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    Don't Gamble With Physical Properties PDF

    Uploaded by

    Juan Pablo Trujillo

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    © All Rights Reserved
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    of 12
    SUCCEEDING AT SIMULATION Don’t Gamble With Physical Properties For Simulations Finding good values for inadequate or missing physical property parameters is the key toa successful simulation. And this depends upon choosing the right estimation methods. Fic €. Carlson, agen Teeny ne hemmical engineers use process simulation to perform a variety of important work. This work ranges from calculations of mast and energy balances of large flow sheets Lo prediction ofthe performanc process alternatives that ean save millions fof dollars. Aa engineer very quickly can define a complex flowsheet and all the process conditions. Desktop computers now allow rating. sizing, optimization, and dynamic calculations that previously required large mainframe computers. In the past, these simulations sere often built by a group of experts, including a physical propery expert. Now, simulators Such as ASPEN PLUS, ChemCAD Ill, HYSIM, PRO Il, and SPEEDUP are easi- fer to use and more powerful than the lalone programs of the past. Today. a single engineer can setup the basic simu lation specifications. including the physi: cal properties. in very litle tire Missing or inadequate physical prop- eies, however, can undermine the accu racy of a model or even prevent you from performing the simulation. That some ce (quired information is missing is not an oversight in the simulator Afterall, for ‘most compounds. physical property” pa rameters are not known for every thermo= dynamic modet or forall temperature oF pressure ranges. Models have built-in as sumptions and practical limits that should apply. I this aniele, we will provide practi cal tips and techniques t help you accu rately describe the physical properties needed in a simulation, Ax an engineer, you always will have to make assump- tions in terms of physical properties, however. The goal of this ancl i a out Jine the appropriate assumptions. and to provide techniques when properties missing. Tho five important tasks Successfully describing the physical propenies 0 be used in a simulation in- volves five tasks: selecting the appropriate physical property methods: 2. validating the physical properties: 3.describing nondatabank compo: nents (chemical species or compound) and missing parameters; 4. obtaining and using physical prop- erty data: and S.estimating any missing property parameters, Tt can be argued that these tasks are ‘ot sequential and, 10 some degree, they are concurrent. During simulation devel- lopment. however, you will need to visit each area to be confident that your simu lation is as accurate as possible — so that important decisions can be made based on the results of your simulations Selecting the appropriate physical property methods This essential first step will affect all subsequent tasks in developing accurate physical properties in your simulation Indeed, the choice of the physical proper= ty models fora simulation can be one of the most important decisions for an eng reer. Several factors need to be consid ‘CHEMICAL ENGNEERNG PROGRESS * OCTORER 205 © 35 SUCCEEDING AT SIMULATION ‘red, and no single method ean han dle all systems, Table I lists some thermodynamic models available in simulators quaint State Models ‘Atv Coeiciont Models “The four factors that you should Bend Wed Fail A oe Star Becton NATL consider when choosing property * “ Table 1. Thermodynamic property models Ered Heyer Cone Fong methods ace arog frie equason of sae for NT. ‘the nature of the propenies of heramesaton™ ScatcharHidebrond interest sets” uxiauac ‘the composition ofthe mixture, Lee fase LK) juntas the pressure and temperature Lee Keser Plochar | Yentes eos ae Feep oteaee AI | ion + the availability of parameters. poietic | yo Prot SK | Seesit odte To ease the selection of the Fight jean IK) | Free atns hysical propery methods, we Sug fegrchsons Son | Brean gest using the decision tees shown in KS or PR wth Wong Son miing rule Chao Sener Figures 1-3. These uees are based on KS o Rich modiea-huronVgal2mx- | Grayean Seed the four Factors for selecting property ingrule enEanberg ‘rethoxds, and can be used when the SateherLacambe for polars Stam Toler chemical components and approxi- ‘male temperature and pressure ranges are known, While these diagrams are Simplifications, they do show the busic steps of the decision-making process, while the noes in the sidebar Amplify some ofthe key points. The nature ofthe properties of in- terest. A question that you may ask yourself when stating & simlation is “Does the choice of physical property methods matter?” The answer 's an emphatic YES. The choice can Strongly affect the prediction of the Simulation, You should be selecting collection of methods that will best predict the properties or results of ine terest 10 you. Because many chemical process Simulations include distillation, stip. | Ping. or evaporation. one important potential consideration for the choice OF physical propenty madels is vaporfiquid equilibrium (VLE). This | isthe area in which the most physical | + Not ned othe Squid phase + SeeFigue? oct NATL ——- tener eectoie <> Peng Roinson eden Kwang Soave, Use Keser Poker | —+ naa seader, | Grayson seeder | Braunk0 | | | se Braun KD property work is focused in chemical enginesring. Liquidliquid equlibn lum (LLE) also becomes important in processes such as solvent extraction and extractive distillation Another critical consideration is pure-component and mixture en= tp men @ nom PD Ricans — AD roses thalpy. Enthalpies and heat capacities — | sre important for unit operations such | Source in a het exchanger, condensers. dis L__ — | lation columns. and reactors 1 Figure 1. The fit eps Jor selecting plyial propery methods 36 + ocrosen ios + chemucaL encmeenine PROGRESS Navigating the decision trees Her re some piers o hep you navigate the decison wees that 26 ba 8 gues 3 nacre pseudcomporents? la many sppicaians wher ny no: oe maeeales ae preset euch a¢m ybrocatbonpocessng and fragh metro 0 complox Wal stesso representing aby athe ‘no Eonar, sea groupe cansuens by same uct! ropery sch as tein pit Ins wey, a mature unsafe Saunt can be reeuced 0 0a ewer The properties ofthese grouped ensivets, ales pstudocomporets, ae representd by an sreage Deng sat specie gravy, and moleslar weigh you 40 nae seudocampanents th canstiuents shoud be deserved by « molecu Ison and ae eletred to ral corpora ‘Why are electra minures erent? Bacvly mints elude omponarts ht are charged molecule ane or ta form ee, Some fmabtors allow eaeunton af elevolye eencion equlean wth pase equlisigm. Ths 2 var power method ard ts usage covers Imany applications euch at eauste rerbding,raurakaian, 34 910 docion, ands pecptation. The tonieaty of lect Slsons “eval cantanag wate can be obsradn Deng Don evan a leg ool gar hat a. ang sas oe sautonto chnge esl ‘ot gass, and a precptaon, The most conman secre et ts a8 te Pasar modal, a the mofed NATL tcwty coecent ‘model of Cher ana cowsters. Some etcuohes, Ie ara ace a [eete 20d, are very ak anda eleva matod nt egured nich type of method shoud be chosen for matures contanng pot companent but eects? There net groupe maths hase on atv cooicense equations af state. Use actey-coet lesen band meade when pesca af owt edu yest ost ‘man 10 aro 150 psa) ani ra components are near ere! pit Ac tty cooler meds go chan are ured to carte peeit ron ideal iid beraor such a or VE and fr LEI cen as, egutbon: Cs-state meteds excl ther aby rapeset data and exap0 ‘wah temperature and pressure up to and above the micare cia! De. Now, however. metho eying on cube equations ef sa wah Predictive ming res efactveN canine the SvengOs ofthe two reho. (Seo Table 2) For maha pessores ane temperatures these ‘Special equates of sae are Bete 2s they were aavloneg 0 ap ‘vader range oftamperatres, These mathade corporate acy eo events nthe ealeiabon of component tea ctans represented Oye cess Gbts re energy. Most a the late use a UNIAC based acy Cecficont mal ata default but you can use ay acim coer "AC smulaton pressures les than Id a ard wher hare ae 80 ear inal component, frie Best asus use te isan NAT, UUNIQUAC Beary pacametrs hat may Se avai ulm estaba, de i bnary pares Yo exper mena at if aeabe) sng Seb featiciem models Trese parameters may have Been detamied ato fern amperatures peeures ard composts than yu re smug seugh, so you my ot ob the Best posse aeutacy. WH etactn parameters ae rt aatabie, howe you can use he UNFAC ethos. When shoul UNPACbe ured? UNSC a er UNF base uty eceticient mages are predictive approaches tat we stuca russ to erate component etsractens Foe sacra ormaton out agate componente uray avaible he Buin aban, UNIFAG abet recite act cet as 2 feedon a em. boston and temperature You ean make use of UNFAC wen you eat inet at 2 nary paremetes of when wf apprcniats ale or stance fr» component wh ow pray ‘scat yes, hare have been roves 1 UAC ite Table 3 throes rr tea ang nl! one ‘ange Recor etn UNPAE peated lca ch {etoguats ad sues ay be shld you can a8 De raps {woes oyu son Samitrs may he 1 fem ory sacton prt ose UMUE, MTL Suna Nata comgonens con be Gesibed ung UNA, hone ad sox ah gop arses ae aie, xslt compensa {ettnw UNFAE gape ace nn egeene an sss Se we hghy recommen sys eg sane rie Binary orterary seme texte. How shud te vapor ose be vet? Te che of he WE sted vg 2 sy ceca model an feos 8 tno ‘oder tb apr pave pon weer pase secon so ned as ie ceo tete Hid he be 90 po moe ‘od be Hyder Coma or Notaget Ase coning he entre mayege a seeal out ree epee el Stream coo hyrgen song. sssen ne var Pst nnave a ong eect on pase ei an era. Vin shoud dete be evnraten er ow pps prove nets? retin ofa hoy an cesy bo wer Cit mtr you slat sooty sce th tt inatots Check he rt ateometten re ela ated ad ar es cue ya xeon of toh eg tow Mate nd deoses cant acute yo stain oS {tno dependent rode has net Recto enge ttre ond posure dependent noe seh 3 08 COSTAL fo pne cenpoes an Anees Palco state AP mated Mesh ‘Soplne Th hace attenconnendee ye st “ono onuy stays asia ome gn evrtono an aaa tte Tre genoa! ste aro coal» ep {tom dea sabe apa nto srs. compres such ae aa ae Haye Cone ate ets i cr ites lrgeraansemal von onda aeprace Uinideraloes casted by varey tes sm liners eager ase eesens Se bee ue cpa ead ent acente ame atl us nay bd toby soars Toscacbeen at age twig ey Wea mmay ae 2 Hee wus tpt congo aed eta, Hs es gas an Sh. and ena ely epic, pte ler sto voor toe ey fear ote ‘cn pss te tran presi, odo aed pss cr tnetn fam be sauce peste be fen peso ints tat ai sgn coeur 2 tad wy are tor tue he capcey oohwona Fo" san compet Be bod Eat mint be scent ha hrconriy pees Th canbevey spent ore eoeg vu penetrates fomete wage rch toner rgpocrnet loop ars fn tant eater td hes apt 69) metas e poe he Sascyl oder coacins isco enter moran propery saosin, puns teat hoger ad Gan ctr, avr egeod atnemedecnlig vacuo gly egret CHEMMCAL ENGINEERNG PROGRESS + OCTORERaH6 + 37 SUCCEEDING AT SIMULATION ——————— 1. wan, usa, r rahe Verarcee Petober M2, dnd Tes Vananees rated i | Pawest snl — | _ io _ WUSON, = | —— senanennuber Reon, | | [ Paar aks wr | Phar XS wit > ibe | e oh | OPS eh v2 PD rasan D> wwe | 1 & Imeraction Parameters vee Source: WW Figure 2, Proceding for polar and nanclecrolte components. zon, NATL UNIUAC, | > oF UNIERC win soe foehosamore Wear , | iene _, to, NATL UGA tL {Bini Gira win ayes OConne uwiauac tr Nehnage E08 ‘ONAC itor NAL. UA, + ertiltac* won ise! Gos cmos & Nie Pint ree sen UNIFAC ands Etensans Sourte10 18 Figure 3. Options jor vaporiphase calculations with ativiy-coefcient models 38 * OCTOBER 1e% * CHEMICAL ENGNEAING PROGRESS re enol cs Praicwe SAKIPSRK) PR with modied Harn Sd? mang ae PR Panagitopols ming rule PR wt Wong Seale msg 0 KS with moda Huoncsh2 ingle KS with Panaioplvs ising KS wit Warg-Sner mixing le PEN tenn Cs Mode! edits Donmundimediee | MME LE, animes | ebereneneian | Veo arises (ish ‘seearbone Lynpby-moctid | vie Hy (Ecese UNIFAE ISB 14) | Era) eae Le ue ‘oso fi wae revsons | we fies) “Inete measurement of polarity. In general, 0,7 mole fraction of acetonitrile. Fig. ents "such as water, aceione. mixtures. of nonpolar components ure 5 presents VLE for a mistore of wldeiyde. and methyt chloride will exhibit less nonideal behavior. two” slightly polar compounds, are sttong dipoles, Many polar com Figures 4-7 ilusrate the effect of toluene and phenol, at { stm. The de Pounds are associative, and form polarity on binary vaporfliquid equi- vation from ieality is. shown by oplexes. oF dissociate into ions. libria, Figure 4 shows the predicted comparing the predicted curve ftom Components like ethane and -hep- and expettmental VLE of two highly an ileal liquid assumption to that vonpolar, You can use your polar components, acctonitrile and froma method predicting nonideality 7 Vana anoin ie (eee Ue Mactan ene Teta rasa, A over az oso os os oF 8 ess t4 Molen Souce:ti_| igure 6 (ubave. VLE of extoheanelbenzene system at Fat 1 Figure 7 (righ) VLE of ethanefpropylene system at 10°F (CHEMICAL ENGMEERING PROGRESS + oCrOSER HE + 39 (9 — tenia Maracion eed (0 == Laud MoatracoonCiz0 the nonrandom we-liquid activity coetficient model (NRTL) and Redlich-Kwong equation of state For the vapor phase), Figure 6 depicts the VLE of a mixture of cyclohexane and benzene at 1 atm. Here, the imerac~ tion of seemingly similar molecules with a diflerence in boiling point of less than 1°C causes an azeotrope ata composition of about 0.54 mole frac: tion of benzene. A mixture such as ethane and propylene (Figure 7) isan almost ideal one, and does not deviate ‘uch from Raoul's law Mixtures of nonpolar and polar compounds, such as water and hydro: carbons, often will form (wo liquid phases that are very immiscible. Fig tres 8 and 9 show examples of mis ble and immiscible systems of lige uidiguid equilibria, respectively at 1 atm. In Figure 8. cyclohexanol is im miscible ia the water phase but the forganie phase contains up 10 0.50 mole fraction water (0.10 mass frac tion water) Figure 9 shows the high degree of immissbilty im both the organic and water phases for a mix: ture of benzene and water where there is less than 0.06% by mole ben zene (0.3% by mass). Because of this behavior, some simulators have a spe cial property method 10 eat the water phase as organic-free (also called Free-Water) Most simulators offer collections fof property methods in predetined sets based upon_methads that fre quently are used for certain types of ‘mixtures, Usually the sets are identi fied by the method used for phase equilibria, When these sets use an equation-ofstate model, the same ‘model is used for many properties, in luding those for phase equilibria The pressure and temperature range. Ths is especially important in choosing the method to perform phase equilibria calculations. Meth- ‘ods that are based on Raoult’ law oF that use activity coefficients are not accurate at high pressure or when the temperature is above the critical tem- perature of & component. You can use Henry's law when you have light gases in suberitical solvents, but it generally is not recommended for concentrations of solute greater than 5%. In general. equations of state are better suited 10 predict VLE over & wide temperature or pressure range, specially at high temperature and pressure The availabilty of parameters Without sufficient pure-component and binary parameters, you will be vnable fo calculate pure-component or mixture propenies. You must choose among obiining and using experi- ‘mental or literature data, estimating parameters. of choosing a less rigor tus method. This should be investiga €d for ll paysieal property methods in- eluding those shown in Figures 1-3, 40 + ocrosen re + crenicaLewamecRe PROGRESS Figure 8 (lef). LE of ejelohexanolwater system at 1am W Figure 9. (above) LLE of bentenetwater system at J atm. Validating the physical properties ‘A necessary step in any simulation project is validation of the physical Droperties. Tis involves repoming, tab lating, or plating pure-component and snixture properties. and comparing the results t© known data or expected be- havior. This isan important step in any simulation and should be performed for databank as well 2s nondatabank com= Ponents. Simulators can provide ese calculated properties in tabula and plot format. This is a usefol tool for under standing how pure

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