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    Up She Goes! Equilibrium-Stage Separation Operations in Chemical Engineering Ernest J. Henley Professor of Chemical Engineering University of Houston and J. D. Seader Professor of Chemical Engineering University of Utal | ‘IPARTIMENTO DI INGEGNERIA HIM .3804ondeisoktanie tite, 22 fe gh, wa ed into Oe ROCESS De MATENAL poston mons pec nthe EI Segundo seiner? of Sano Oi Ce of Salas California, Western Operations, Inc. The lift was one of the heaviest ever N Ei ‘Buono N. sont. wait rte Ha ey st Cea JOHN WILEY & SONS\ey “45 gag Ee Refer. 37, Na. 2, V8 (I95B)}, Colum akon wes designed by ene of the New York + Chichester - Brisbs authors. Copyright © 1981, by John Wiley & Sons, Inc. At rights reserved. Published simultaneously in Canada Reproduction or ansition of way part of this work beyond that permitted by Sections 107 and 108 of the 1975 Unites States Copyright ‘Act without the permission ofthe copyright, ‘owner is unlawul. Requests for permission ‘or farther information should be adesse8 0 the Permissions Department, Jon Wiley & Sons. Library of Congress Cataloging in Pubcon Data Henley, Brest 3 Equiibrum-sageseparition operations in chemical engineering. Includes index. 1. Separation (Technology) 2. Chemical ‘equiiviom. 1. Seader, J.D. jot author Tae TpIs6SesHss — Go028 80-1393 ISBN O4T1-37108-4 Printed in the United States of America 39 29 25 27-26 25 24 23:22 Printed nad boon by Quinn - Wooing, Ine The literature abounds with information on all Phases, of distillation calculations and design. here has been such a bewildering flow of in- formation, dealing especiatly with the principles of stage calculations, that the engineer who is not a distitiation expert finds himself at a loss as to how to select the best procedures for solving his dis- tilation problems. James R. Fair and William L. Bolles, 1968 PREFACE ical engineering has changed so dramatically in the past decade as that of design pracedures for separation aperations based an the ‘equilibriura-stage concept. Ten years ago, design of fractionators, absorbers, Strippers, and extractors was often dove by approximate calculation procedures: and reboiled absorbers and extractive distillation columns were often “guess- timated” from experience and pilot plant data. Today, accurate ther~ modynamics packages coupled with sufficiently rigorous computational al- gorithms enable engineers 10 solve rapidly on time-shared computer terminals, without leaving their desks, what were once considered perversely difficult problems. Commercially available computer programs for stagewise com- putations ate now so robust and reliable that one can say of them, as was once said of the army, that they were organized by geniuses fo be run by idiots. (One of the premises of this book is that what was once good for the army is not necessarily good for the engineering profession. The availability of commercial process simulation computing systems such as CONCEPT, DESIGN/2000, FLOWTRAN, GPS-II, and PROCESS has, in many instances, seduced the engineer to the status of an army private. Most often, his under- graduate training did not cover the modern algorithms used in these systems, the User's Manual contains only vague of unobtainable references to the exact computational techniques employed, and the Systems Manual may be pro- prictary, so the design exercise degenerates into what is often a “black-bo} operation, the user being left in the dark. The aim of this book is to bring a little light into the darkness. We made a careful study of all major publicly available computing systems, ran a fairly large number of industrially significant problems, and then used these problems as vehicles to bring the reader to an in-depth understanding of modern calculation procedures. This approach enabled us to trim the book by eliminating those techniques that are not widely used in practice or have litle instructional value. vit Preface Instead, we include topics dealing with sophisticated and realistic design prob Time, Indeed, we hope the terms “realistic” and “industrially significant” are (he refjetives that reviewers will use to characterize this book. We did our best 10 ‘tell it like i is. The material in the book deals with topics that are generally presented in undergraduate and graduate courses in equilibrium-stage processes, stazewise seeeration processes, mass transfer operations, separations processes, andlor eparation Processes oor ich vane Ameen ‘rbot seme estar pot (aiocard ‘mecery taeee) e {sor ‘asian abate (aestanard Figure 13. Process for recovery of ight hydrocarbons frm asinghead eas. product, consisting of 99% hydrogen chloride with smal amounts of H 1,0, CO, and COs, requires no purification. Such simple commercial proc that cequie vo equinment for separation of chemical species ave very rare Some industrial chemical processes involve no chemical reactions but only operations for separating chemicals and phases together with auxiliary eauipy ‘ment. A typical process is shown in Fig. 13, where wet natural ga8 is con- tinuously separated into light paraffin hydracachoas by a train of separators including an absorber, a reboiled absorber,* and five distillation columns.” ‘though not shown, additional separation operations may be required to dehy. drate and sweeten the gas. Also, it is possible to remove nitrogen and helium, if desired Most industrial chemical processes involve at least one chemical reactor accompanied by a numberof chemical separators. An example isthe continuous direct hydration of ethylene to ethyl alcohol.‘ The heart of the process is a See Table 1.1, Industrial Chemical Processes 5 seme ketene Even hyravon "ined od cob vetor Etro ‘draoed Figure 14. Hypothetical proces oF hydration of ethylene to ethanol fixed-bed catalytic reactor operating at 2994C and 6.72 MPa (STOR and 975 psia) in which the reaction C:H,+H;0>CiH,OH takes place. Because of thermo- dynamic equilibrium fimitations, the conversion of ethylene is only 5% per ‘pass through the reactor. Accordinaly, o large recycle ratio is required to obtain essentially complete averall conversion of the ethylene fed to the process, If pire ethylene were available as a feedstock snd no side reactions occurred, the relatively simple process in Fig. 1.4 could be constructed. This process uses a reactor, a partial condenser for ethylene recovery, and distillation to produce aqueous ethyl alcohol of near-azeotropic composition. Unfortunately, as is the prevalent situation in industry, a number of factors combine to greatly increase the complexity of the process, particularly with respect to separation require- ments, These factors include impurities in the ethylene feed and side reactions involving both ethylene and feed impurities such as propylene. Consequently, the separation system must also handle diethyl ether, isopropyl alcohol, acetal- dehyde, and other products, The resulting industrial process is shown in Fig. 1.5 After the hydration reaction, a partial condenser and water absorber, operating at high pressure, recover ethylene for recycle. Vapor from the low-pressure flash is scrubbed with water to prevent alcohol loss. Crude concentrated ethanol containing diethyl ether and acetaldehyde is distilled overhead in the crude 4isilation column and catalytically hydrogenated in the vapor phase to convert acetaldehyde to ethanol. Diethyl ether is removed by distillation inthe light-ends tower snd scrubbed with water. The final product is prepared by distillation in the final purification tower, where 93% aqueous ethanol product is withdrawn several trays below the top tray, light ends are concentrated in the tray section above the product withdrawal tray and recycled to the catalytic hydrogenation proé that ‘oper men ‘inw inch Ath drat desis ‘acco direc See 6 ‘Separation Processes Exile oop tyne vert be tyleehyation "iedbed u os saul reter aster om i let eter amex tana ove portation soe (aotaint Faced cena cod Fire 15. Indust process for hydation of ethylene to ethanol reactor, and wastewater is removed from the bottom of the tower. Besides the separators shown, additional separators may be necessary to concentrate the ethylene feed (0 the process and remove potentiaf catalyst poisons. ‘The above examples serve to illustrate the great importance of separation operations in the majority of industrial chemical processes. Such operations are ‘employed not only to separate feed mixtures info their constituents, 10 recover solvents for recycle, and to remove wastes, but also, when used in conjunction with chemical reactors, to purify reactor feed, recover reactant(s) from reactor ‘effluent for recycle, recover by-product(s), and recover and purify product(s) to meet certain product specifications. Sometimes a separation operation, such as ‘SO, absorption in limestone slurry, may be accompanied simultaneously by a ‘chemical reaction that serves to facilitate the separation, 1.2. Interphase Mass Transfer Separation Operations Uf the mixture to be separated is @ homogeneous single-phase solution (gas, liquid, or solid), a second phase must generally be developed before separation of 4.2. Interphase Mass Transfer Separation Operations 7 chemical species can be achieved economically. This second phase can be treated by an energy separating agent (ESA) ot by a mass separating agent (MSA) such as a solvent or absorbent. in some separations, both types of agents may be employed. Application of an ESA involves heat transfer and/or work transfer to or from the mixture to be separated. Alternatively, a second phase may be created by reducing the pressure. ‘An MSA may be partially immiscible with one or more of the species in the mixture. In this ease, the MSA is frequently the constituent of highest concentration in the second phase. Alternatively, the MSA may be completely miscible with the mixture but may selectively alter species volatilities to facilitate a more ‘complete separation between certain species when used in conjunction with an ESA, as in extractive distilation, in order to achieve a separation of chemical species, a potential must exist for the different species to partition between the two phases to different extents, This potential is governed by equilibrium thermodynamics, and the rate of approach to the equilibrium composition is controlled by interphase mass transfer, By intimately mixing the two phases, we enhance mass transfer rates, and the maximum degree of partitioning is more quickly approached. After sufficient phase contact, the separation operation is completed by employing gravity and/or a mechanical technique to disengage the two phases. Table 1.1 is a list of the commonly used continuous separation operations based on interphase mass transfer. Symbols for the operations that are suitable for process flow diagrams are included in the table. Entering and exit vapor and liquid and/or solid phases are designated hy V, L, and S, respectively. Design procedures have become fairly well standardized for the operations marked by the superscript letter 4 ia Table Lt These are ow described qualita- tively, and they are treated in considerable detail in subsequent chapters of this book. Batchwise versions of these operations are considered only briefly. ‘When the mixture to be separated includes species that differ widely in their tendency to vaporize and condense, flash vaporization or partial condensation ‘operations, (1) and (2) in Table 1.1, may be adequate to achieve the desired separation. In the former operation, liquid feed is partially vaporized by reducing the pressure (€.g., with a vaive), while in the fatter vapor feed is partially ‘condensed by removing heat. In both operations, after partitioning of species by interphase mass transfer has occurred, the vapor phase is enriched with respect to the species that are most volatile, while the liquid phase is enriched with respect to the least volatile species. After this single contact, the two phases, which are of different density, are separated, generally by gravity ‘Often, the degree of species separation achieved by flash vaporization or partial condensation is inadequate because volatility differences ate not sufficiently large. In that case, it may still be possible to achieve the desired Table 1.1 Continuous separation operstions based on interphase mass transfor Initia Developed Unit or Food or Added Separating Industetat Operation Symbol” Phase Phase Agents) Example® Flach 2 ina Vapor Pressure reduction Recovery of water fom seawater ‘apoticatont (Wot. 22,p. 20) wy 7 Partial . Vapor igi Heat tanser (ESA) Recovery of Hy sid No fom condensation’ fH ‘emionia by partial cendensation 2 nd bigh-pressute phase A Separation (Vt, 2 99, 282-283) Distlaton® Vapor anor Vapor and Heat transfer (ESA) and Stabilization of natural gasoline by o Tigi Tui ‘sometimes Work distillation to remove sobutsne : cmaester nd lower molecular weight rs Inydrocarbons (Vol 13:7. 24) Extractive Vapor andlor Vepor and Liquid Solvent (MSA) ard Separation of toluene from clost- Distilation? wud tial Heat transfer (ESA) oiling nonaromatic compounds @ by using pheno as a solvent to improve ihe separability. Val 2p. S41) Reboiled Vapor andlor Vapor and Liquid absorbent (MSA) Removal of ethane and lower shaoetion iui Tig nd bext ances (ESA) molecular Went Hydoearbns o from the mai fractiontor loverbead ofa catalytic cracking plant (Vol. 15, pp 25-26) Absorption! Vapor Lig Liquid absorbent (MSA) Separation of carbon dioxide trom o ‘ombustion prodoets by ‘absorption with aqueous Solutions of an thanalyine (Wel 4,» 58,362) ‘Sirippine Lava Vapor Stippiog vapor (MSA) Steam striping of naphia, a kerosene, and ga ol side cuts Irom = erude disiltion uit remove light ends Wal. 15, pp 8) Reflux stripping Vapor andlor ‘Vapor and Sting vapor (MSA) —_Disttation a reduced exute ait (steam g tigi guid fand heat transfer (ESA) under vacuum using steam as Aistifation? = ripping agent (Vol. 15. $8) ® Reboiled i Liguie Vapor Heat transfer (ESA) Removal of light ends from 2 strppine? c ‘pha cit Voh45, 9.19) o aweropic = ‘Vapor andlor Vapor and Liquid entraner (MSAy, Separation of acetic aid from ‘distin "hee, gui Tid heat transfer (ESA) water Using a-butl acetate as an aa ee ntainer to Form 32 szeotone sith water (Vol 2p 851), Liqui.guie 4 Liquid Liquid Ligud solvent MSA} Use af propane a a saver to ‘extraction = easphalt a reduced crud oi ap (ot 2,77) u Table 13 @onts tna Developed unit or Feed or Added Separating lndustal Operation Phase Agents) Example i ui Ligid Two ghd sents ‘Use of propane andere aid “Secon = “Nisa an MSAD Ss sleet to seperte prfine tester ftom amas to pte: rs (Wa. Ie 5758 setcegey Uda ten Vapor Gas MSA) andor test Remo of water fom pli eR transfer ®3A) “hone win oti a oary Shyer (Wal hep. 35378) on ; : v Meat antes ESA) Evaporation of wate fom a oo Mew a ‘solution of urea and water (Vol. a i, 3p.50) Cnptalization ° Liguid Solid (and Heat transfer (ESA) Ceystalization of p-xylene from 8 om 3. = from gu contaiting Ns. Os, COs, CO, H.0, and other organic T compounds by condensation to the Solid sate (Val. 1, p41) Desatinaton a sou Met Taser {SA)——Racvey of phn aide ‘ aE Leaching ac Sib sigsis guid slvent (MSA) Aqueous leaching of sme 19 on aa) Tecover copper sulfate (VoL 6, “ 167 ‘Aatsorgtion yee Waporertiquid Said Slid adsorbent (MSA) Removal af water fom ai by a8) ‘sdeorplion on activated alin (ol p 40) * Design proceduras aro fairy wel standardized * Trays ae shown for columns, but alternatively packing can be used, Mutinte feeds and side streams are often used and may be added to the symbol (see example (9 Fig. 17h. "Cations reer 10 volume and pages) of Kirk-Othmer Encyclonedia of Chemical Technology 2nd e4., John Wiley and Sons, New York 196-1960, 2 Separation Processes chemical separation without introducing an MSA, by employing distillation (3), the most widely utilized industrial separation method. Di mutiple contacts between liquid and vapor phases. Each contact consists of mixing the two phases for partitioning of species, followed by a phase separa- tion. The contacts are often made on horizontal trays (usually referred to ac stages) arranged in a vertical column as shown schematically in the symbol for distillation in Table 1.1.* Vapor, while proceeding to the top of the column, ig increasingly enriched with respect to the more volatile species. Correspondingly, liquid, while fowing to the bottom of the column, is increasingly enriched with respect to the less volatile species. Feed to the distillation column enters on 4 tray somewhere between the top tray and the bottom tray: the portion of the column above the feed is the enriching section and that below is the stripping section. Feed vapor passes up the column; feed liquid passes down. Liquid ic required for making contacts with vapor above the feed tray and vapor is required for making contacts with liquid below the feed tray. Often, vapor from the top of the column is condensed to provide contacting liquid, called refer, Similarly liquid at the bottom of the column passes through a reboiler to provide contacting vapor, called boilup. ‘When volatility differences between species to be separated are so small as to necessitate very large numbers of trays in a distillation operation, extractive distillation (4) may be considered. Here, an MSA is used to increase volatility differences between selected species of the feed and, thereby, reduce the ‘umber of required trays to a reasonable value. Generally, the MSA is less Volatile than any species in the feed mixture and is introduced near the top of the column. Reflux to the top tray is also utilized to minimize MSA content in the top product. If condensation of vapor leaving the top of a distillation column is not readily accomplished, a liquid MSA called an absorbent may be introduced to the top tray in place of reflux. The resulting operation is called reboiled absorption (or fractionating absorption) (5). If the feed is all vapor and the stripping section of the column is not needed to achieve the desired separation, the operation is referred to as absorption (6). This procedure may not require an ESA and is frequently conducted at ambient temperature and high pressure Constituents of the vapor feed dissolve in the absorbent to varying extents depending on their solubilities. Vaporization of a small fraction of the absorbent also generally occurs. ‘The inverse of absorption is stripping (7). Here, a liquid mixture is separated, generally at elevated temperature and ambient pressure, by contacting liquid feed with an MSA called a stripping vapor. The MSA eliminates the need ite internat construction of sisilation, absorption, and extraction eavipment is described in Chapter 2. ‘1.2 Interphase Mass Transfer Separation Operations. a to reboll the liquid at the bottom of the column, which is important if the liquid is not thermally stable. If contacting trays are also needed above the feed tray in ‘der to achieve the desired separation, a refluxed stripper (8) may be employed If the bottoms product from a stripper is thermally stable, it may be rebered without using an MSA. In that case, the column is called a reboiled stripper (9) The formation of minimum-boiling mixtures makes azeotropic distillation » useful tool in those cases where separation by fractional distillation is. not feasible. In the example cited for separation operation (10) in Table 1.1, n-butyl acetate, which forms a heterogeneous minimum-boiling azeotrope with water, 1s used to facilitate the separation of acetic acid from water. ‘The azeotrope is taken overhead, the acetate and water layers are decanted, and the MSA. is recirculated (Hauid~Liquid Extraction (11) and (12) using one or two solvents is a widely used separation technique and takes so many different forms in industri! practice that its description will be covered in detail in later Chapters. ‘Since many chemicals are processed wet and sold dry, one of the more Common manufacturing steps is a drying operation (13) which involves removel id by vaporization of the liquid. Although the only basic requirement in drying is that the vapor pressure of the liquid to be evaporated be higher than its partial pressure in the gas stream, the design and operation of dryers represents a complex problem in heat transfer, fluid flow, and mace transfer. In addition to the effect of such external conditions as temperature, ‘humidity, air fow, and state of subdivision on drying rate, the effect of internal Conditions of liquid diffusion, capillary flow, equilibrium moisture content, and heat sensitivity must be considered. Although drying is a multiphase mass transfer process, equipment design procedures differ from those of any of the other processes discussed in this chapter because the thermodynamic concepts of equilibrium are dificult to apply {o typical drying situations, where concentration of vapor in the gas is so fay from saturation and concentration gradients in the solid are such that mace transfer driving forces are undefined. Also, heat transfer rather than mace {ransfer may well be the limiting rate process. The typical dryer design pro, Gedure is for the process engineer to send a few tons of representative, wet, sample material for pilot plant tests by one or two reliable dryer manufacturers and to purchase the equipment that produces a satisfactorily dried product at the synonymous in the scientific sense; however, usage of the word humidification or dehumidification implies that one is intentionally adding or removing vapor to or from a gas. ‘The major application of evaporation is humidification, the conditioning of 14 Separation Processes and cooling of water. Annual sales of water cooling towers afone exceed $200 million. Design procedures similar to those used in absorption and distillation can be applied. Crystallization (1S) is a unit operation carried out in many organic and almost all inorganic chemical manufacturing plants where the product is sold as, 4 finely divided solid. Since crystallization is essentially a purification step, the conditions in the crystallizer must be such that impurities remain in solution while the desired product precipitates. There is a great deal of art in adjusting the temperature and level of agitation in a crystallizer in such a way that proper particle sizes and putities are achieved. Sublimation is the transfer of a substance from the solid to the gaseous state without formation of an intermediate liquid phase, usually at a relatively high vacuum. Major applications have been in the removal of a volatile com- ponent from an essentially nonvalatite one: separation of sulfur front impurities, Purification of benzoic acid, and freeze drying of foods, for example. The Feverse process, desublimation (16), is also practiced, for example in the reco- very of phthalic anhydride from reactor effluent. The most common application (of sublimation in everyday life is the use of dry ice as a refrigerant for storing ice cream, vegetables and other perishables. The sublimed gas, unlike water, does not puddle and spoil the frozen materials. Solid-tiquid extraction is widely used in the metallurgical, natural product, and food industries. Leaching (17} is done under batch, semibatch, or coatinuows operating conditions in stagewise or contimuous-contact equipment. The major problem in leaching is to promote diffusion of the solute out of the solid and into the liquid. The most effective way of doing this is to reduce the solid to the smallest size feasible. For large-scale applications, in the metallurgical industries in particular, Jarge, open tanks are used in countercurrent operation. The major difference between solid-liquid and liquid-liquid systems centers about the difficulty of transporting the solid, or the solid slurry, from stage to stage. For this reason, the solid is often left in the same tank and only the fiquid is transferred from tank to tank. In the pharmaceutical, food, and natural product industries, countercurrent solid transport is often provided by fairly complicated ‘mechanical devices. Pictures and descriptions of commercial machinery can be found in Perry's handbook.’ Unii) very recently, the use of adsorption systems (18) was generally limited to the removal of components present only in low concentrations, Recent progress in materials and engineering techniques has greatly extended the applications, as attested by Table 1.2, which fists only those applications that have been commercialized. Adsorbents used in effecting these separations are activated carbon, aluminum oxide, silica gel, and synthetic sodium or calcium aluminosilicate zeolite adsorbents (molecular sieves). The sieves differ from the 4.2. Interphase Mass Transfer Separation Operations 8 ‘Table 1.2 Important commercial adsorptive separations Miscellaneous Separations and Dehydration Processes Purlications Gases Liquids ‘Materiel Adsorbed Materia) Treated Acetylene Acetone Acetylene Liquid oxysen ae ‘Avetoirite Ammonia Cracked Argon Acrylonitrile ‘Ammonia Reformer hydrogen carbon dioxide Allyl chloride 2utene Tsoprene Chlorine Benzene Carbon dioxide Ethylene Cracked gas Butadiene Carbon dioxide aie Ethylene Butane Carbon oxide Inert gases Helium Butene Carbon monoxide, Hydrogen methane Hydrogen Butyl acetate Hydrogen chlotide Carbon tetachloride Compressor oil Many kinds of enses Hydrogen sulde —Cyotohexane {Cycle hydrocarhons —Naphthenes and purfis Natural pas Dichloroethylene thane! Diethyl ether Nitrogen Dimethy sulfoxide Gasoline components Natural gas Oxyeen Ethanot rydrogen sue Reformer hydrogen Ethylene ditromige ‘Hydrogen sulfide SelluehersBaccide Ethylene dichloride Hydrogen sulle No. fue oil Krypton ydrozen mHeptane Mercaptans Propane Berane ‘Methars jet eter Troprene ‘Methylene cMoride Refeigerant 114 Tnopropanet Nivogen| ydrosen Tet foe NO, NO,, N.0 Nitrogen Liguetes Oil vapor Compressed gases petroleum gas Methyl chloe onyeen ‘Arron Mined ethyl ketone Unsaturates Diethyl ether Others (Color, oor. and Vegetable and ania! taste forme ‘ls, suger yrens, ‘tser and 20 04 vitae Fermentation mixes “Turbidity formers Beet, wines ‘Source. FJ, Henley and H. K. Safin, Stagewise Process Design. John Wiley & Sons, lc., New “York, 1963, 50 - ‘Separation Processes other adsorbents in that they are crystalline and have pore openings of fixed dimensions. ‘Adsorption units range from the very simple to the very complex. A simple Sevice consists of litle more than a cylindrical vessel packed with adsorbent through which the gas or liquid flows. Regeneration is accomplished by passing a hot gas through the adsorbent, usually in the opposite direction, Normally two or ‘more vessels are used, one vessel desorbing while the other(s) adsorb(s). If the vessel is arranged vertically, itis usually advantageous to employ downward Slow to prevent bed lift, which causes particle attrition and a resulting increase pressure drop and loss of material. However, for liquid flow, better dis- tribution is achieved by upward flow. Although regeneration is usually ac- complished by thermal cycle, other methods such as pressure cycles (desorption by decompression), purge-gas cycles (desorption by partial pressure lowering), and displacement cycies (addition of a third component) are also used. In contrast to most separation operations, which predate recorded history, the principles of ion exchange were not known until the 1800s. Today ion exchange is a ‘major industrial operation, largely because ofits wide-scale use in water softening. Numerous other ion-exchange processes are also in use. A few of these are listed in Table 13. fon exchange resembles gas adsorption and liquid-liquid extraction in that, jm all these processes, an inert carrier is employed and the reagent used to remove a component selectively must be regenerated. in 3 typical ion-exchange application, water softening, an organic or inorganic polymer in its sodium form removes calcitim jons by exchanging calcium for sodium, After prolonged use Table 1.3 Applications of lon exchange Process Material Exchanged Purpose Water teatment Calcium ions Remoeal Water deattyfization Dicartonate Removal Aluminum anodization bath Aluiotm. Removal Pating baths Meta Recovery ‘Rayon wastes Coppee Recovery Giycerine Sodan chioride Removal ‘Wood pulping Recovery Formaldehyde manufacture Recovery Ethylene glycol (rom oxide) Canty ‘Sugar solution Removal Grapefruit processing Recovery ecortamination Removal ‘Source. BJ. Henley and H, K. Safin, Stagewise Process Desig, John Wiley '& Sons, Inc, New York, 1983, 3 Interphase Mass Transter Separation Operations 7 the (spent) polymer. which is now stturated with calcium, is regenerated by contact with a concentrated brine, the law of mass action governing the degree ‘of regeneration. Among the muny factors entering into the design of industrial exchangers are the problems of: 1. Channeling. The problems of nonuniform flow distribution and subsequent bypass is generic to all low operations. 2. Loss of resins, Ultimately, the exchange capacity of the resin will diminish to the point where it is no longer effective. In arsystem where resin is recirculated, loss by attrition is superimposed on the other losses, Which also include cracking of the resin by osmotic pressure. 3, Resin viiliration. This is the ratio of the quantity of ions removed during treatment to the total capacity of the resin; it must be maximized, id, the limiting rate step is often 4. Pressure drop. Because ion exchange is r diffusion info the resin. To overcome this diffusional resistance, resin size must be reduced and liquid flow rate increased. Both of these measures result in an increased bed pressure drop and increased pumping costs. Fe tenn et wi \ Figure 1.6, Dorreo Hydto-softene fr water. 1 ‘Separation Processes werent Lule etm Figure 17, Complex reboiled absorber ‘Methods of operation used in ion exchange reffect efforts to overcome design problems. Yon-exchange units are built to operate batchwise, where a fixed amount of resin and liquid are mixed together, as fixed beds, where the solution is continuously pumped through a bed of resin, or as continuous countercurrent contactors. In general, fixed beds are preferred where high purities and recoveries are desired; batch processes are advantageous where very favorable equilibrium exists or slurries must be handled; continuous countercurrent operation offers more effective utilization of regeneration chem- icals and geometric compactness. 1.3. Intraphase Mass Transfer Snparation Operations ” Ove of the more interesting methods for continuous countercurrent ion exchange is the use of fluidized bed techniques for continuous circulation of the resin. Figure 1.6 shows the Dorrco Hydro-softenes. In the fluidized bed, a solid phase is suspended in a liquid or gas. Consequently, the solid behaves like a fluid and can be pumped, gravity fed, and handled very much like a liquid. The fluidized resin moves down through the softener on the right and is then picked up by a brine-carrier Auid and transferred to the regenetator on the left, Bach equipment symbol shown in Table 1.1 corresponds to the simplest configuration for the represented operation. More complex versions are possible ‘and frequently desirable. For example, a more complex version of the reboiled absorber, item (5) in Table {.t, is shown in Fig. 1.7. This reboited absorber fas two feeds, an intercooler, a side stream, and both an interreboiler and a bottoms reboifer. Acceptable design procedures must fandle such compfex situations. 1.3. Intraphase Mags Transfer Separation Operations Changing environmental and energy constraints, a source of despair and feu tration to those who are most comfortable with the status quo, are an oppor- ‘tunity and a challenge to chemical engineers, who, by nature of thei (raining and orientation, are accustomed to technological change. Distillation and extraction are highly energy-intensive operations, the latter also sequising elaborate solvent recovery of cleanup and disposal procedures where environmental standurds are ‘enforced. New technologies, responsive to changing social needs and economic conditions, are emerging in the chemical industry and elsewhere. The appliance industry, for exemple, is turning to dey, electrostatic coating methods to avoid paint solvent recovery and pollution problems; the chlorine-caustic industry is Geveloping electrolytic membranes to solve its mercury disposal woes; freth- ‘water-fromscawater processes based on membrane and freezing. principles rather than evaporation suddenly appear to be considerably more competitive. Similarly, liquid-phase separation of aromatic from paraffinic hydrocarbons by adsorption as an alternative to extraction or extractive distilation; or gas-phase separation of low-molecular-weight hydrocarbons by adsorption as an alter- native to low-temperature distillation; or alcohol dehydration by membrane permeation instead of distilation—are all processes where technical feasibility has been demonstrated, and large-scale adoption awaits favorable economics. The separation operations described so far involve the creation or removal of a phase by the introduction of an ESA or MSA. The emphasis on new, less energy- or materil-intensive processes is spurting research on new processes to effect separations of chemical species contained in « single fuid phase without the energy-intensive step of creating or introducing a new phase. Methods oS accomplishing these separations are based on the application of barriers or fields 1.8. Intraphase Mass Transfer Separation Operations a1 to cause species to diffuse at different velocities. Table 1.4 summarizes a number of these operations. An important example of pressure diffusion (1) is the current worldwide competition to perfect a low-cost gas centrifuge capable of industrial-scale separation of the ™*U, and ™U, gaseous hexafluoride isotopes. To date, atomic bomb and atomic power self-sufficiency has been limited to major powers since the underdeveloped countries have neither the money nor an industrial base to build the huge multi-billion dollar gaseous difusion (2) plants currently required for uranium enrichment. In these plants, typified by the U.S. Oak Ridge Operation, “UF, and "UF, are separated by forcing a gaseous mixture of the two species to diffuse through massive banks of porous fluorocarbon barriers ‘across which a pressure gradient is established. Membrane separations involve the selective solubility in a thin polymeric membrane of a component in a mixture and/or the sé M4 1.9, 9. 896 g 5 3 & fon of water, recovery, Va p.413 ‘hydrogen and desterium, Vol6,p 898 ‘austie sods from rayon proces liquid, Vo. Germanium paiication, Enzyme and dye 5 5 Vol 2, p 680 Separation of gaseous “Hotopic wétures, Vol 7p bt Separation of < Mixed vapor sol Dehydration of lopropano ol Recovery of purifed Separation fis 4 De nd membranes Membrane and lect eld interface force Porous bariee Bete td Separating ‘Agent Temperature ‘eadint CCentitugal Membre Solids Foam pressures sufficient to overcome both osmotic pressure and pressure drop through the membrane must be applied. In_per ‘meation (4), osmotic pressure effects are negligible and the upstream side of the membrane can be a gas or liquid mixture. Sometimes a phase transition is involved as in the process for dehydration of isopropano} shown in Fig. 1.8. 1a addition, polymeric liquid surfactant and immobilized-solvent membranes have been used, Dialysis (5) as @ unit operation considerably antedates gas and liquid permeation. Membrane dialysis was used by Graham in 1861 to separate colloids from crystalloids. The first large industrial dialyzers, for the recovery of caustic. from rayon steep liquor, were installed in the United States in the 1930s. Industrial dialysis units for recovery of spent acid from metallurgical liquors have been widely used since 1958. In dialysis, bulk flow of solvent is prevented by bala the osmotic pressure, and low-molecular-weight solutes are recovered by pref. ‘erential diffusion across thin membranes having pores of the order of 10cm, Frequently diffusion is enhanced by application of electric fields. In adsorptive bubble separation methods, surface active material collects at solution interfaces and, thus, a concentration gradient between a solute in the bulk and in the surface layer is established. If the (very thin) surface layer can be collected, partial solute removal from the solution will have been achieved. The major application of this phenomenon is in ore flotation processes where solid particles migrate to and attach themselves to rising gas bubbles and literally float out of the solution. This is essentially a three-phase system. Foam fractionation (6), « two-phase adsorptive bubble separation method, is a process where natural or chelate-induced surface activity causes a solute to ‘migrate to rising bubbles and thus be removed as a foam. Two government. - Kik-Othmor Encyclopedia of Chemical Technology, ‘overcome ormotc pressure Menbrane Forced flow thro Semiermeable membrane by cenfogal force and D.F. Othmer, Eds, Forced fw through ‘Brough metal ingot porous barriers, Pressure gradient to charged membranes membranes lec eld plus ‘Method of Seperation Pressure gradient induce Blectrc field plus J Mek Phase State ‘ed, John Wiley & Sons, New York, 1968 as or guid 3 5 Ss Solis Liquid Liguia Gas Gas Liquid Unit Operation ‘iffsion 2) Reverse ‘osmotis (3) Permeation 4) 9) fractionation (6) (Chromatographie Separations (7) Zone melting (8) hectotsi * Catone rete tH. F. Mark, Pressure ‘diffusion (1) Gaseous Dia Foam & 2 ‘Separation Processes carte mi apropano—wat) Figure 14, Disgram of liquid process. More permeable molecules are open icles Adapted from [N.N-Li.R.B: Long and EJ. Henley, "Membrane Separation Proces 05 Ind. Eng. Chem, 81 G), 18 0365 ‘eter (aopronanel) funded pilot plants have been constructed: one for removing surface-active chelated radioactive aietals from solution; the other for removing detergents from sewage. The enrichment is small in concentrated solutions, and in dilute solutions it is difficult to maintain the foam, A schematic of the process is shown in Fig. 1.9. ‘When chromatographic separations (7) are operated in a batch mode, a portion of the mixture to be separated is introduced at the column inlet. A Solute-free carrier fluid is then fed continually through the column, the solutes separating into bands or zones. Some industrial operations such as mixed-vapor solvent recovery and sorption of the less volatile hydrocarbons in natural gas or rnatural gasoline plants are being carried out on pilot plant and semiworks scales. Continuous countercurrent systems designed along the basic principles of dis- {illation columns have been constructed. "Zone melting (8) relies on selective distribution of impurity solutes between fa liquid and solid phase to achieve a separation. Literally hundreds of metals hhave been refined by this technique, which, in its simplest form, involves nothing ‘more than moving a molten zone slowly through an ingot by moving the heater Or drawing the input past the heater, as in Fig. 1.10. If a temperature gradient is applied to a homogeneous solution, concen- tration gradients can be established and thermal diffusion (9) is induced. Al- 1.3. Intraphase Mass Transfer Separation Operations 2 wl 1 ‘oui Figure 19. Foam fractionation column, ‘though there are no large-scale commercial applications of this technique, it has been used to enhance the separation in uranium isotope gaseous diffusion cascades. Natural water contains 0,000149 atom fraction of deuterium. When water is decomposed by electrolysis (10)* into hydrogen and oxygen, the deuterium ‘concentration in the hydrogen produced at the cathode is lower than that in the ‘water remaining in the air. Until 1953 when the Savannah River Plant was built, this process was the only commercial source of heavy water. ‘The principle of operation of a multicompartmented electrodialysis unit (11) is shown in Fig, 1.11, The cation and anion permeable membranes carry a fixed charge: thus they prevent the migration of species of like charge. In a com- mercial version of Fig. 1.11, there would be several hundred rather than three Compartments, multicompartmentalization being required to achieve electric power economics, since electrochemical reactions take place at the electrodes. + xcoded from this discussion are electrolysis and chemical reactions tthe anode and cathode Pn Separation Processes Frecting esting ole waking ‘ert Ms inate PPeure 10. Diagram of zone refining ' = i ct ‘igure 1.1. Principe of electroisysis 1.4 The Equilibrium-Stage Concept The intraphase mass transfer operations of Table 1.4 are inherently nonequili- bbrium operations. Thus the maximum attainable degree of separation cannot be Dredicted from thermodynamic properties of the species. For the interphase operations in Table 1.1, however, the phases are brought into contact in stages. If sufficient stage contact time is allowed, the chemical species become dis- tributed among the phases in accordance with thermodynamic equilibrium considerations. Upon subsequent separation of the phases, a single equilibrium contact is said to have been achieved, Industrial equipment does not always consist of stages (e.g, trays in a column) that represent equilibrium stages. Often only a fraction of the change from initial conditions to the equilibrium state is achieved in one contact. 1.4 The Equilibrium-Stage Concept 25 Eula iu om acter ste frown | Ecpitriom e = Esteli id han ent, Jatt ‘roe ae Evite avd phase 2 (horton) testa Figure1.2. Representative equilbrum stage Nevertheless, the concept of the equilibrium stage as proved to be extremely Useful and is widely applied in design procedures which calculate the number of 17 Explain, Derive Equations 1-14, Using Fig. 1.17 with data from Appendix I, plot log a eltive volatility) of Cato Ernomal paras sored en Cs aati ce et oC retsonable temperature and pressure, On the same pot show fp for C, omates (benzene, toluene, ethylbenzene, ete), aso with reference to mc, Wak separations re posible By ordinary dilaton, sesuming ture of font paras and aromatic compounds? (E. D. Olver, Difusonal Sepsion Peat ses: Theor, Design & Evaluation, 1 Wiley & Sons, New York, Btu, Chava ih 15, 149, and 1-20 Discuss the possible methods of separating mixtures of o-Xylene, m-Xylene, P-Xylene, and ethylbenzene in light of the following physical propertis, eee o-xylene m-Xylene Xylene Ethyibenzene Nermalboig oin"F 92S] Feet pint F na Se Te ‘tree ieprFimae 000M 306 gga ggan ie wont, 1a, a Oe ao Dec conan 3% ea Deny 39 lem? osm dase dao dao 1s handbooks, Using the physical property constants from Appendix 1 and va discuss what operations might be Used to separate mixtures of (@) Propane and methane () Acetylene and ethylene, () Hydrogen and deuterium. (@) o-Xylene and p-xylene () Asphalt and nonasphalti ol, (O Calcium and Strontix 90, (@) Aromatic and Nonaromatic hydrocarbons (h) Polystyrene (MW = 10,000) and polystyrene (MW = 100,000), (Water and NaCl It is required to separate the indicated feed into the indicated products, Draw a simple block diagram showing a practical sequence of operations fo acconplin the las 126 Lay 12 129 Problems 45 Feavired results, State briely the reasons for your choice Feed Products 45% Alcohol 1. 98% Alcohol, 2% B. 4556 Organic solvent 2. 8% Organic solvent B containing 2% alcoho 10% Soluble, nonvolatile wax. 3, Solute wut in solvone perties ‘Normal boiling pt alcohol = 120°C [Normal boiling pt organi solvent B = 250%. Viscosity of soluble wax a 10% concentrion is similar to water, ‘Yiscotiy of soluble wax at SO% concentration is simiar these? oto ol ‘The alcoho is signicantly soluble im water, ‘The organi solvent Band water are essentially completely immiscible The nonvolatile wax is insoluble in water ——________ terse Clapeyton vapor pressure equation to derive an algebraic expression for Trott rtionship given in Fg. 1.17. Use your expression in cogheneean woe meee Sie fo check Fig. 1.17 for 8 boling-pointdifernce of so ea mixture boiling point of 100°C. Consider the separation of mintre of propylene, propane, and propaiene. Show by diagrams like those in Fig. 1.19 mon (a) Two sequences of ordinary dstilation column (©) One sequence based onthe use of extractive dsiltion with a polr solvent n Aaditon to ordinary citation faeapaute of 70% benzene, 10% toluene, and 2056 ortho-xylene is to be separated cncheak ag mponeats by a sequence of two ordinary distiation columns, Becca oe Faspectihe following heuristics (rules), make diagrams lke those of Fig: Las eta preferred sequence. (@) Separate the more pleatiful components ealy, if possible. (©) The most dificult separation is best saved fer last, Pf elon a scheme for separating a mixture consisting of $0, 10,10, and 30 mote dhe ra pemeene toluene, and oxtho-xslene, respectively, by dition ace the two heuristics given in Problem 1.27, ee seowshce 0 separate the reactor efluents from acrylonitrile manufacture (@C3H.+ 30,4 2NH, > 2G, N + 6H,0), mints e ttueat 40% iner gases, 40% propylene, 8% propane, 6% sre to le 5% water, and 196 heavy by-product impurities. Design coun gene eto ent ert gases without excessive loss of acrylonitrile or propylene 1 5 Recyel the propylene to the reactor without recycling the sep lone 3 Purge the propane to prevent propane buildup in the texetor, as Separation Processes 44 Recover the aerylontril for final purification. (D. F. Rudd G. }. Powers, and Recontt ala, Process Synthesis, Prentice-Hall Book Co. 1973, p. 176 Lav Show as many. separation schemes as you can forthe problem of Fis, tt. Stow a that in the presence of furfural as an MSA, n-butane is more vol assuming and that ordinary distilation cannot be used to separate n-butane than, |-butetecene-),Furfural less volatile than n-pentane, One such scheme is shown in Fig. 1.20. 2 Equipment for Multiphase Contacting TT Because distillation is a very important industrial process for separating chemical components by: hysical means, much effort has been expended to Merease the performance of existing distillation equipment and to develop new types of vapor fiduid contacting devices which more closely dian equilibrium (the condition of 100% efficiency) between the distilling phases. William G. Todd and Matthew Van Winkle, 1972 Gren thermodynamie data, efficent algorithms for accurately predicting the Se required for & specific separation are readily availabe. However, when it stages restne mechanical design of the equipment, to quote D. B. McLaren and J.C. Upchurch: ‘The alchemist is still with us, although concealed by moun- tains of computer output. The decisions and actions that Iead to trouble free operation depend on the “art” of the practitioner. One dictionary defines art as a “personal, wn Bhalyzabie creative power.” it is this power, plus Gaperience, that makes the difference between success oF failure of process equipment.’ Chemical companies usually do not attempt the mechanical design of theit wn qrocess equipment. Their engineers perform the calculations and condi’ are epreriments required to fill out a vendor's design data sheet such as shown Tt Fe. 21 fora vapor-liguid contactor. The vendo, who very frequently isnot Wd Fis torent is to be processed, submits a quotation and a recommended va steal design. This imust then be evaluated by the chemical companies’ mezncors because, even though there may be performance guarantees, Plant Shutdowns for modification and replacement are costly. a ” Equipment for Multiphase Contacting Process Design Data Sheet Item No. or Service» Tower diameter, LD, Tray spacing. inhes ‘ova trays in section Max. 4? mm He Condi at Fray NO. Vapor ta tay," Pressure Compresstity "Density. eu. “Rate, cn Tse. tcl6) etsV DD, =D Liquid tom tay, °F Surface tension Viscosity. ep “Density, eu. Rate, he GPM hot liga oaming tendency “These values ate required ia thie forn fr direct computes input Nigh Severe NOTES: 1, TWis form may’ be used for several sections of trays in one tower, for several towers, oF for various lading cases. Use sional she's necesiary 2. Temaximom capacity at constant vaporigudeaiodesged?————— 3: Minimum rate as 96 of design rae:——% 4 AMlowable downcomer velocity (if speied):-———fusee ', Numbet off paths or passes: ——-

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