the material-balance equation (137-18) be teen Land yand x, equation (13.729) is used to generate anew presste protile. This pro- ed sss is then 148 DERIVATION OF FINITE-DIFFERENCE NUMERICAL METHOD FOR ASYMMETRIC MEMBRANES 138A. Countercurrent Flow The dow diagram for the numerical method is shown in Fig, 138+. Using the method de- Fived by McCabe etal. (MS) and taking an area tthe mass balanees on both streams ean he writen as We be «13s The value of y cam be calculated from Eg. (137-27) using for € and vg fot 9". AKO, yay ‘an be calelat2d similarly fom vq. Then. writing balance on. Avy, = Late «a3s2y Te Fiovee ISL Flow dy ‘ienen cam for ountereuren fw ith usinmete membrane wig fe Chapne 8 Membrane Separaon Processeswhere = Uy + a)/2: Substituting Le from Eg. (13.81) into (1382). «383 Equations (137-27), (138-2), and (138.3) can be solved numerically starting at the feed 1 = ty to determine the permeate AV and y, for each AA, and increments of x tox, atthe ‘outlet reject, Usually 1 or so increments of from x, 10x, are siliient Then to obtain the values of V and the bulk composition y as afunetion of. the eae lations started at, Using Equations (13 8:4) and (138-8), the increments of AV are added toget Vand yiscalslated for each AA, increment up t 4a the feed inet ve dav anes) wav y ae (138-5) For cocurrent cr parallel ow the only difference is in calculating V. Starting at inlet and wsing Eqs (13844) and (1385), the increments of AV are added to get V up 10 ‘Tocaleuate the area for countercurrent or cocurtent flow, rewriting Eq. (137-4). Pinon — 2 (386 where r= pip. The average diving forces (= 29 Ine [i = 8) + an = 8a «387 Solving for Ay. aves TPG de — I Starting a 4, i calculated foreach increment to obtain S 4A, versus. aay (138.8) IAB Short-Cut Numerical Method ‘Making an approximate material balance to obtain an OF yp forthe total area from yj to (M65), vis e+ ah 389 An overall and component material balance gives by het % 3810) Ls = batt Vy asin Substituting Eg (138-10) into (3811), Lay = (by ~ Velho Ved (3s. Equation (138-12) can be solved for V,and (138-10) solved for Pare? Separation Process Pracpleswm To calculate the approximate area for countercurrent or cocurtent How, Ey. (13.88) is rewritten forthe total area A: Voy case) An” (PT 7m and (¢, ~ 79). Since plots of rand y versus ofthe Ay cal where Ue — 19) i the In mean of 4 ~ 195 ight Lines, this approximate area within about 15 Agate approximately st ‘ulated by the fnite-tference method EXAMPLE [3.8-1. Air Separation Using an Asymmetric Membrane for Countercurrent Flow Wis desired to design a hollow-fber asymmetric membrane fr ae separation 10 produce 4 residue which contains 970% N; using countercurrent How. ‘The {dense polymer layer i inthe inside ofthe tubes and the feed is in the tubes. Ew perimental values for commercial membranes give separation factors a of (0,/N; between 3 and 7 (H2) with atypical value of 50 (Gil). Permeance values of Pile are given (H2) of 5 10°10 250 x 10cm! (STP) (sem em Hg) with atypical value of 20% 10°" (GI). The 1ypical values wil be used. The feed oF tube side pressure is 1034 KPa abs and the shel side or permeate i 105.4 kPa “The feed ate of ait is 10D (STPY Ih {a) Using the fnite-dfference method, calelate the permeate composition, ‘he fraction # of feed permeated, and the reside and permeate Rows Assume negligible pressure drop in the tubes. Calculate the composi- ton y ofthe permeate aa function ofthe residue compositions (b) Caleulate the membrane stea needed. (6) Using the short-cut procedure, calculate the permeate composition, 0 hows, and membrane area, be Lo, 2037] ero Peni Ficune 138-2. Finetifoence tomes for coumecnvent tow in Example 34 Chaper Membrane Sepa Processes ald | {(8) Repeat (a for cocurrent flow: Plot x.y. and for countercurrent and cocurrent flow versus area, Solurion: For part (a), Pap) WR KPa, Pl ing Table 13.31, ha (STP YH, 4, = 0.208, x, = 005, p, = 104 201% 10) "em" (STP) (sem sem Hg). a* = $0, Us Plt = 20% 10-")(7501 X10) = 1.800% 10 "mn (STP Ys mPa) 1 = pin, = WORANOM = O10 Starting atthe fed inlet (Fig 13.8.2), where from x;= 4) = 209102; 0209, ysing am area Ay. going 194) and using Fg. (137-27) 0 calculate ¥ vi eins — (pleads) - qo 37.29 197 T=) = Wren =) ee “The solution to ‘hiss given bythe quadratic equation (134-7 = batho te ase7) wherea =I = afb =—1-4a" 4 Lir+ sina — Vande= ~o%es, Substtut ing and solving ory, where x, = 0.208, 5, = 020, 22.36 + [(22.36¥ — 4 3-40) 108)" asia ‘Again for xy = 2.190 Then. y= iy #902 4. (13853), 1.4830 obtained from Ey. (137-27), (0.5L88 + 04830)/2 = 0.4989. Substituting into Lugar — 35) _ 10.40.200 ~ 0.190), 2002 EH gous mt (a — 0) {0.4989 — 0.190) Y Then by Ey. (12841). L vay) 1, = AV, = 1000 — O61Sh = 9389 mh (049840 6151) = 0.3089 For the second increment for A in Fig. 1882, saving for ¥ with 6, = 4170 a= 40, B= 140 + 40(10.170) = 208 6 = —SIK0.170) Using Eq. (1347), xi = O4N71, Then yi = (4 19) = A465 2 = (assy + ass7H 2 Part? Separation Prosess Princes“Tyme 138-1. Componitions and Areas for Numerical Method it Example mtr an Counsrcurent Cocuren 0209 03st sits sis 0.190 02983 0.4989 04800 0470 02769) ost? oar 0480 0.2549 (04637 oss os 2m a6 0.3665 oto 9.200 42a ot 1.0% ost 4021 02726 oro 0.1593 02108 050 0.1322, 0.529 00 oto 03st 101 gy, Hane) (0190-037) on min eas) ose ait) Also, Ly = by — AV, = 9.3849 ~ 06364 = 8.7489 ms i AV: = 46511 0.6360) = 0.2958 “This is continued, and for the eighth inerement, x5 = 0.07. xy = D050, ¥, = (0.2198. y= 0.1629, yg = O.19T4, AV = 0.7757, and Ly = 4.7088, For the final for ninth increment, p= fy = 0050. & = 0.00, yp = 0.1629, yg ~ 0.1014, 0.1322, AV, = 09215, :ind Ly = Ly = 3.7873 mh. The permeate flow rate <1. = 10.00 = 39873 ~ 62127 m'/h, The stage cut 8 = 6.212710.00 = “Tocalelate the bulk composition yas afunetion of «for countercurrent low, itisnecessary tostart atx, Using Eq. (1384), v= Dav For caeulation of v using Eq. (138-8). WV, _01522009215) _ 4218 Ve ons 092s For the eighth plus ninth increments, Vig + AV, = 0+ 09215 = 09215 By % = 0322 Vee Dav avs ay, 1921S + 0.7757 = 1.6972 Zvg AV _ O12EE + 0.1918(0.7157) wey Loar “This caution is continued up to the feed entrance. Values of sx and are sven in Table IBS+L sas Charter 12 Membrane Sparnion Process“To calelate yas. function of x for cocurremt flow itis necessary to soe a, For the fist increment, from Eg. (138-4) v= Dav =0 4 av, = + 61st = a61st Soy A _ O4NNOIST) aM v7 Geist ~ a6isi ~ ne ro) For the second increment. Ve Sava yy + av, © 6151 + 06360 = 12511 0.3089 + 4.4651(0.6360) eee = 04817 This calculation continued upto the outlet at, For part (h). Eq. (138) is used starting atx, for both countercurrent and cocurrent flows. For te fist inerement, the ow rates in mh are converted to rms by multiplying by (1/3600). Also, x) = 0209, x D518 ‘1.4880. v4, = 0.889, AV, = 0615] mh, and py © 1034 KPa, Caleulating x 79" 1 points [and 2and the average (x ~ r¥) [rom Eq, (1387) y= ry} = 0209 — O.IKOSTA8) = 0.15752 0.190) — 9.146.4430) = (ery) = (O1STS2 + 0.14170)2 = 0.1496 14170 Using Eq. (1388). {46151 (1/3600 (0.4989) TR > 1050-1496) 64m! (500% 10 046$1, and Vs = For the second inerement, x) = 0170, 9) = OTE. (06360, Then, as y} = 04si70 ry —2¥1 = MAD 010.4471) = 0.12529 (9 = rq = (4170 + 0.12529) = 0.3350) 940 1/3600)(04651) (1.500 10 "(2034 ¥105)(0.13380), aa, = 2988 “This is continued, and the results ate given in Table 138-1 The final total area is 4591 For pat (¢) asing the shortcut procedure. Ey, (188.9) gives the value of, bp Mae = (95 4 002 = (OSHS + 0.101492 = 03081 “This value of WISI compares 40 O.3ISI for the numerical method. Making a ‘component balanee in Eg, (138-12), Lay = Uy = Vile Vets 1010209) = (100 ¥,)003 + V0.8)plete Area Far 1383. rvs re for manera tad Solving, Vp = 6487 and £., = (10.00 ~ 6.37) = 3.563. This gives a stage cut = 643710001 = (.6437, a compared with 0.6213 or the mumerigal method. To calelat the sea the Utiving foroes are sy — Fs} = 0.00 ~ o.10)05148) = 0.45752 5, ~ 185 = 0030 ~ 0.10(0.1014) = 0.01986 (0.15752 ~ 0.01986) igo. t37Sz;0 01956) ~ MOS Ue Wa The atea from Eq. (138-13) 6.237(/3600)(03081), (1.50050 10 )N4 x TOKO) An S843 This value of $3.43 is about 16% greater than the numerical method. plot of these dat forthe numerical method is piven ia Fig. 13.83. IASC Use of Spreadsheet for Finite Difference Numerical Method. The numerical method can easily he adapted tha a spreadsheet can be used to solve the problem forassmmerie membranes. Using Exeel” or other programs. basi formulas can be entered into cels ‘Gust dats fom a spreadsheet are given in Table 138-2 for Example 138-1. Input data for the caelations are briefly as follows: cells D3-DIO known values are entered. In cell DIL the equaticn for r= pip i given bythe formula SDSN/SDS7. Row 1 is ese lo keep track of the indexes use in this past ofthe ealeuation. Row 14 sts the input ales ofr. and son, In rows 15-8 the vales of a,b ean y” are ea ulated using Eqs. (134-7) and (137-27). Far example, in cell BIS the formula entered apts IE Membrane Separation Provesoa sopdanneg song nomads out ‘Tony 1382 co we " 1 1 k 5 a ae bes a T[T,Afoed rey WCaxcou 7 be 3] 3 (Ormole 20 or poe Tas Pa =a ean Taxa Pa STPY | Som Pa t awar wen [eee | asco | Sou) | eae ine soico | erro, erort | user Sat ToUsT Slot | omnes Ee | veOm | UNISS Seco 8 i r = z are oer con enc E00 wore HEe0 sole se nse ‘cons = omnes oONor | omc _| oes | omer ‘omit | anon | Oe om | one's | an = 0 wafer 10) 6 x 5 oF Membrane Separation Process apie 1weve | a SO oF or cai wav [ome ao | aw wir iF is ir eH} | svosy au 2 in iiso_| sose SLi i Faust [onset [0c ae wee olses [OIF Tinos | se 6 Ts Z re LC z z Forze [cnoseny on SpA w > Supartion Poses Principles Pant?is =(-BlO+SORT(BU6*BI6—4BL"BIM)) BIS). In row TH y= (9h 9H) In row 20, AV is gleulate from Eq. (138-3), The formula in cell C20 6 = B2IMBLE=CLy, (C19~Cid) and in DI =C2171C14=-DU4y(DI9=DI4), In tow 21, L is ealetated from Eg, (ASD) where Ly = Ly ~ AV, by using the formula in cell C21, which s = (C20~B21), tor C22, = =(D20= B21). and s0.0n. Row 23 is mew set of mdenes for countercurrent Ho Ty calculate V in row 23 Using F4, (13841, where V = SAV. and starting atthe outlets. the formula in cell K24 nd so on. For ow 25.tocaleulate S AV. the formula in cel fs =K2.in 2, =120rK24, 1K25 #5 =K19°K20, in J25, J19*320-+K25, and so on. For the bulk. permeate composition, v 's calculated in vow 26 from Eq, (135). where y= Sv V/V. Th cell B26, the Form is 25 B24, Rows 28-32 ate optional and are used to check the mass balances forthe inlet and ‘outlet streams. fo cell B29, the mass in is =3DS4: the mass out in BAO is lori cell BSE 8 =SDS4°SDS5 and B32 is =B2WB26¢ KUKI, For cocurent flow starting a4 Eg, (1384), where V = SAV. s calculated in row 3S, In row 36, Sv, AV is calelated using the formula in esll C36 of =19°C2, in D3, =DI9*D2+ C34, and so.on. Then Eg. (13.85) is used to calculate the bulk composition y fram S APIV in now 37 To cafeubte the areas. in row 41 (c= 19%} is calelated for each increment, us ing Ey. (138-5). The formula in ell BA is =((BIS~ SDSEI"BI8)+(CHI-SD5IL*C18)2 In cell BA2 the conversion of V mith to mS and KPa to Pa is perlormed using ‘SD99°SDS71000°3600). In row 43, using Eq, (1388) to calculate A. the formula in coll B3 is C19*C204(SBS42°Bdl). In row 4 all of he AA, values in row 43 are added to get the total A sing =SUM(B83: 43), HFK, Simi ISD Caleultion of Pressure-Drop Effets on Permeation 1. Estimation of numberof ubes and length. In order to calculate the pressure drop inside {the hollow-Aber tubes. the dimensions, numberof tubes, and area A,, ofthe membrane must be known. The following procedure can be employed. The shorteut procedure is frst used with Eqs (1389)-(138-13), This gives Ly. L.Vp Vad Ay. Then the average Now rate in the tubes is cakulated from the equation Ly = (Ly + £72 “The nutter of thes in parallel Ny mmist he estimated from typical laboratory or com- mercial data, For example, for air with a Mow rate of | mY, 3.8 % 10" fibers QN;) are used with an 1D of wm. anda length (2 ~ z;)of #8.26cm. Fora lw rate Lot 10.0 mh in Ex ample 135-1 and to keep a similar and reasonable velocity inthe tubes. the V; needed wll be Uirectly propentional to the inlet Ly. Then, knowing the Ay, an estimated total length (cs s,) ofthe tubes can be eaeulate from Fg, (138-14): a (3819, Ay = DN 2. Pinteaiffernce mertod 1 dnclude eet of pressure dep. For the fnie-ifference ou ‘merical method, Eq, (13814) can be retiten as Ay = ZN casts) Aso, Bg. (1338) can he reuriten fr a finite increment of Az length doy _ =! (, Tm) «3810 av IT iw . CChaper 13 Membrane Separation Processes 7 | | | I‘The following steps. which may requite several iterations canbe use in the inite-iflerence numerical method to aslude th effect of pressure drop inthe tubes 1. For the fist ineremsnt shown in Fig. [B82 constant inet pressure py (8 wed for Pon wealouate yand 5, AV. Ls and Ay, fom Eqs (13.727). (381 C1889). (13 87) and 1388), 2, The value of Ny is ebtained from typical data as discussed above in Subsection 1, Using Eq. (138-15) the insemental length 2 i obtained 3. Using f= (Ly + 12 and the inlet 74. Pg the py for the frst increment scale Fated fom Eq, (13816). 4. For the second iteraion. the new pt use icaleulated from Py. = pay ~ Apa/2. A new value of the outlet p= pay ~ Apy ivused to recaleulate a new y! from Eq. (137-27). The value of yj remainsthe same, Then by repeating steps I through 4, new value of 3p) ‘obtained, Usually only three or so iterations are needed t obtain a constant vale OF 3, Pha: ANd AA. Using a spreadsheet as in Ex. 1381 this procedure can be repeated for ‘eth finite ection, 4 Determination of effet of pressure drop using shorteut method. The vale f Bags Ni An ‘and overall length (2: ~ 1%) are obtained from the shortcut calculation in Subsection 1 above The shortcut value ofthe overal pressure drop (p= Py.) can be oblained from Eg. (138-16) ‘using p atthe inlet as 7, and the overall length (=: ~ =). Thon fr a second and final tera tion, the new and corrected pressures Paw = P~ APv!2 and py, = Py ~ Ap are used in Eqs. (137-27) and (1385-11383) to recaleuate¥,.¥. Vp and Ay again, This recalculated Ay will nclode an approximate effect of pressure drop inthe tubes 1X9 REVERSE-OSMOSIS MEMBRANE PROCESSES, HOA Introduction 21. Inroducion. Tbe usetul for separation of diferent species. a membrane must allow passage of certain molecules and exclude or greatly restrict passage of others. In osmesis. spontaneous transport of solvent occurs from dilute solute oe salt solution oaconcentrated solute or sat solution a:tens semipermeable membrane which allows passage of the solvent Dbut impedes passaze of the sal solutes. In Fig, 128-1a the solvent water normally ows ‘through the semipermeable membrane to the salt solution, The levels of bath Hiquids ate the same as shown, The selvent flow can be reduced by exerting a pressure on the sal-sltion side and membrane, shown in Fig, 139-1, until at a certain pressure called the osmotic pressure 7 ofthe sal solution, eguilibriun is retched andthe amount the solvent passin fm opposite directions & equal, ‘The chemical potentials of the solvent on oth sides ths membrane ate equal. The properties ofthe solution determine only the salu ofthe smote pressure. not the membrane. provided that iis truly semipermeable. "To reverse the Mavs of "the water so tht i ow rom the salt soln tothe fresh solvent, as in Fie. 139-Te the pres sure isnereased shove the osmotic pressure on the solution side This phenomenon. called reverse anos, used in» sumer of processes, An impor lant commcrsial use is in the desalination of seawater or brackish water to proce Iresh water. Unlike distillation and freezing processes used to remove solvents, reverse osmosis «can operate a ambient temperature without phase change. This process is quite useful for the processing of thermally and chemically unstable products, Applications include concensae iH B solvent flow feos : THe +H water membrane solvent T NaChwater co) oy © Plover 1861. Osmosis ant verse womens ta) mons eb) omic equi, rm cheese whey: and concen sion of fut juices and milk, recovery of protein and sug tration of enzymes 2. Osmoric presure of solutions. Experimental data show that the osmotic pressure = of Solution is proportional 10 the concentration of the solute and temperature T._Vanit Mott Originally showed that the relationship i similar (0 that for pressure ofan ideal gas. For ex ample, for dilate water solutions. (B94) ‘where isthe umber of ke mol of solute, V, the volume of pure solvent water in m? associ ted with » kg mol of solute, R the gus law constant 2.087 10-*mm!-atm/kg mol-K.and 7 is temperature in K. If solute exisis a 060 oF more ions in solution. 11 represents the fol numberof ions. For more concentrated solutions, Eq, (139-1) is moditied using the osmotic oetcient which isthe ratio of the etwal osmotic pressute tothe ideal 7 calculated from the equation. For very dilute solutions has a value of unity and usualy decreases as con ‘centration increases. In Table 13:1 some experimental values of x are given for NaCl sole: tions, sucrose stations and seawater solutions (S3. 55). ENAMPLE 13.9-1. Calculation of Osmotie Pressure of Salt Soluion CCaleulate the osmotic pressure ofa solution containing 0.10 g mol NaCW1000 g H.0 at 28. Solution: From Table A.2-. the density of water = 997.0 kgim'. Then, = 2 0.410% 10° = 2.00 % 10 kg mol (NaCI ges two ions). Also. the volume ofthe pure solvent water V, = 1.00 kg/(997.0 kal’). Substituting into Ey. (139-1, 200 WQS) Town NA This compares withthe experimental value in Table 18941 of 4.56. Chapter 8 Membrane Separation PrvesesVaae LAV. Osmotic Pressure of Various Aquos Solutions a 28°C (PL ° wo a ° ° ome a7 10 Ts has on) maya sms 78 os uaa mae 780 wwe a831 lo tae? aS 000 a) 28k 2m usm 4 Types of membranes for reverse osmosis, One of the more important membranes for ve ‘erse-osmossdesalinition and many other reverse-osmosis processes is the cellulose acetate membrane. ‘The asyrmetric membrane ws made as a compesite fn i which a thin, dense layer aout 1-10 jn thick of extremely fine pores & supported upon a much thicker (50-125 jam) layer of microporous sponge with little reistanee to permeation, The thi. dense layer as the ably (o block the passage of quite small solute molecules. In desalins tion the membrane rejects the salt solute and allows the solvent water 10 pass through. Soliates ovhich are mo effectively exchaded by the cellulose acetate membrane ate the salts NaCl, NaBr, CaCl ard Na,SOg: suerose: and teralky! ammonium salts. The main lita tions of the cellulene avetate membrane ate that fr the most part it can only be used in a ‘uy solutions and tha it must be wsed below about 40°C. ‘Another importan| membrane usclul for seawater, wastewater nickel plating rinse sol tions. and other solutes is the synthetic sromatic polyamide membrane “Permasep.” made in the form of very fine, voll fibers (L1, P8). When used industrially this type of membrane withstands continued operation al pH values of 101011 ($4). Many other anisotropic mem trans have also been sathesize from syntheti polymers, some of which ean be used in or anc solvents, at hight temperatures, and a high or low pH (M2. RD 1898 Fluy Equation for Reverse Osmosis 1. Basic models for membrane processes. ‘These are eso basic types of masstransport mechanisms which eve take place in membranes. In the firs hasi type using tight mem trans. which are capible of retaining solutes of about LO As size oF es, diflusion-type transport mainly eveurs, Both the solute andthe salvent migrate by molecular or Fokian di fusion inthe polymer, driven hy concentration gradients setup inthe membrane by the ap plied presure difercnee. Inthe second hasic type, using loose, microporous membranes Ich retain particles larger than 10 A. a sieve-type mechanism occurs, where the solvent moves through the merapores in essentially viscous flow and the solute molecules small enough to pass theough the pores are carted by convection withthe solvent. For details of this second type of mechanism, se (M2, WI Past? Separasion Pros Prbipes2, Diffision-sype model. For sifusion-type membranes, the stealy state equations govern ing the transport of solvent an solute ae to frst approximation as follows (M2. ML), Fie the ditusion ofthe solvent theough the membrane. as shown in ig. 139-2 », N, = [MAP ~ Aa) = AlaP ~ an) (139.2) P 5 41393) where Ny, isthe solvent (water) Hux in kgs-m"; P, the solvent membrane permeability, kg solvents-m-atme Z, the membrane thickness, mt, the Solent permeability constant ke solventis-m? atm: AP = P ~ P. (hydrostatie pressure difference with Py pressure ex erted on led and Pson product solation), atm: and Amr = my ~ ms [osmotic pressure of feed Solution ~ osmotic pressure of product solution). atm. Note that subscript | isthe feed or up. stream sige of tte membrane and 2 the produet or dowasteeam side ofthe membrane For the iusion of the solute through the membrane. an approximation for the Rx of the solutes (CML) Dé Ale, es) (294) 11398) ‘where N, i the solute (salt us i kg solute’s- mr D, the diffusivity of solute in membrane, mis K, = cq iistribution coeticient). concentration of solute in membrane concentration ‘of solute in olution: 4, is the solute permeability constant, mse; the solute concemteation in upstream oF feed (concentrate) solution, kg solutes’ and es the solute concentration in LUownstream or product (permeate) solution, ke solu’, The distribution eostcient K, is approximately constant over the membrane “Making material balance at steady state for the solute, the solute diffusing through the ‘membrane mus’ equal the amount of solute leaving in the downstream or proguct (permeate) solution: 1139.6) where eis the concentration of solvent in stream 2 (permeate) kg solvent im! IF the stream 2s dilute in solute, css approximately the density of the solvent. fn everse osmo~ sis. the solute rejection Fis defined as the ratio concentration diference across the men- membrane product permeate 1g rr Shtion Py FiGURe [39-2 Conca a fsx eer oumnons proves feed cencentrate “|r solution A Chapier BV Membrane Separon Proveaesbane divided by the bulk concentration on the feed or concentrate side (faction of solute re maining in the feed steam) =1- «39.7, “This can be related the Muy equations as follows, by fist substituting Eqs. (139-2) and (139-4) into (139-6) 0 eliminate Ny and Nin Eg, (1396). Then. solving fr cle and sh stiuting this result into Eq, (139-7), Baran) nos “7s BaP - aay (398 PA 8 z (139.9) DeRose Aes where Bis in ain. Note that is composed ofthe various physical properties. D,.and ofthe membrane and mus! be determined experimentally for each membrane. Usually it isthe product 2X, that is determined. not the values of D, and K, separately. Alba, many of the data reported in the lterature give values of (P,/L,) or im kg solvent Sm atm and (D,K, ig) OF A, mssand not separate values Of Ly. Py. ad 30 on EXAMPLE 139-2. Experimental Determination of Membrane Permeability Experiments at 25°C were performed to determine the permeabilities of cellulose acetate membrane (AI, WI). The laboratory test section shown in Fig. 13.9.3 has membrane area A= 200 10-Pay The inet feed so centration of NiClisc) = 10.0 kg NaCl sation (10.0 g NaC Lp, = 1004 kg solution’m'). ‘The water recovery is assumed low so thatthe concentration cy in the entering fecd solution lowing past the membrane and the concentration of the exit feed solution are essentially equal. The product solution contains £0139 kg NaClim"' solution (= 997 kg solution!) and its measured fw rate is 1.92 > 10" m' solution’. pressure differential of S514 KPa (S442 atm) inused. Caleute the permeability constants of the membrane and the saute rejection R Solution: Since esis very low (lute solution) the vale of cys can he assumed asthe density water (Table 139-)), oF és = 997 ke slvent/im’ To convert the product Mow rate to water Mux, N, asing nea of 2.00% 10°" m N,, = (1.82 % 10 “m/s (997 kg solventim")(112.00 10°!) = 957 10 kg solvents? 4 fa “—] = he SSSR pent —— (a ‘membrane —+ exit feed solution Ficure 13.83, Proves flow aan Pan Separation Proves Principles ow0 Substituting into Eg. (189-6), Nyes _ (0374 10 V0.9) Nene 7 = A744 % 10 Pky solute NaCUs- Ti Uetermine the osmotie pressures trom Table 139+, the concentrations are converted a5 follows. For ej 10 kg NaCl 8 in 10 ke. solution im? oy = 1005), Then, 1004 ~ 10 = 994 kg H.O in Tm solution, Hence, in the feed Solution, where the molecular weight of NaCI = $845, (1000 % LOM)! (994 > 5845) = 0.1721 gmol NaCkg HO. From Table 139.1, x) ~ 78Datm by Tinear interpolation, Substituting ito Eg. (13.9-1), the predicted 7) = 8.39 atm, ‘which is higher than the experimental value. For the product solution, 997 — 0.39 = 9966 kg HO. Hence, (0.39 % 100)/(9966 S845) = 1.00670 g mot NaClkg HO, From Table 18941, 75 = O32 am, Then, A= 780) — 0.32 = ToS atm and SP = 5442 tm, Sobstiuting into Fg (139-2), P, Ne = 957 w= Tae = am) = F549 ~ 748) En 4, = 2039 % 1D "ky solsentis-m-atm, Substituting ino Solving. (2.11) Eq. (139), DK. no DK 744 10% @ OE, ey 1.00 ~ 039 Solving. (D,Kfog) = A, = 3896 10? ms. Tivcalelate the solute rejection & by substituting into Eg. (139-7), ee, mon 039 Ren 1000 = 0.61 Also substituting into Eq, (139.9) and then Eq, (1398), °° TD Rilalea G89 x 10a OSMPat Bah = 39) _nsw9ista2=748) PS BAP as)” Tr os2a98h2 ~ 728) 1310 APPLICATIONS, EQUIPMENT, AND MODELS FOR REVERSE OSMOSIS ILIOA_Ettects of Operating Variables {Im many commercial units, operating pressures in reverse osmosis range from about 1035 up to 10380 KPa (150 up 10 1300 psi. Comparison of Eq. (13.92) for solvent Mux with Eq, (13-4) forsolute fax shows thatthe solvent Mux 4, depends only on the net pressure ultference, while the solute Hux N, depends only on the concentration difference. Hence asthe Teed presse is increased, Solvent oF vaer Now through the membrane increases nd the solute fae remains approximately constant, giving lower solute concentration in the prodet sobation. Ciuper 8 Membrane Separation ProcessAta constant applied pressure. increasing the feed! solute concentration inereases the product solute concentration, ‘This is caused by the increase i the feed oamotie pressure Since as more solvent s extracted from the feed solution (a8 water feewvery increases), the solute concentration becomes higher and the water Muy decreases. AI, the amount of ‘alte present inthe pret solution inereases because ofthe higher feed concentration a reverse-osmosis unit has a large membrane area (a8 ina commercial unit) and the path between the feed inlet and outlets kang, the outlet fed concentration can be consid bly higher than te inlet feed, ‘Then the silt will be greater atthe outlet feed as com pared to the inlet /K2), Many manufacturers use the feed solute or st concentration aver faye between inet and outlet to calculate the solute or salt rejection in Eg. (139-7) EXAMPLE 1310-1, Predietion of Performance in a Reverse-Osmosis Unit A reverse-oxmesis membrane to be used af 25°C for NaCl feed solution con taining 25 p NICU L (25 kg NaClin', y= 999 kg/m has a water permeability constant A= 481 < 10°" kgs-nv -atm and a solute (NaCl) permeability con stant, = 44210. 7miS(A1), Caleulate the water uy and solute Hu through {he membrane Using AP = 27.20 alm and the solute rejection R. Alsocaleulate c ‘of the product solution, Solution: the feed solution. c, = 2. kg NaCl/m' and = 999 kg solu tion/m’. Hence, or the feed, 98) ~ 2.5 = 996.5 ky H.O in 1. m' solution: also for the feed, (2.50 * 1000)/(996:5 > S848) = 292 g mol NaCl/kg HO. From Table 139-1, = 197 atm. Since the roduet solution eis unknown, value of 6 = 0.1 kg NaCl willbe assumed, Also, sine this quite dilute, ps = 97 ke Solution in” and Cys = 997 kg solventinr, Then for the product solution {0.10% 104n (9969 % 88.5) = 000172 g mio! NaCikg HO and xy = OA am, Also. = 4, = 1.97 ~ 008 = 1.89 am, Substituting into Ey, (139-2 AMAP ~ Sm) = ASL 1042720 ~ 189) XW kg HOI em" For calculation of R substituting first into Ey. (139-9. 4 asic! “gs hom a Fe Noe AD 107 ORF Next substituting ino Eq. (1395). Biase) _Lanaqe720— 1.99) k = 0965 TS APH ae) T= 109909730 — E89) Using this value of in Eq, (139-7) 6 280-6 R= 096s = "s 0875 ke NaCl forthe praguet solution. This iselose enough 10 the assumed value of r= 0.10 that will not change significantly on a second trial. Hestce the final vali of 8 (M0875 ky NaCTAN (DUNTS g NACL). Solving. Parr? Separation Pros PrsipesSubstituting ino Ey, 1394) N. 42 10-712.50 = 0.0875), Ale - 6) [0 2610 NaC 1108 Concestration Polarization in Reverse-Osmosis Diffusion Model In desalination localized concentrations of solute build up at the point where the solvent leaves the solution and enters the membrane, The solute accumulates in a relatively’ stable ‘houndary layer (Fig, 13.9:3) next 1 the membrane. Concenteation polsization, 8. is defined "asthe rato of the sal concentration at the membrane surface to the salt coneentration inthe blk feed steam, Concentration polarization causes the water Mux to decree. since the ‘osmotic pressive m, increases as the boundary layer concentration increases and the overall Uriving force (AP ~ A) decreases. Ao, the solute Hux increases, since the salute concen ‘ration ineeases at the boundary. Hence often the AP must be increased to eompensie, which results in higher power costs (K2), The effect ef the concentration polarization fcan he included approximately by modi ing the value of Aa in Eqs. (19-2) and (13.9.8) as flows (Pa): Aa= pam, or leis assumed thet the osmotic pressure is drcetly proportional to the concentration, which is approximately correct, Also, Eq. (13944) ean be masdiied as N= A(Be, ~ 03) (13402) “The usual eoncentrtion polarization ratio (K3) i 1.2 10 20, hati the concentration in the boundary layers 1-2-2.0 times, inthe bulk feed solution, This ratio is olten dificult to predict. In dessination of seawater sing values of about TINO psia = AP. can he large Increasing this; by factor of 1.22.0 can appreciably reduce the solvent flux. For brackish waters containing 2-10 g/L and using A? values of 17-58 atm abs, the value of is low and concentration polarization is nt important The boundary layer can he reduced hy ieteasing the turbulence by using higher foed- solution velocities. However, ths esta low results in a smaller rato of product solution to Teed. Also, sere eam be pt inthe th to induce turhulence. Equations for predicting the rmass-translereweficient 0 the surface and. hence. the concentration polarization, are given for spectic geometries such a8 low past plats, inside tubes, outside tubes, and so-on (HD, NI). Thea equasions for the fax of water ean be used with these mass-transfer catciets in rane similar to that for altailtration given in Section 13.11 1310C Permeability Permeability constnts for membranes must be determined experimentally fr the particular type of membrane to he used. For cellulose acetate membyanes ypical water permeability constants a, rage from about 1 10-10 5 10-*kg solvent/s-my?-atm (AL. MB, WH) ‘Values for other types of membranes can dilfer widely Generally the water permeatilty onstant fora particular membrane does not depend upon the solute present For the solute permeability corstants A, of cellulase acetate membranes, some relative typical values are 3¢ Fallows, assuming a value of A, = 45 10m tor NaC La % 10" mis (BaCl). 2.2% 1? (MaC1),24 1 (CAC). 44 10-7 (NaS). 40 % 1 (RCD, 60% 10-7 (SHED EAN) onstants for Reverse-Osmosis Membranes Chuprr 88 Membrave Separation Prvenses 41310 Types of Equipment 1 Reverse Osmosis “The equipment for eserse osmonisis quite similar to that for gas permeation membrane pro cesses described in Section 133C. In the plitesand-frame-type unit thin plastic support pales with thin ginoves are covered on both sides with membranes asin filler press. Pres $urized feed soution flaws between the closely spaced membranes (L1). Solvent permeates through the membrage an! flows in the grooves to an outlet. Ln the tubular-type it. men vanes in the form oftubes are inserted inside porous-lubs casings, which serve asa pressure veel, These those then arranged in bundles like a heat exchanger Tn the spiral-wound type planar membrane is used and fa, porous support m {is sundwiched between the membranes. Then the membranes support, and a mesh feed side spacer are wrapped in a spiral around a tube, Inthe hollow-fiber type fibers of 101-200 jm ameter with wally about 25 jn thick ate arranged in a bundle similar to a heat exchanger (LI. Rp. Complete-Mising Model for Reverse Osmosis The process flow diagram forthe complete-mixing model i shown in Fig. 13.101. ‘The model is simplified one for use with low concenttations of salt of ahout 1% oF so. such a oxen brackish waters, Also, relatively low recovery of solvent occurs andthe effects of concen tration polarization are small Since the concentration ofthe permeate i very low. the per mate side acts as though it were completely mixed or the everall material balance for dilute solutions antes asi.) where g, i volumetric fw rate of feed, m's: gs flow rate of permeate, ms; and gy ow rae of residue or ex mS. Making a solute balance 104) a + exh Defining th cut or faction of solvent recovered 36 # © qui Eg. (1310-4) becomes 6 == We, +e a s) The equations previously derived forthe Muses and rejection are useful inthis case an ae ss Follows Nu = AMP 8) a9) r rejet out nit fe feedin aS Kosai wT 84, Flouit [31041 Presson for comphteaniing mde for revere Punt Separation Process Pencils sonN= Ale) (394) Res «139-7, Ty WAP an) Bea ‘When the cut of action recovered is specified, the solution is trial and error. Since the permeate and rejet concentrations cand care unknown, a value of eis assumed. Then is caleulated ftom Eq, (13105). Next, N, is obtained ftom Eq. (1392) and e: ftom Eqs. (13.9-7) and( 13.98), I the ealeuated value of es does not equal the assumed val, the procedure is repeated ‘When concentration-polarization effects ae present an estimated value of Bean be used tomake an appresimate correction for these elfects, This is used in Eq, (13.101) tabtain a walue of A for use it Eqs (139-2) and (13958). Also. Eg (13.1042) wil replace Eg, (13 9-4) A more detailed analysis of this complete mixing model is given hy others (HI. KI}. in which ‘he mase-transfercoelicient in the concentration-polarization boundary layer is used. “The cronsflew model for reverse osmosis 8 similar to that for gas separation by men branes which war discussed in Section 136, Because of the small solute concentration, the permeate sie acts as if completely mixed. Henee, even if the module is designed for coun tercurrent or cosurrent flow the eessflow model is valid. This is discussed in detail else where (HI). IML ULTRAFILTRATION MEMBRANE PROCESSES ILIA Introduction Utieaitation isa membrane process that is quite similar to reverse osmosis. ILisa pressure driven process where the solvent and, when present, small solute molecules passthrough the riembrane and ate collected as a permeate. Larger solute molecules donot passthrough the ‘tembrane and ate recovered ina concentrated solution. The solutes or molecules to be sep arated generally have molecular weights greater than SW) and up {160 00D0F More, Such 3S ‘macromolecules of proteins, polymers, and starches as well a colloidal dispersions of las, Tatex partite, and microorganisms Unlike reverse osmosis, ultrafiltration membranes ae too porous toe used for dealt ing, The rejection R-often called retention, is aso given by Eq (139-7), which defined for reverse osmosis. Uraitration is also used to separate a mintore of eiferent-molecula ‘weight proteins. The molecular-weight cut-off ofthe membrane is defined as the molecular ‘weight of globular proteins, which are 90% retained by the membane. A rule of thumb is that the molecular mass must differ by a actor of 10 for a good separation (PT), Ueaitratin i used in many diferent processes at the present time. Some ofthese are separation of oil-water emulsions, concentration of latex particles, processing of Blood and Fractionaion o separation of proteins, recovery of whey proteins in cheese manufac moval of hacteria and other particles to sterilize wine, and clarification of fruit juices “Membranes ior ultrafiltration ae in general simi fo those for reverse osmosis and are commonly asymmetric and more porous. ‘The membrane consists of avery thin, dense skin Supported by 3 relatively porous layer for siength. Membranes are made from aromatit Chapter 8 Membrane Separation Proceses 7polyamides, exlutes a so forth (MD, Po, RI). sate, cellulne nitsate, polycarbonate, polyimides, polysulfone. and IIIB Types of Equipment for Ulrafitration “The equipment for ultrafiltration i similar to that wed for reverse osmonis and pos separ tion processes described in Sections 15.3C and 13.100. ‘The tubular-type units ess prone te Fouling and more ely cleaned than any ofthe eter theee types: however this type i tee tively costly Flat shoot menvbranes in a plate-anc-frame uni olf the greatest versatility hut atthe highest eapital cost (Po). Membranes ean easily be cleaned of replaced by disassembly of the Unit. Spizalwound modules provide relatively low costs por unit membrane area. These lnits are mote prone to fouling than tubule units but see more resistant to fouling than hol low-fiber unis, Hollow-ftber modules are the least resistant to fouling as compared to the ther three types. However the hollo-siber configuration has the highest ratio of membrane area per unit volume Crossflow filtration i the most common type of model used (P7). Spiral-wound fat sheetsare used mos of all followed by hollow-fber units. Batch processes are also quite com rion, Stirred tanks witha membrane ate used which approximate cross-flow operation (RI) ASIC Flay Equa “The Muy equation fr diffusion of solvent through the membrane isthe sime as Eg (139 + for Ultrafiltration for reverse osmosis Ny = AAP ~ Sz) as In ultrafiltration the membrane does not allow passage of the solute, which is ene inscromolecule, The concentration in moles/lite of the large solute molecules is usually nce. the osmotic pressure is very low and can be neglected. ‘Then Fy. (139-2) small. H becomes N= AAP asuey Utraitation units operate at about 5-100 psi pressure drop, compared 4 40) -2U00 for Fe verse osmosis. For low-pressure drops of sak. 5-10 psi and dilute stations of yp to 1 wt oF 0, Eg, (1311-1) peeicts the performance reasonably well for well-stired system. Since the slates rejected by the membrane, it accumulates and starts to bill up atthe surface of he menthrane. As pressure drop i increased and or concentration of the solute is increased, concentration polarization occurs, which fs much more severe than i reverse rons. This is shonin Fig 1311-1, wht othe eoneentratin of the solute inthe balk solution, ke solute. , fs the concentration of the soe al the surface ofthe membrane and cis the concentration in the permeate ‘As the pressure drop increases, this iereases the solvent Mus N. 10 and through the membrane. This results higher convective transport ofthe solute {othe membrane, that isthe solvent carrics with it more solute. ‘The concentration ¢, increases and gives a larger hack molecular diffsion f solute from the membrane to the bulk solution, At steady slate the convective Nu equals the dilfasion ux é Mee p, sat wf asan2y 1 Foes Princes, angnbrane Dandie oe y, ., aA wae Nel an we boundary boundary hee ver et @) ob) Deon el ormat “hy concen pre wit a eke formed where Nycip = [kp solvent (s-m)]tke solute m)(kg solvent") = kg solutls- ms Dy is ifusvity of solite insolvent, ns: and distance, m. Integrating this equation Hetween the mits of = Oande =e, and v= Bande = cy Ne (Dw ( oF) og (OOS we (Ee) 2) = ean SS *) (313) where isthe mass-ransfer evetcient, mi. Further increases in pressure drp increase the value of c toa limiting concentration. at which the accumulated solute forms a semisolid ge where g,~ ¢,,asshown in Fig. 13.11-Ih, For the usual ease of almost complete solute rten tion (P7), 6, = Band Eq, (13.113) becomes i, Iie) «3a Sul further increases in pressure drop do not change ¢, and the membrane is said 10 be gel polarized” Then Eq, (13.113) becomes (PI, Po, RI) en(2) suns With increases in pressure drop, the gel layer increases i thickness, causing the solvent us to decrease becuse of the alded gel-layer resistance, Finally. the net fx of solute by con- ‘ective transfer becomes equal tothe back difusion of solute into th bulk solution because of the polarized concentration gradient as given by Eq. (13.115). The aded gel-layer resistance next tothe miembrane causes an increased resistance 10 solvent fax, a gen by 316) pier 14 Manbrane Separation PresetWhere IIA, isthe membrane resistance and Ry isthe variable geluyer resistance, (5+ atm)/kg solvent. The solvent ox in ths gel-polarized regime is independent af pressure di ference and is determined by Fy. (13.11) for back dilfusion, Experimental dat confirm the use of Eq, (1311-5) for large numer of macromolecular solutions. stich as proteins and forth as well a colloidal suspensions, sue as latex particles and so forth (PI, Po) IAD Efedts of Processing Variables in Ultrafiltration {A plot of typieal experimental data for uy versus pressure difference i shown in Fig, 13.1-2 (111 Po), At iow pressure diferences andor low solute concentrations, the data typically fo low Eq, (1311-1), Fora given butk concentration, ¢, the Nox approaches a constant vale at high pressure diferences. as shown in Eq. (1311-5). Also, mores protein concentra tions give higher flux rates, as expected from Eg. (1311-5). Most commercial applications are fux-limited by concentration poariation andl operate i the region where the Mux is appeo% imately independent of pressure difference (RI) Using esperimental data.a plot of Np versus Inc isa straight line witha negative slope 0 the mass transtercoetiient, ay shown by Eg, (13.11-5). These pts also give the vale fof the gel concentration. Data (PI) show thal the gel concentration for many macromol cular solutions is about 25 wt %, with a range of S 10 50%. For colloidal dispersions itis bout 65 Wt. with a range of 50 40 75 ‘The concentration-polatization effects for hollow fibers are often quite small. due to the Jow solvent us. Hence, Eq. (1311-1) describes the flax, Ih order to increase the ultraftr tion solvent Aux, ross-flow of uid past the membrane cam be used to seep away part ofthe polarized layer. thereby increasing, in Eq, (13.11-5). Higher velocities and other methoss are used to nctease turbulence and hence f,. In most cases the solvent Nu is too smal 6 op eae in single-pass mode. Iv is necessary to recirculate the Teed past the membrane. with re ireulation rates of 10/14 1001 often use Methods for predicting the mass-transer coelicient kin Eg. (13.11-5) are given by ‘others (PI, Po) for known geometries such as channels ad so forth, Predictions flax in known geometries using these methods and experimental values ofc, in Eg. (13.113) in the Eq. (1310-1) pe, Ap——> Fic 1311-2. aro presi divence on wen fa Pans Separation Process Prisel polarization regime compare with experimental vulues for macromolecular Solutions within about 25-30%. However. for colloidal dispersions the eyperimental Rus is higher than the theoretical by factors of 20-30 for laminae lw and N-10 for turbulent floss Hence, Eq. (1211-5) isnot useful for preieting the solvent fa accurately. Generally. or design of 1 uns itis novessaey to obtain experimental data on single moles 112 MICROFILTR ATION MEMBRANE PROCESSES, 112A. Introduction {In mierotiltration, pressure-driven flow through a membrane is used to separate micron-sire particles from fuids. The size range of particles ranges fom (02 jem 40 10 mH). This rmicrotiltation separates particles from solutions. The particles ae usually larger than the solutes in reverse osmosis and ltrabltration. Henee, osmotic pressure i negligible, AC the very low end ofthe size range very large soluble macromolecules are retained, Bacteria and ‘other mieroorgcnisms (P7) are also retained on these membranes. Other particles inthis sine ange are paint pigment, east cls, suspended matter such as eels [rom fermentation broth particles in beer pasteurization, and so on. ‘The dividing line between ulrailtration and mi éroiiltration is not very dstinet The pore sizes of the membranes and the permeate ax ae typically larger than for re Yetse osmosis and ultralitration. Usually the pressure drop used across the membranes varies from I psi to 50 psi (H2). Types of membranes are extremely varied and can be ce ramies, polymers, and son, Many dife‘ent geometries of membranes are used. ‘These include spirul-wound, pate and trame, hollow ber. cartridge flters with pleated membranes, and so on. Disposable ca. ridges are aso sed, 13128 Model for Microtitration 1. Dead-end microfitotion flow motel. In many laboratory bate filtration the batch pro- ‘ess un in deadnd! low, with the membrane replacing the conventional filter paper. The particles build up wit time asa cake and the earfied permeate is forced through the mem. brane, as showin n Fig. 13.12-1a, The permeate Mux equation is (H2) ae wR, = RO ™, aay where 's the solvent flu in kgi(s +), AP is the pressure difference in Pas viscosity of the solvent in Pes. Ris the membrane resistance in me/kg, andl. is the cake resistance in kg. hich increases with time de to cake buildup This Eq, (1312-1) i similar to Ey, (1428) for ordinary filtration given in Section 14.2 of this text, Solutions to this equation are also given there 2. Crossfow merofitration flow model tn the crss-ow model shown in Fig. 13.12-Ibthe ‘operation i similar to that for reverse osmosis and ultrafiltration in thatthe Row of bulk ol tion is parallel te the membrane surface and not through it (H2). The permeate flow through the membrane carries patiles to the surace, where they forma hin layer. relatively high ‘ow rate tangential to the surace sweeps the Jeposited particles tcward the iter exit leaving Chapter Membrane Sepirion Proveses adTEESE S seaataosbbent 8, hoy | rermeats Permeste FiouRe IIL Proce fow foricrfivaton fa) dead-end (1 eos 2 relatively thin depesited cake layer. This thin cake layer i similar to the gel ayer formed in Uultefiltration, This cross-flow iy effective in controling concentration polarization and cake buildup. allowing relatively high faxes to be maintained “This concentration-polarzation model of convection of particles to the cake layer is al anced by particle difusion by Brownian diffusion away from the cake surface. This model is similar tothe Mux Eq(13.11-3) forultraitration. Other models are also given eewere (H2), PROBLEMS ids and a@ Membrane. membrane prosess is being de = 20% 10 kg mol Aim mbrane IRA. Diffusion Through Li signed to recover solute A from a dilate solution whet by dialysis though a membrane toa solution where cs = 0. © 10 2, The thickness 159 > 10° m. the distribution coetiient K” = 0.75, Dy = 35% Hh i's in the membrane, the mass-ransfer cactlicient in the dite solution is) = 35% 10 Sms.and he = 20% 10 (2) Calculate the individual resistances. total resistance. and total percent re sistance ofthe two fis, (b) Caleulate the Mus at steady state and the total atea in m! for 8 transfer of (001 ke mol sole’, (6) Increasing the velocity of oth gud phases Rossing past the surface ofthe -membrare wil increase the mass-transfercoeticents, which are approxi ‘pately proportional to !, where ws velocity. If the velocities are dow bed, calculate the total percent resistance of the two fils and the percent increase fo. Ans. (a) Total resistance = 6823 10'sim, 11.17% resistance: CO), = 2492 10 "ke mol Ame atea = HLS my 1322, Suitability of a Membrane for Hemodialysis. Experinvents are being conducted to ‘etermine the suitability of cellophane membeape (1024 mint thick for use in an artiicia-kidney device. In an esperinent at 37 Casing NaCl asthe diffusing salute the membrane separates two components conisining stirred agucous solutions of Cl where = 100% 10) moliem' (100g mom’) andes = 41> 10°” The mas ansfer coellvients on either side of the membrane have been estinisted 38 ky =rt. 142. 148, .. = 524% 10-7 ms. Experimental data obtained gave a Aux Vy = SLL 10% g mol NaC Sm" at pseudosteady-sate conditions (a) Cakulate the permeability yin S:9d D yA" in {t) Cakulate the percent resistanee o fusion in the igi films. Gas-Permeation Membrane for Oxygenation. Yo dlermine the suitability of sil cone rubber for its use as a membrane Tor a heart-lung mchine to oxygenite Ble an experimental value of the permeability at 30°C of oxygen was obtained. where Py= 650% 10 em’ On (STPY/s-eny =e Heim) {a Predict the maximum Mus of O: in ky mols ith an ©, pressure of 700 tr Hg on one side of the membrane and an equivalent presure inthe ‘Blond in side of 5) mi, ‘The membrane 0.168 min thick. Since the gas fis pure oxygen. the as film resistance i 2er0, Neglect the blood film resstance in this ese (>) Assuming a maximum requirement for adult of Sm em O, (STP) per ‘minute, calculate the membrane surface area requited in m, (Note The ne- tual atea needed should be considerably larger since the blo film resist- ance, which must be determined by experiment. ca be appreciable) ‘Ans. (b) L953 m= Derivation of Equation for Permeate Concentration, Derive Bq. (134-11) for Case 2 for complete mixing. Note that, from Eq, (1349) must fst be substituted inte Fq.(13.466) before multiplying ou the equation and solving for ¥, Use of Complete-Mixing Model for Membrane Design, A membrane having thick- nies of 2% 10 em, permeability Py = 400 % 10-""em! (STP) -em/(s ent -em He), nd a” = 10s to be used to separate a gas misture of and The feed Now rate {Ly = 2 « 10° em*(STP)s and its composition is «j= Dall. The Feed-side pressure i ‘Siem Hg and the permeateside pressure is 20 cm Hy. The reject composition i 0 bec, = 0.30, Using the complete-mixing model calculate the permeate composition {action of feed permeated. and membrane area, Ams. y, = 0678 Design Using Complete-Mixing Model. gsscous feed stream having a compos tion t= 0.50 and a Now rte of? 10'em' (STP) is tobe separated in a membrane Unit. The feed-side pressure is 40cm Hg and the permeate is 10cm Hg. “The mem: brane has a thickness of 15 * 10°" em, permeatality 2% = 40 % 10°" em® (STP)- ‘m/{s+em'+em Ha). and a” = 10. The fraction of feed permeated i 0.529 (a) Usethe complete-mixing model to calelate the permeate composition, re ject composition, and membrane ate (ho) Caketate the minimum reject concentration, (6) Ifthe feed composition is inereased to 4, = O40 whats this new minimum rejest concentration? AMS. (3) Ay = SSH % 107 em) 4p = 0.2478 Effect of Permeabilities on Minimum Reject Concentration. For the conditions of lem 134-2, 4) = 0413, e° = 10, p= 20cm Hg, pj = 80 em Hig, and &, = 30, culate the minimum reject concentration forthe fellowing cases & (2) Caleulate ty forthe given conditions. () Cafeuate the effect ony if the permeability of If increases so that a’ Ue cremses 105, (6) Calatate the Himiting value of x,y when as lowered tis minimum value OF 1. Make a plot of Yersus a for these three cases Clap HE Membrane Separation ProcesesASS, Minimum Reject Concentration and Pressure Effect. For Example 134-2 for separ tion of i, ca follows (a) Caleula the minimum reject concentration, (b) Ife pressure on the feed sde is edced hy one-half coleuate the effect Ams. (b) ae = 00624 ABSA, Separation of Multicomponent Gas Mistures. Using the same feed composition and Aow rate pressures. and membrane asin Example 135-1. do the following, using the complete-mixine model (a) Calculate the permeate composition, eject composition, and membrane area fora fraction permeated of 0.50 instead of 025. (0) Repeat arta) but for #= 0, (6) Make plot of permeate compeniton yyy versus and sus using the caleulated values fr #=0.25, 0,50, and 090 Separation of Helium from Natural Gas. A ypical composition ofa natural gos (S1) i80.5% He 14), 17.0% N: (B). 705% CH, (C). and 6.0% highes hydrocarbons (D), ‘The membrane proposed (o separate hel his a thickness of 2.54 % 10" em, ane the permeabilities are Py = 60> 10°! cm (STP)-cmi{semr -em He). Py 30% 10-".and P= 1.5% 10°". Ieis assumed thatthe higher hydrocarbons ate es sentially norpermeate (Pi, = 0). The feed flow rate is 200% 10° em (STP). The Feed pressure p, S00 cm Hig and the permeate pressure p= 20cm He. (4) Fora fraction permeated of 0.2. caleulate the permeate composition eject. ‘composition. and membrane area using the complete mixing model (b) Use the permeate from part (a) as feed 10 a completely mixed second stage. The pressure py = 500m He and p, = 20-em. Fora fraction per~ mated of 0.20, caleulate the permeate composition and membrane area 16-1, Design Using Cross-Flow Model for Membrane, Use the same conditions for the separation of an air stream as given in Example 136-1. "The given values are 209, 0° = 10. p= 190 em He. py = Wem Hg, Ly = 1% WP em (STPDS. Py = 500 10°" cm’ (STP) -emi(sem?-em Hg). and ¢= 2.54% Kem. Doras follows using the eros Rae model (a) Caleulate and Ay for # = 0. () Caleulatey, and x, ford = 0 ‘Ams. (a), = 052, x, = (0808. Ay, = 64 1 em ($6), (UP) 5, = 655.4, = 0209 Equations for Cocurremt and Countercurrent Flow Models. Derive the equations for the following cases (a) For eveurtent flow, show the deailed steps for deriving Eqs. (137-38) and (13736) (0) For sun from (137-4) and Fg (13.728), 187-2. Design Using Countercurrent-Flow Model for Membrane, Use the same con 4 given in Example 186-1 forthe separation of an airstream, The given values te 8) = 0.209.010, p, = Mem He, py = 19 em Hg Ly = 1 MP cm (STP). Py = S03 10 em" (STP) -env(s em -em Hg). and 1 = 2.54% 10 em, Using the ‘ountercurrea-fos model caeulate and A, foe = 00. (Note that this pr urtent flaw: show the detailed sles in obtaining Ey, (137-22) Sh Alo. show the detailed steps to derive Pur Separation Piss Prices13st. 1, 1383. 139.2, lem involves a triahandherror procedur ferential equations) slong withthe numerical solution of two dif Effect of Pressure Drop on Asymmetric Membrane Calculations. Using the same conditions asin Example 133¢1. do as follows (2) Use the shorteut method (o calculate the overall pressure drop 3p, using Eq, (138-16) over the entire length. Use typical data for aie given in Se tion 138C to calculate Nj, fiber length and so forth, Assume T= 25" +273 K and py = 1OS4KPA, T, = 273 K.p, = W325 KPa, Ub) With the above values ofp, use the shortcut method ina sesond iteration torecateulte A, (Be sure to correct for Py tay.) {) Calsulate the pressure drop ithe sumer of tubes Nin part (a) is reduced by 0%, Ams. (a) p= 1267 104 (2s 20.74 KP tba 96 KP Spreadsheet Cateulation for Asymmetric Membrane. Using the conditions for Ex ample 138-1. write the detailed spreadsheet and calculate the results, Compare these osults with those in Table 13.82, Comparison of Experimental and Predicted Spreadsheet Results in a Pilot-Unit Asymmetric Membrane. A pilotsize membrane used to separate air inorder to ob- tain nitogen has the following dimensions with the feed inside the tubes: total Np = 33 % 10! bers ID = 98 jm, OD ~ 135 ym, length of fibers = Lin, Ane Petimertal run gave the following eesuts. Feed rate Ly = L086 mh, L, = 0684 = 0.480 mh, «, = 0067 mole fraction oxygen, 9p = O:t13. 4 — TOBE KPa, RIO KPa, and 7 = 25°C. The permeances determined previously are 0) = 1.80 10" m! (STP)/(s-m?*Pa), (PINs) = 247 10" Flow i counter current, Doas follows: (a) Predict the pressure drop in th tubes using the shorteut metho. () Using a spreadsheet, predict the performance of this run and compare these results with the experimental values, Note that thsis tial and error, since the area is fixed but the value of 5, not. First assume a vale ox, ‘Then divide the diflerence between x, ~ 0.200 and, ito nine equal parts and perform the spreadsheet calculation. Ifthe calelated and actual areas {do not agree, assume another value off, and so forth, Neglect pressure drop. ‘Ams. (a) Apy = 4.455 KPa: (b) x, = 0079, V, = 0442 mh yy = 0.398 Osmotic Pressure of Salt and Sugar Soluions, Caleulte the osmotic pressure ofthe following solutions at 25°C and compare with the experimental values: (a) Solution of 0.50 g mol NaCiky HO, (See Table 19-1 forthe experimen tal value.) (b) Solution of 10g suerose/kg HO. (Experimental value = 0.0714 atm.) (6) Solution of 10g MgClxkp H,O. (Experimental value = 0.660 am.) ‘Ams. (a) # = 2439 atm: (b) = = D713 atm: (c) = 0.768 atm Determination of Permeability Constants for Reverve Osmosis. & cellulose-acetate ‘membrane with an area of 40 10" m*is used at 25°C wo determine the permeabil ity constants for reverse osmonis of a feed silt solution containing 120 ke NaCl (p = WES kg/m’). The product solution asa concentration of 0.468 kg NaCliin? Chapter 8 Membrane Separation Prveses193, 13304 1102, 13.0.3 1a a. way wy «By «sy « «Gh Pu (p= 9973 haven’). The measured proxi Now rate is 388% 10" m's and the pres sure diflererce ws is S610 am, Calculate the permeability constants andthe sate rejection R Ans A, = 2008 10 ‘kp solvent 6m? atm, R= DML Performance of a Laborators Reverse-Osmosis Unit, 9 {ood solution at 25°C con tains 3500 mg NaCUL (p = 999.5 kpim'). The permeability constant A, = 8SI >» Ii" kgsolsent sm -atm and a, = 2.50% 10 "ma. Using a AP = 35:50 am, cake late the faxes, solute reeetion Rand product solution concentration in my NaC Repeat. but ssing feed solution of 35H mg BaC lL Use the same vale of Ay. but A= 100% WI mS (AT) Effect of Pressure on Performance of Reverse-Osmosis Unit. Using the same condi tions and permeahility constants as in Example 13 10-L-caleulate the fluxes solute re jection K.aud proxuct concentration «for AP pressures of 17.2, 27.20. and 37.20 ‘ain, (Note:The values for 27-20 atm have already been calculates.) Plot the Muxes. and ¢, versus the pressure Effect of Concentration Polarization on Reverse Osmosis: Repost Example 13.el but use'a eoseentration polarization of 1-5. (Note: The Mux equations and the solite rejection R should he calculated using this new value of) ‘Ams. Nj = 1171 10" hg solvent ms = 0.1361 ky NaCin® Performance of a Complete-Mising Model for Reverse Osmosis, Use the same teed ‘conditions and pressures piven in Example 1310-1. Assume thatthe eu or fraction reconered ofthe solvent water il be 10 instead ofthe very low water recovery a sumed in Example 13.10-1. Hence, the concentrations ofthe entering feed soltion And the exit eed wll not be the same, The few rte g- ofthe permeate water soltion is 100 gal/h. Caleulatee, snd cs in hy NaCl’ andthe membrane ares in mx ‘Ams. = 277 kyl = DITS kgim' area = 8.68 m Flux for Ulrafitration, & solution containing 09 wt % protein is to undergo uh rafliration using & pressure dilerence of S psi. The membrane permeability is Ay = 137 xP hgA-ar ann, Assuming no ele on, predict he Hy ings on wnd in units of ga -day which are often used in industry ‘Ans, 9.88 gait y Time for Utrafitration Using Recirculation, is desived $0 use ulteailiratin for iW Kp of a solution containing 0S Wt "% ofa protein 9 obtain solution of 110 wt 4, The feed is recirculated past the membrane with u surface area of 9.90 m", The permeabiityof the membrane is, = 2.8) > Il)" kps=m-atm. Neglecting the e: Fectsof concentration polarization, if an; caleuate the final amount of solution and the time to achieve this, using a pressute diflerence of 50 at REFERENCES ‘Acnavest Band Souninasan.S. dnd. Eng, Cent, 911), 62 (1969) Bearsori CT. and Kanuranryes, K, Chem. 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