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    thermodynamics

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    © All Rights Reserved
    Download as PDF or read online from Scribd
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    19 views7 pages

    ThermoModels ElliotLira

    Uploaded by

    Rioneli Ghaudenson
    thermodynamics

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
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    of 7
    APPENDIX MODELS FOR PROCESS SIMULATORS D.1 OVERVIEW ‘There are so many thermodynamic models commonly used in chemical process simulators that it would be overwhelming to cover all of them in great detail. This is why the discussion in the text focuses on a few representative models. Nevertheless, students interested in process engineering will often face the need to choose the most appropriate thermodynamic model, and the most appro- priate model may not be one of those that we have covered in detail. Fortunately, the differences between many of the thermodynamic models and the ones that we have studied are generally quite small, In this appendix, we review some of most common thermodynamic models and put them into context with others that we have studied. This should help students to feel a bit more comfort able wading through the wealth of models from which to choose. ‘Students interested in becoming process simulation experts will be interested in reading the recent articles reviewing the selection of thermodynamic models, Schad (1998) and Carlson (1996) provide some significant examples and cites several relevant articles. A common thread throughout these articles is the emphasis on accurate application of thermodynamic principles. I is interesting to see the large number of examples in which practical engineering applications were so deeply affected by the fundamentals of thermodynamics. D.2 EQUATIONS OF STATE We have covered the Peng-Robinson and virial equation in fair detail, but there are many others. ‘Some that we have mentioned but not treated in detail are the Redlich-Kwong (1949) equation (homework problem 69), the Lee-Kesler (1975) equation (Eqn. 6.11 on page 202), and a popular form ofits extension to mixtures, the Lee-Kesler-Plocker equation (Plocker etal, 1978), the Soave (1972) equation (Eqn. 6.49 on page 225, also known as the Soave-Redlich-Kwong or SRK equa- tion), the ESD equation (Elliott, et al.,1990) and the SAFT equation (Chapman ct al., 1990). A slight variation on the Soave equation is the API equation (Graboski and Daubert, 1978); it changes 624 Appendix D Models for Process Simulators only the value of x as a function of acentric factor in order to obtain a slight improvement in the pre- dicted vapor pressures of hydrocarbons. A specific implementation of the virial equation isthe Hayden (O'Connell (1975) method. The Soave equation, Peng-Robinson equation, Lee-Kesler-Plocker, and the API equation are all very similar in their predictions of VLE behavior of hydrocarbon mixtures, They are accurate to within ~5% in correlations of bubble point pressures of hydrocarbons and gases (CO, CO2, N2, 02, H2S) and about 15% for predictions based on estimated binary interac tion parameters. The Lee-Kesler-Plocker equation can be slightly more accurate for enthalpy and liquid density for some hydrocarbon mixtures, but the advantage is generally slight with regard to enthalpy and there are better alternatives to equations of state for liquid densities if you want accu- rate values. The cubic equations have some convergence advantages for VLE near critical points and their relative simplicity makes them more popular choices for adaptations of semi-empirical ‘mixing rules to tune in an accurate fit to the thermodynamics of a specific system of interest. The i best choice among these is generally the one for which the binary interaction parameters have been determined withthe greatest reliability, (Accurate reproduction ofthe most experimental data atthe conditions of your specific interest wins.) ‘The primary role of equations of state is that they can predict thermodynamic properties at any conditions of temperature and pressure, including the critical region. The disadvantage is that they tend to be inaccurate for strongly hydrogen-bonding mixtures, This disadvantage is diminishing in importance with the development of hydrogen-bonding equations of state like the SAFT and ESD equations), but it is not clear at ths time whether these newer equations of state will displace any of the long-standing cubic equations of state with their semi-empirical modifications. D.3 SOLUTION MODELS ‘We have covered many solution models in fair detail: the Margules equation, the Redlich-Kister expansion, the van Laar equation, Scatchard-Hildebrand theory (the most common implementation ‘of regular solution theory), the Flory-Huggins equation, the Wilson equation, UNIQUAG, and UNI FAC. There is one more that deserves mention: the NRTL equation (Renon and Prausnitz, 1969). ‘This a very slight modification of the Wilson equation which enables correlation of liquid-liquid equilibria as well as vapor-iquid equilibria. Once again, the best choice will most often depend on the availability of binary interaction parameters wiich are relevant to the specific conditions of ‘The primary role of solution models isto provide semi-empirical models which have a greater degree of flexibility than equation of state models, owing to the greater number of adjustable parameters and their judicious choice such that both magnitude and skewness of the free energy ‘curves can be accurately tuned, D.4 HYBRID MODELS ‘Another set of models that have been developed relatively recently can be referred to as “hybrid” models in the sense that they combine equation of state models with solution models. The two most prevalent of these are the Modified Huron-Vidal (MHV) method and the Wong-Sandler mixing rules. The basic idea is to apply a solution model at high density or pressure to characterize the ‘mixing rules of the equation of state and then interpolate from this result to the virial equation at low density, These methods tend to compete with the hydrogen bonding models in the sense that they enhance accuracy for non-ideal solutions at high temperatures and pressures. They are more jonD.5 Recommended Decision Tree 625 empirical, but they tend to leverage the well-developed solution models (like UNIFAC) more directly. They also tend to be more efficient computationally than the hydrogen bonding equations D.5 RECOMMENDED DECISION TREE When faced with choosing a thermodynamic model, it is helpful to at least have a logical procedure for deciding which model to ty first. A decision tree is included in Fig. D.1, For non-polar fluids, an equation of state may suffice. For polar fluids, a fited activity coeffecient model is preferred, possibly in combination with the Hayden-O'Connell method or in combination with some other Classify the components in your process: | gases, non-polar, associating, solvating, electrolyte. Try Peng-Robinson, SRK, API, | [Tey NRIL, Pitzer, or Bro- miley, whichever has all BPP’. Try NRTL, UNIQUAG, FH, Wilson, or Van Laar, whichever has all BIP's, Nofsip’s all known) S¥ ‘Any gases (e.g. NH3, ©02)? or P>10bars? Yes — ‘Try UNIFAC. If possible, estimate BIP’s for missing| components only Yes polymers ‘Try SAFT, ESD. No L___] Yes P< 10 bars? = aaannnaneeeeet ny cers oer No Sa | | Try ESD, SAFT, MHV: {___) ong- Sandler. Figure D.1 Flow chart so select the best thermodynamic model The abbreviation BIPis used to mean binary interaction parameters. 626 Appendix D Models for Process Simulators ‘equation of state for the vapor phase (like the Peng-Robinson equation). This approach can often provide satisfactory predictions as long as the pressures are 10 bars or less. Predictions by this approach should be checked against literature data to the greatest extent possible. If there are no experimental data for one ofthe binary systems in this event, then UNIFAC can be used to generate ““pseudo-data” that can be used to predict the Gibbs excess energy for that binary, and these pseudo- data can be used to regress UNIQUAC or NRTL parameters if desired (homework problem 11.40). ‘Above 10 bars, the choices are not so obvious. The most obvious method to try if you are satisfied with the corelations below 10 bars is to apply the MH or Wong-Sandler approach. If you need to predict phase behavior over a broad range of conditions based on few data in a narrow range of con- ditions, a hydrogen bonding equation might provide more reliable leverage in light of its clearer connection with the physical chemistry in the solution. If you are dealing with compounds which dissociate electrolytically or associate strongly and specifically in solution, then it will probably be necessary o apply a simultaneous reaction and phase equilibrium approach. These kinds of systems sre common in gas strippers for compounds like CO2, HS, and amines. For these systems, itis especially important to check your correlations against experimental data near the conditions of your specific interest. D.6 THERMAL PROPERTIES OF MIXTURES ‘A problem not treated explicitly in the text is the performance of energy and entropy balances for mixtures. We mentioned that energy departures for mixtures are just like those for pure fluids, after the mixing rules are defined. But we never showed how that rigorous approach for treating the mix- ture properties can be used in solving practical engineering problems, Process simulators deal almost entirely with mixtures and energy balances play a major role in process simulation, soit is essential to have a framework for characterizing the thermal properties of mixtures as they flow through throtles, turbines, or reactors In discussing thermal properties of pure fluids, it was suficient to define the reference state to be, say, the saturated liquid at its normal boiling point, such that every component had an indepen- dent reference state. In mixtures, especially mixtures that may change composition owing to reac- tions, reference states must account for energetic differences between components. This fact was recognized when dealing with heats of reaction, and especially in dealing with adiabatic reaction temperatures, but ideal gases were assumed in those examples. The extension to thermal properties ‘of reacting mixtures requires a simple combination ofthe approaches used for pure fluids and react- ing mixtures. Briefly, the standard states for all components can be set as the elements at 298 K and 1 bar in the ideal gas state. For example, the enthalpy of a flowing liquid benzene + styrene stream. ‘at 310 K includes (a) the heats of formation of the ideal gas components, (b) the integral ofthe ideal {gas heat capacities, and (c) the enthalpy departure of the benzene + styrene mixture. The enthalpy Of this stream will be large and negative, but not as large and negative as the same stream trans- formed into benzene + polystyrene at the same temperature, because the heat of polymerization ‘must be removed to maintain constant temperature. Section D.6 Thermal Properties of Mixtures 627 ere a ed ie ‘An equimolar mixture of benzene and styrene is contained in a reactor at 400 K and 10 bars ‘hen itbegins to leak. The Environmental Protection Agency would like to know the concentri- 1 eee if die reactor contents mixed with air after release, fonming a dispersion elov fi {© model this process is asa series of isnt Hashes by slowly amereasing the ‘amount of air in the mixture ‘© conespond with varying breadihs of the dispersi Seen {anol of air is mixed each one kino! of reactor leakage, eee Simaluoro ate Sprodcled i a process simlator by feeding cae ‘nto a “mixer” then sending the outlet ftom the mixes obtain Separate esults for the vapor and liquid streams. Ifthe mi reat it should check the ‘energy balance to make sure the outlet enthalpy. py is the tes en il pile wick ts emp. conc ae siyrene, You cun check whether these are being used 2s the reference conditions fo 4 simulator by typing 1 kil forthe stream flow withthe mole fraction ofthe desired component | set to unity, setting the temperature to 25°C and the pressure to Some suitably ows value, 8, 16 ay Smart inet sem soa set 25°C and ar an te cata ot at stream should be near zero, since ai is composed of ~79mole% nitrogen and 21% oxygen, both | elements: If-your simulator uses dtferent values forthe heats of formation at these conditions, vite them down and sobsiute them appropriately inthe calculations below. tetrconteis 9 400 Kad 10 bars av actly igi, So we ned to meget bin the ideal gas enthalpy at 400 K, then apply the enthalpy departure at 400 K and 10 b TAs pd Tare canes cre cad ete eae since there is 50 heat of mixing ideal gases, The combined ideal gas enthalpy change from 298 16400 Kis 220. Te FU opin cn he PROX EXE pogtam provide the heey Copa functions, The value of the departure function at 400 K and 1 MPa is (H!— H'8)/RT- 7906, Tlcnlng "OH 2256 eos, Conblnng i corsinaons fom es eran he ‘deal gas, and he departure function gives an enthalpy for the reactor steam of 94.76 KJmole

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