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    AVTrias wae er 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. Erie C. Carlson, Aspan Technology hemical engineers use process simulation to perform a variety of important work. This work anges from calculations of ‘mass- and energy balances of large flow- sheets to prediction of the performance of process alternatives that can save millions Of dollars. An 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 were often built by a group of experts, including a physical property expert. Now, simulators such as ASPEN PLUS, ChemCAD III, HYSIM, PRO Il, and SPEEDUP are easi- er to use and more powerful than the standalone programs of the past. Today, a single engineer can set up the basic simu lation specifications, including the physi- cal properties, in very litle time. Missing or inadequate physical prop- cents, however, can undermine the accu- racy of a model or even prevent you from performing the simulation. That some te- {quired information is missing is not an oversight in the simulator. After all, for ‘most compounds. physical property pa- rameters are not known for every thermo- sala & Electolytes: OD Beams — AD res Broun K-Qor dest Source:(7) 1 Figure 1 The first steps for selecting physical property methods. (OCTOBER 1856 » CHENICAL ENGINEERING PROGRESS Navigating the decision trees ere are some pointers to help you navigate the decision trees that ap pear as Figures 1-3 What are peeucocomponents? In many applications where clynon- polar molecules are present (such asin hySrocarbon processing andre Iii] de istte is so compl that stead of epreserting ty alle nawn constuons, ts ease to group the consttuents by some useful propery such a bing pint. nis way, mature of hundtecs ot con- ‘sues canbe reused to 30 or fewer. The propor ofthese grouped onsttbons, calles peeudocomponens, are represantd by an average boiing pon. specif gravy, and molecular weight. Ifyou donot use pseudocomponens, he constituents shout be desribed bye molec Fa formula and are oteredto as eal componont. Why are elective mires citeren”Eleaye mirurs acute ‘components tht ara charged molecules (ons) or hat fern sats. Some Simulators allow calelaton of elecicte reacton equliiom vith phate equibium, This i avery ponerul methed and ts usage covers Imany appicatons evch 9 caustic scrubbing, nwvalaation, acd pro- Suction, and sat precipitation Tho noridoaiy of electro solutions, ‘sally containing water canbe observed in bong son vation sal ing outa! gate (hai, adding sats the Sluton to changathe soli ity of gases), and sat paciptaton. The most common elclye met ods ate the Per mocel and the modied-NRTL activity cooicient ‘model of Chen and coworkers. Same elecohres, ike formic acd and ‘esti acid ae vary weak and an electrolte meted isnt requed, Which type of method should be chosen for mixtures containing polar camparants but no slecvalres? There as two groups of matods| = based on activity cosets or equations of sat, Use aciviy-coet ‘eiet bases methads when pressures ae low to madam pica less than 10 aro” 150 sia} and ira components ae near erical pit Ac tiny coefficient modes also often are used 10 accurately pred no: ideal iuidbehavar such a8 fr VLE an for LL. In const, equ of-tate methods excel i heir abi to represent data and extrapolate wth temperature and peassure up fo 266 above the mature citcal Drint. Now, however mthaderalyng on cube equations of state th Prodictive mixing ules eecivaly combine the stents ofthe two ‘methods. [Seo Table 2) For higher pressures and temperatures. hese ‘Special equations of tate are beara thay ware developed appl to ‘8 wrdec range of temperatures. These methods incorporate activity coe ficients nthe calelation of eomponemt intracons represented by ex ‘cess Gitbe fee anergy. Most of he ater use a UNIFAC-bsed acy ‘oefcient model as the deta bt you can use any acttycoeficient. ‘A simolaon pressures less than 10 atm and where there are no naar eitealcorponent, forthe best ests ase the Wise, NATL oF UUMIQUAC binary paramaters that may b avaiable in buitin databanks, ‘or ft binary parameters to experimental data avalablel using act cafiint made. Those pararaters may have been detrmined ati feconttemperaturs, pressures, and compositions thn you ar simulating. ‘ough s0 you may not obtan te Best posse acura. iterecton parameters arent sable, however, you ean use the UNIFAC mathod ‘When should UNIFAC be used? UNIFAC another UNA asad a tiny coeticient models are predictive approaches thet use seustura ‘soup t estimate component interaction. From structural information| [bout organic componans usualy avalale inthe bun databank, UNIFAC sable to prec the actistycoofconts asa function of eon pasion and tompeature You can ake us of UNIFA wien you donot fave oxparimontal data orbnary parameters or when an approximate ‘leis acceptable fr instanea, fora comgonent wit lw rai. recent years, thare have been ingroveronts to UNFAC (ee Tale 3) ‘hat can bat predict VLE heat of mixing, ané LE oer 2 wide temper tur ange. Regent extensions to UNIFAC proposed for laces such 33 refrigerants and sugars maybe Useful, nd you can ad the groups ‘and parameters to your simulation. Simulators may ave the ably tO generate binary interaction parameters for Wilson, UNIQUAG, or NRTL from UNIFAC. Net all components can be described using UNIFAC, however, and rot al fou intractons are avaible, Examples of components hat ‘ot hae UNIFAC groups include metals, erganometals, and phosphates. So, hgh recommend always doing » search fr avaabe data on binary or teary systems ofintarest, ‘ow should the vapor phase be treated? The ehsice of the VUE rmathod using an actvtyeoetilont mada also requires a choi ot ‘adel forthe vapor phase properties. I vapor phase association is ob- served (asin the case of acetic acd), then the vapor phase mod shoul be Hayder-0'Comsel ar Notimage. A system containing yeto- ‘G20 Huorde may requir a special model to represent the high cereal association due to hysrogen bonding, Associaton inthe vapor phase am havea song eect on phase equlbia and enthaly When should defauite be overridden for other physical propery imatheds?Pradicon of dans, erhaay. and wscosty also are impor tant in simulators, and you soviet automaticaly accept the default maths. Check the simulstr documentation forthe deat athod and mixing res ‘Vapor density sealed by an aquaton of sat or the idea 5 tow Mature gud densities can be calcletad by an equation af state, temperatrs-depandant model such a that of Racket, or by a temper ture: and pressure dependent madel suchas the COSTALD. For psusdo- ‘omnes, an American Pavol Insite (AP!) method epialy is lamployed. The Racket mel is ecommonded for ganecl use. ‘Vapor entnalpy usualy ealeusted via an eal gat assumption tm equoon of state, The equstion-o sate methods calculate a dopa. ture from dealt cal the vapor enthalpy depanure. For components Such a5 acai ai, the Hoyce-O'Connel model is bes. ad wil calev Tate a largerthan-norma per enthalpy separure Liquid enthaipis ae cae sates by vty a methods. the sim lator uss the ideal as asthe raferance stato, then the pue-component liquid enthalpy is ealeuated fram the ideal gat enthalpy ard guid on- thaly departure, This ean be writen as Hed a His eH He) 1 whore His the pure: component iui enthalpy, H'sis th deal gas on thalpy, and (Hse uid enthalpy deparue. Tis deparur in ‘des the hest of vacation, the vapor ethalpy separa rom the seal pressure tothe saturation pressure, and the lewd presure cor feet tam the saturation pressure to the real pressure. Simulators also alow separate calulatns for Kuidemtaly directly from te liquid-heat capacity plyeomi. For sorte companens, tre method in 1 wil ot be accurate enough for liguid-heat-capaciyprotctons. Ths canbe very import yu are expoting your propery information te anather program sh a nef rigorous naat-exchanger design Yow ean use he late iqud heat capaey (pL) method ro improve the ac curacy of quid heat capes. \sconyis another impor property for sng of siping, pum, heat exchangers, and distilton columns, There ae venous vapor an liu etd for calculatng viscosity ard, general, he parameter ‘ukements for tase mothds are substantial CHEMICAL ENGINEERING PROGRESS © OCTOBER 1996 © 37 SUCCEEDING AT SIMULATION (Tet nar untauac, Bnd Ther Vacances io _ WILSON, NeTL UNIQUAC, 0 Sn Tha Variances yar UNIFACLLE Ye No ty UNIFAC andi io, Brensons Pctober (Seeatso Figures) Poe Nor-letrhes Yes Sehwartanruber Remon, Prorsks wen WS, PR or KS wath MV? P> tober a at PSR, | Lite aor wit me > vests & lnsreton arama W Figure 2. Proceeding or polar and nonelecrolye components. Souroei7 ‘ison, NATL_UNIQUAC, ‘5 or UNIEAC wit special ES fochexamers = _@ ‘Waser, NATL, UNIQUAC, won yous NATL __Dimers __.UNIFAC with Hayden O'Connell uae ornatgel £08 NAD rr an RTL UAC, rac re ie Simeos & Vapor hase Asotin Dees Pomersion “UAC ods ersions saurcein 1 Figure 3. Options for vapor-phase calculations with aetvity-coefficent models. 38 + OCTOBER 1995 * CHEMICAL ENGINEERING PROGRESS Dre ence Cues Predictive SRK (PSRK) PR wth modes Huon Vde-2 ming rule PR wth Panegitopous mixing rule PRiwith Wong Sandler mixing rule KS with madiied Huron Mie sizing le KS wih Panaitoplous mixing rule KS with Wang Sele rising rule Pee Caetad eo ns Mod Dormund-medied | VLE LE, 77 UOMAC 36 Kaiverexersion | VLE of lorinated fis hydrocarbons Lynabymodiied | VLE, My (Excess LUMtERC586) (1) | Emap) ‘UMIFRG, LE ue (0 iy ia, revsions | VLE tis “nite-siuion avy coetcont In addition, density, viscosity, pH. and thermal conductivity may be es- sential for other process calculations. ‘Transport. properties are important when doing equipment sizing calcula tions. Also, processes such as metallur- gy and mining will require calculations for phase equilibria including solids. The composition of the mixture Composition will influence all proper- ties, due to the way mixture properties are calculated. It will affect phase equilibria greatly because ofthe inter: action of the components in the mix- ture. Usually, the interaction in the Tiquid phase is the more important be- cause of the close proximity of the molecules in that phase. The nature of the vapor phase also can be significant if the components form complexes. The important intermolecular forces are electrostatic, induction, attraction, and repulsion between nonpolar com= ponents, and chemical forces such as hhydrogen bonding. A good overview of these forces is given in Ref. 1 © = Vapor Moloracton © =Liuid Moltracton W Figure 4 (above). VLE of acetonitile/water system at I atm. Figure 5 (right), VLE of toluene/phenol system at I atm. ‘The magnitude of the electrostatic simulator to report the dipole mo- water, a 1 atm. The azeotrope is ac- and induction forces is related to the ments of databank components as one curately predicted at approximately polarity of the components. Compo- measurement of polarity. In general, 0.7 mole fraction of acetonitrile. Fig- nents such as water, acetone, mixtures of nonpolar components ure 5 presents VLE for a mixture of formaldehyde, and methyl chloride will exhibit less nonideal behavi two slightly polar compounds, are strong dipoles. Many polar com- ‘Figures 4-7 illustrate the effect of toluene and phenol, at 1 atm, The de Pounds are associative, and form polarity on binary vaporiliquid equi- vation from ideality is shown by ‘complexes or dissociate into ions. libria. Figure 4 shows the predicted comparing the predicted curve from Components like ethane and nhep- and experimental VLE of two highly ideal liquid assumption to that tane are nonpolar. You can use your polar components, acetonitrile and from a method predicting nonideality 02 03 04 0S 08 G7 OB agerys| Source:(15) 1 Figure 6 (above). VLE of exelohexanelbenzene system at 1 atm. Figure 7 (right), VLE of ethane/propslene system at 40°F. oF Moleraction ‘CHEMICAL ENGHIEENING PROGRESS. + OCTOBER S56 © 39 SUCCEEDING AT SIMULATION Figure 8 (left). LLE of eyelohexanoUwater system at 1 atm. Wi Figure 9. (above). LE of benzene/water system at 1 atm. (the nonrandom two-liquid activity sets based upon methods that fre- Val coefficient model (NRTL) and quently are used for certain types of the physical properties Redlich-Kwong equation of state for mixtures. Usually the sets are idemti-. A necessary step in any simulation the vapor phase). Figure 6 depicts the fied by the method used for phase project is validation of the physical VLE of a mixture of cyclohexane and equilibria. When these sets use an properties. Ths involves reporting, tab- benzene at 1 atm. Here, the interac- equation-of-state_model, the same _ulating, or ploting pure-component and tion of seemingly similar molecules model is used for many properties, in- mixture properties and comparing the with a difference in boiling point of cluding those for phase equilibria. results to known data or expected be less than 1°C causes an azeotrope ata The pressure and temperature havior. This isan important step in any ‘composition of about 0.54 mole frac- range. This is especially important in simulation and should be performed for tion of benzene. A mixture such as choosing the method to perform databank as well as nondatabank com: ‘thane and propylene (Figure 7) is an phase equilibria calculations. Meth- ponents. Simulators can provide these almost ideal one, and does not deviate ods that are based on Raoult’s law or calculated properties in tabular and plot ‘much from Raoult’s law. that use activity coefficients are not format. This is a useful tool for under- Mixtures of nonpolar and polar accurate at high pressure or when the standing how pure-component and mix- compounds, such as water and hydro- temperature is above the critical tem- ture properties, such as density, heat ca- carbons, often will form two liquid perature of a component. You can use pacity, and excess properties, vary with phases that are very immiscible. Fig- Henry's law when you have light temperature, pressure, and composition, tures 8 and 9 show examples of misci- gases in subcritical Solvents, but it and how they behave when extrapolat- ble and immiscible systems of liq- generally is not recommended for ed. Similarly, such results can be used to Uid/liquid equilibria, respectively, at | concentrations of solute greater than generate plots of VLE and LLE to com- atm. In Figure 8, cyclohexanol is im- 5%. In general, equations of state are pare to diagrams inthe literature and ac- miscible in the water phase but the better suited (0 predict VLE over a tual field data. Some simulators have organic phase contains up to 0.50 wide temperature or pressure range, the capability to generate residue curves ‘mole fraction water (0.10 mass frac- especially at high temperature and for distillation of ternary mixtures. The tion water). Figure 9 shows the high pressure. residue plot capability also is a powerful degree of immiscibility in both the The availability of parameters. tool for distillation analysis organic and water phases for a mix- Without sufficient pure-component Use the tabulation and plotting ture of benzene and water where and binary parameters, you will be tools to determine the cause of dis- there is less than 0.06% by mole ben- unable to calculate pure-component or _crepancies in properties. If a mixture zene (0.3% by mass). Because of this mixture properties. You must choose property is incorrect, investigate if a behavior, some simulators have a spe- among obtaining and using experi- single component is the cause by re- cial property method to treat the mental or literature data, estimating porting pure-component properties. water phase as organic-free (also parameters, or choosing a less rigor- Another useful technique is to com: called Free-Water). ‘ous method. This should be investigat- pare the same flowsheet or property- Most simulators offer collections ed forall physical property methods in- table results while using different of property methods in predefined cluding those shown in Figures 1-3, physical property methods. 40 + ocroBen 195 » CHEMICAL ENGINEERING PROGRESS. By default, most phase equilibria calculations are performed assuming ‘vapor and liquid phases. If your pro- cess involves two liquid phases (VLLE), be sure to specify three- phase calculations. If not, you will et incorrect results. AS a part of the validation, you also should check that ‘your property methods do not falsely predict two liquid phases ‘Simulators let you specify that only fone phase is present in a stream or a unit operation. If vapor and liquid phases are possible, however, you should use the two-phase specification, Nondatabank components and missing parameters ‘When you want to simulate non- databank Components or have compo- nents for which parameters are miss- ing, ask yourself the fol- lowing: create a list of parameters that are missing. You should detail this infor- ‘mation when communicating the a of the simulation to other users or your management. Certain property parameters always fare required for a simulation. These can include molecular weight, vapor pressure, and ideal-gas heat capacity constants. The need for other parame- ters depends upon your choice of physical property methods. The simu- lator manuals should include the infor- ‘mation about the parameter require ments (7). There also are parameters that will be required for calculating the hheat of reactions or the reaction equi- librium constants. This includes the heat of formation and the Gibbs free energy of formation of all components that participate in the reactions, es PN erences, check for different ordering of atoms For instance, ammonia can be de- scribed as HN instead of NH,, Ref. 2 contains a formula index of organic compounds and isa good resource for alternative names. ‘Once you have determined the pa- rameter requirements that are not sat- isfied, the next stage should be ob- taining and using physical property data, Obtaining and using physical property data Sources of dara. To provide pa- rameters for. nondatabank compo- nents or t0 do regression for pure= component and binary parameters, yu will need to search for available Gata, Such data may be found ina va riety of sources, including data-com- hand: books, journals, and inter- + Is this @ major compo- Techniques to remove or minimize nal data collections. nent in the mixture? If itis While most streams in minor, can T take it out of the impact of specific parameters simulations contain mix- the simulation? ** Does the component take part in VLE? + Is the component non- volatile? *Is it polar or nonpolar? + Will reaction (including decom- position) cause this component to be depleted? ‘+ What properties need to be accu- rate for the chosen property methods? ‘These questions will help you to identify the parameters that are need- ced based on your choice of physical property methods. If these parameters are not available or cannot be deter- ‘mined through literature search, re- gression, or estimation, then you will have to reevaluate your choice of physical property methods or obtain data by measurement, ‘You should determine what the pa- rameters will default to if the simula- tor does not find any available. It is dangerous to assume that the physical property parameters were available just because the simulator did not give you an error message. Use the simulator manuals and on-line help to should be used with caution. ‘You can use your judgment about the importance of a parameter to set ‘nominal values for unimportant prop- erties. For example, if you know that ‘a component is very nonvolatile and fare using Antoine's equation for vapor pressure (In P = A + BI(T+C)), ‘you can set the value of parameters A, Band C to -100, 0, and 0, respective ly. (Tis temperature.) This will assign the vapor pressure used in Raoult’s Law a very small value, almost zero 3.7 x 101), This and similar tech niques to remove or minimize the im- pact of specific parameters should be used with caution, however. If you can’t find a component in the simulator’s databanks, make sure ‘you check for synonyms. For exam- ple, methoxybenzene may be listed as, ‘methyl phenyl ether or anisole. A ‘good approach is to search for the ‘component using its formula, When selecting the component by formula, tures, accurate property cal culations are not possible without accurate pure-com- ponent properties. The im- portance of pure compo- nent data should not be underestimat- ed as they are the basis for both pure- component and mixture properties. For instance, pure component proper tis such as vapor pressure will be used in phase equilibria calculations ‘Table 4 contains common sources for pure component properties, while Table 5 lists common sources for mixture properties. The recommended order of data search is 1 ctitically evaluated data sources; 2. nonevaluated sources; 3. experimental measurements; and. 4. estimation techniques. Binary parameters for phase equi libria. Because of the large number of binary pairs in even a simulation ‘of only ten components, we recom- mend ranking the components so as to prioritize the pairs and focus the literature search and measurement ef- forts on the most important parame- (CHEMICAL ENGRIERING PROGRESS. © OCTOBER 1586 © 41 SUCCEEDING AT SIMULATION * Pans ofthese sources are avalabe on-line from tional or Technica Databases Services, In. TDS) ters. First, divide the components into three groups: high, medium, and low priority. Base the priority on eri teria such as composition, and the purity specifications of the process ‘a component purity is specified, that component is important even if it appears only in low concentrations, Second, pair the components into highhhigh, high/medium, high/low, medium/medium, medium/low, and low/low groups. Search the available sources, including in-house ones, for any data for all groups. If certain ‘component pairs are known to be- hhave ideally, they can be excluded from the search. Next, use the UNI FAC method for the missing pairs in the medium/medium, medium/low, and low/low categories. UNIFAC is ‘ot recommended, however, for any pairs that include the components of high priority. A secondary literature search can be used to find binary data for similar compounds and those pa- Tameters then substituted. Propose experimental work if any binary pa- rameter data are still missing or if data regression exposes data as inad- equate (3). Cryer re of pure component data is Source Generally Raina? ‘ica Data of Pure Substances, DECHEMA® Ciealy [CRC Handbook of Chemisy and Physics (Beltsin)"| — Nonerticaly Yes DIPPR Data Compiation® Cite Yes of Chemicals, Orgs, and Biologists | Noneritially Yes of Polymer Science and Engineering | Nonetialy Yes SOU Validated Enginerng Data Index Nonericaly ves Hendbook of Thermophysicsl ropes of Gases | Nonereally Yes and Uiuids LIANAF Themochanica Tables Critcaby ves Lange’ Handbook of Chemisty Nonertaly Yes Poms Chamica Engineo’s Handbook Nonriiaty ves Properties of Gases and igus Nonerticaty ves Selected Values of Proprtas of Chemical Criaty Yes. {Compounds cr" Vapor Pressure of Pure Substances Nonestiealy Yes DIALOG infomation Services, STW Intra Regressing data Data regression is a powerful toot for engineers not just to make the best of available daa, but also to ana- Iyze the goodness of ft of a physial property model tothe data. Most sim- Uulatos include a data regression fea- ture, Examples of commonly re- sressed data include binary VLE and LLLE, vapor pressure, heat of vapor- ization, density, and heat capacity Data regression finds the best fit of parameter estimates tothe experimen tal data. The best fit is represented by finding the lowest value of an objec- tive function while matching the phase equilibrium or other constraints One common regression technique is called Maximum Likelihood Estima- tion, The objective function for this method is Zw(Cr-Crv6%) 2) where is a data group, C7" and Cy are ‘measured and estimated variables, re spectively, such as temperature, pres- sure, composition, or heat capacity, 6, is the standard deviation or the err in the measurement of the variable, and vw) is the weighting of the data group. 42 + OCTOBER 96 + CHEMICAL ENGINEERING PROGRESS When fitting phase equilibria data, the regression algorithm attempts. to re- duce the objective Function while the physical property method is being used to check thatthe components meet the constants of phase equilibria, ‘The work of a successful regres- sion involves selecting the right phys- ical property model and parameters, representing the data propery, choos. ing appropriate standard deviations of the data, and stating with suitable initial estimates of the parameters The following are general guidelines for data regression *Make sure that you are regress: ing the right parameters. Use the same physical property method and but-in databank that you will be using in the simulation, Choose pa- rameters that have impact onthe data being used. For example, when using an equation-f-state method such as Peng-Robinson or Redlich-Kwong- Soave, you should determine the aceniric factor, ©. But, if you are using an activity coefficient method, you should determine two or more constants forthe Antoine model *Estimate as few parameters as possible. Tere is a tendency to use a Targe numberof parameters when fit ting a model to data such as tempera- ture-dependent properties or binary phase equilibria. Try to regres the data with as few parameters a8 possi- ble. If the regression results report thatthe standard deviation ofthe est- mated parameters is ofthe same order of magnitude asthe values of the pa- rameters, you may be estimating too many parameters for your given data The larger the temperature range of your data, the more parameters that you can estimate * Watch out for incomplete data. A regression may yield poor results if there are missing data points, paricu- larly composition data. For example, some authors do not report all com: Positions in VLLE of immiscible LLE. You may need to estimate the missing. compositions so that phase equilibrium can be calculated for all ‘components. Find out how your sim ulator handles missing data 10 best deal with incomplete data * Specify the right number of phas- es A regression will yield incorrect results if the number of phases is not specified correctly. This is a common, problem in VLLE systems. For some literature data, the number of phases is hard to interpret because ofthe pre- sentation of the data or lack of dk scription. Often in VLLE data, only a total liquid composition is reported even though two liquid phases were present. The author may be reporting a heterogeneous azeotrope — an azeotrope where the vapor composi- tion equals the total liquid compos tion but two liquid phases are present. When doing the regression of a het: erogeneous azeotrope. divide the data into two groups, the VLE data and the VLE data. This will ensure that the correct phase equilibria is considered. In regressions such as this, it is im- portant t0 use the property tabulation and plotting Features of the simulator to check that the parameter estimates cconrectly reproduce the original data * Use a model's full functionality. A physical property model may be used to calculate several properties. For ex ample, you can use binary excess-en- thalpy (#,) data and binary VLE or LLLE data to determine binary parame- ters for activity coefficient models. For cequation-of-state models, you simulta- neously can use liquid- and vapor heat capacity, vapor pressure, and heat of vaporization data. If data are available for these properties, use these data to- gether to estimate the parameters, Data _2roups of different types can be used together in the same regression. Uf necessary, regress parameters even if values are available in the databank. The physical propery pa- rameters found in the built-in pure- component and binary databanks gen- erally are very reliable. You may find, however, that you need to determine new parameters 10 replace the data- bank values for your application Check the built-in parameters to en: sure that the recommended tempers ture, pressure, and composition range ‘Ac Coofiens a ifnite Dion, DECHEMA Chemistry Sais Binary VLE Data fie, DIPPR Dortmund Databank (superset of DECHEMA data collection)” sof Mixing Data Collection, DECHEMA Chemisty Series Liquid-Liguid Equiium Data Colction, DECHEMA Chest Seis nd Enthalpes of Electro Solutens, DECHEMA Chemistry Series ‘Vepor iui Equitrium Data Collection, DECHEMA Chemistry Sories \Voporiqud Equilibrium Det for Bleeaye Soluians,DECHEMA Chomisty Sores Vaporiqud Equiv for Miaures of Low Boling Substances, DECHEMA Chemistry Series 1s of Chemical Compounds, Texas A&M University Sol-Liquid Equlbium Data Cllecton, DECHEMA Chemisty Series Phase Equi Selected is not outside the range of your simu- lation. For example, vapor pressure parameters may not have been deter- mined at temperatures below the nor- ‘mal boiling point. Most physical prop- erty models extrapolate outside the temperature bounds reasonably well but at some compromise in acura cy. The parameter values also may apply toa very wide range of tempera. ture and thus not provide as good a fit if you only need a narrow range in the simulation. For phase equilibria calcu- lations, to improve the accuracy of VLE or LLE predictions, you may ‘want to use ternary or quaternary data to fine-tune binary parameters. that may be available in the simulator. * Check that the parameters repro- duce the data, The simulator will re- port qualitative results of the regres- sion, including the residuals (experi ‘mental minus estimated variables). Use the property tabulation oF plotting fe: tures to reproduce the data atthe speci- fied conditions. This can be performed. in the same regression run, Check that the comet number of phases is pre- dicted by allowing two-liquid-phase culations for the property table or plot. In addition, your simulator may have an option wirere you can evaluate the fit using the existing parameters and model with experimental data without doing a regression, + Remove components not in phase equilibria. If components that are solids oF ions do not appear in a SER eC ce eee phase, you can remove them from the phase equilibria constraints. This is useful in VLE. Fenerate equilibrium data. It ‘you have binary parameters for an ac tivity coefficient or equation-of state model. your simulator may be able to ‘generate VLE or LLE data for regres- Sion tsing these parameters, You can regress these “data” with another physical property model. This allows consolidation of known parameters into a single property method, *Fit other data. Your simulator may have a data fiting feature that c bbe used for plant data. This method ‘may not be as useful for predictive simulation, though. if the data are not from a wide variey of conditions. Estimating missing property parameters Property estimation usually is done after a data search is performed, 10 supply missing property parameters, You can use builtin estimation meth- fos to fill in some gaps in your physi- cal-property-parameter requirements. Simulators include one or more esti mation methods for each of the most common parameters. There are two types of estimation methods for pure component parameters: structural ‘group, and corresponding states. Structural group methods are based ‘on the idea that contributions of the pars or structural groups of the eompo- nent are additive for properties such as CHEMICALENGINEERING PROGRESS * OCTOBER 195 + 43 Table 6. Comparison of estimated and experimental parameters for phenetol (CyH,,0). * at atm, 25°C oridal gos iMotecaor weight Crea wmporatre Crical presse Nine ies volume iKnle Standard heat offormation® | Jkmole * att aum, 26°C ride gos formal boiling point, critical tempera ture, ential pressure, ideal-gas heat ca pity, and Standard beat of formation Some methods suchas that of Benson, ‘contain additional corrections for next nearest-neighbor atoms or for rings. Structural group contributions are deter- mined by taking an average contebion thased on knowin physical constants of many organic compounds, Because the Benson, Jahack (10), and other strie al-group methods are based mainly fon data for organic compounel, they ‘cannot be used for inorpanics including metals, or ions, In addition, structural ‘group methods do not accurately repre: sent very large organie molecules (that is, ones with a molecular weight > 206) such as proteins, New geoup-contrbu tion methods like that of Constantino and Gani (4) potentially may provide better estimations for organics. Other possibly useful methods are proposed in the literature but may apply to only cer tain families of components. 161857 | Formula esess12 | Ambrose 085.350 Ambrose casas | Fadore 15530000 Benson Corresponding states methods are based on empirical mathematical re Iationships among properties, For ex ample. the Letsou-Stiel method r lates liquid viscosity to critical tem- perature, critical pressure, and acen- trie factor. These methods most likely will be inaccurate when used for compounds unlike these upon which the correlation was based, 1004 approach for both group contribution and corresponding states methods is 10 cheek the accuracy of fas many methods as possible for compounds for which properties are known and which are structurally Similar to the compound you are est mating. The following example shows the use ofthis concept. Estimating the properies of propyl phenyl ether Let's say that you are modeling a process containing propyl phenyl ether (PPE), also called propyloxy benzene. The only dat you have are its boiling point 44 + ocToseR 1906 + cHENNCAL ENGINEERING PROGRESS Property Name sEmor_| Estimation Method Cites temperate 158

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