Chapter 2 Application Guidelines

This section presents simple heuristic rules for selecting suitable methods for performing thermodynamic property calculations.
Note: Although these rules were developed specifically for the

PRO/II software, the general guidelines still apply to fluid flow applications. However, the examples at the end of this section were developed specifically for this program.

General Information
Usually, there are several thermodynamic methods suitable for any given application. The user always should try to determine which methods give the best representation of the whole flowsheet, while trying to select the simplest, most appropriate thermodynamic options. The user should bear in mind that the best thermodynamic method is the one that gives the best agreement with reality. When laboratory or actual operating data are available, it may be necessary to try several options and compare the results to obtain the best possible model. The following guidelines are divided into four basic categories of applications. These are:

Refinery and Gas Processing Natural Gas Petrochemical Chemical and Environmental

For each application, the various types of unit operations encountered have recommended thermodynamic methods.

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Refinery and Gas Processing Applications

Water Handling
For most systems containing water, it is perfectly satisfactory to use the default water decant option with the simpler hydrocarbon thermodynamic methods. These are: SRK, PR, CS, GS, CSE, GSE, IGS, BK10, BWRS. For each of these methods, the amount of water dissolved in the hydrocarbon phase is calculated using either the SIMSCI or the KEROSENE correlation. The SIMSCI method is based on the solubility of water in the pure components, while the KEROSENE correlation is based on the solubility of water in kerosene, given in the API Technical Data Book, Figure 9A1.4. In addition, SRK and PR can use the EOS method for calculating the water solubility. See Table 1-7 on page 2-1-35 for other water solubility options. The remaining water may be decanted as a pure liquid water stream. The properties of this pure water stream can be calculated using saturated water properties or by using the full Keynan and Keyes equation of state for water. The Keynan and Keyes equation should be used if water is present as super-heated vapor. The program uses the vapor pressure of water at the temperature of the system to calculate the amount of water in the vapor phase. The user can select either the (default) built-in steam tables or the GPSA Data Book, Figure 20-3 for the water vapor pressure. The GPSA values should be used for natural gas systems above 2000 psia (136 atmospheres). For systems where the solubility of hydrocarbon in water is significant, a more accurate method should be used. The Kabadi-Danner modification to the SRK equation of state (SRKKD) is recommended. This method may be selected by using either SYSTEM(VLLE)=SRKKD or KVALUE(VLLE)=SRKKD on the METHOD statement. The SRKKD method performs rigorous vapor-liquid-liquid equilibrium calculations to predict the amount of water in the hydrocarbon phase and the amount of hydrocarbon in the water phase. It uses interaction parameters for the water and hydrocarbons based on the amount of water present in each phase.

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Application Guidelines

Low Pressure Crude Systems

Vacuum towers and atmospheric crude towers are representatives of low pressure crude systems. These units generally exhibit nearly ideal behavior, and simpler methods can be used very successfully. The accuracy of the results depends much more on the characterization of the crude feed than on the thermodynamic method chosen. The BK10 method usually is adequate and quicker than more complex general hydrocarbon methods such as GS, SRK or PR. The user may wish to solve the unit with BK10 as a first attempt, and then use a more complex method if the results are not satisfactory. If the results do not agree with plant data, the user should try different assay and characterization methods before employing other thermodynamic methods. The API method should be used for calculating the liquid density. Thermal cracking is a common source of error when modeling vacuum units. A laboratory analysis of the vacuum tower overhead product can be used to estimate the amount of light ends to be added to the feed stream in order to correctly model the column. In lieu of a direct analysis, methane can be added to the feed and adjusted until the temperature profiles match the plant data. Recommended Methods
BK10

Comments
Fast and easy to use, and gives acceptable answers.

GS / IGS / GSE Comparable to BK10 for low pressure systems. Substituting LK for CP enthalpies may improve answer. SRK / PR The results will be somewhat better than with BK10 near the top of the tower where light ends may predominate. May require more CPU time than BK10.

High Pressure Crude Systems, FCCU, and Main Coker Fractionators

Towers above atmospheric pressure usually contain greater concentrations of lighter components and therefore require more complex thermodynamic methods. BK10 has been used extensively in the past for these types of applications, but PR, SRK, GSE, IGS, and GS can be expected to give better answers. The user should remember that the characterization of the petroleum fractions is more important than the thermodynamic method for obtaining good agreement with plant data. The API method should be used for the liquid density.
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For Fluidised Catalytic Cracker Unit (FCCU) main fractionators, the petroleum fractions are much more hydrogen deficient than are crude fractions. Since most characterization correlations are derived from crude petroleum data, it is expected that the results will be less accurate than for crude fractions. Recommend ed Methods Comments

GS / GSE / IGS Usually faster than SRK or PR, but less accurate in the presence of a high concentration of light components. Substituting LK for CP enthalpies may improve the answers. SRK / PR Use SRK or PR if light crudes dominate the top of the tower.

Reformers and Hydrofiners

These units contain streams with a high hydrogen content. For the SRK and PR methods the component databanks contain extensive binary interaction parameters for component pairs involving hydrogen. The API method should be used for the liquid density. Historically, GS has been used successfully with hydrogen rich systems. In general, SRKM and PRM should give better results with the improvement in interaction parameters over previous versions. Recommended Methods
SRKM / PRM

Comments
Recommended because of the high concentration of hydrogen present.

Lube Oil and Solvent De-asphalting Units

These units generally have non-ideal components present and require a more complex thermodynamic method. SRKM or PRM is recommended, but the answers will only be as good as the interaction parameters supplied by the user for the non-ideal components. This complex method should not be used unless such data are available. If no specific data are available, SRKM yields results comparable to SRK, and the general SRK or PR method should be used. The API method should be used for the liquid density.

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Application Guidelines

Recommended Methods
SRKM / PRM SRK / PR

Comments
Recommended when using user-supplied interaction data for non-ideal components. Use in place of SRKM or PRM when no usersupplied interaction data are available. These methods require less CPU time than SRKM or PRM.

Natural Gas Systems

For systems with less than 5 percent N2, CO2 or H2S, general equations of state such as SRK, PR, or BWRS provide excellent answers. The interaction parameters for hydrogen, carbon dioxide, nitrogen, and hydrogen sulfide are estimated using general correlations when user-supplied interaction parameters are not available. The BWRS method should be used with more caution, since it does not extrapolate as well as SRK or PR into the supercritical region. For systems with higher concentrations of the sour gases, the default interaction parameters may not produce the best possible answers. A general equation of state should still be used, but the user should supply better interaction parameters to obtain good results. The default water decant option is usually acceptable. However, for high pressure systems where the solubility of hydrocarbon in water is significant and the solubility correlations of water in hydrocarbon break down, the Kabadi-Danner modification to SRK should be used with the VLLE option. The Kabadi-Danner option as implemented has been extended to include nitrogen, hydrogen, carbon dioxide, carbon monoxide, and hydrogen sulfide as specific components. Petroleum fraction components are approximately identified as paraffins, olefins, aromatics, or naphthenes, according to their Watson characterization parameters, when suitable interaction parameters are supplied by the user. For systems containing non-hydrocarbon components (such as methanol and glycol acting as inhibitors), more complex mixing rules must be used to obtain good results. The SRKM and PRM methods work well for these systems, but the user must ensure that all the relevant interaction data are entered. These methods automatically access the SIMSCI databank to retrieve all available interPRO/II Thermodynamic Data Keyword Manual 2-5

action data, but the user may have to supply additional data if the data for a component pair are not in the bank. The VLLE option must be specified on the METHOD statement if two liquid phases are expected. Use the COSTALD method to calculate the liquid density for Tr < 0.95. This option is not the default method and must be specifically requested. Recommended Methods
SRK / PR / BWRS SRKKD

Comments
These methods give good results for most hydrocarbon and hydrocarbon-water systems. Use SRKKD(VLLE) for high pressure systems containing hydrocarbons and water. SRKKD uses more CPU time than SRK. Do not use SRKKD if other polar components, such as methanol, are present. Use these methods for systems containing water and other polar components, such as methanol. Always use the VLLE option with these methods for this type of system. Simpler versions of SRKM and PRM. These methods are not as good as SRKM or PRM and do not significantly reduce CPU time.

SRKM / PRM / SRKS

SRKP / PRP

Glycol Dehydration Systems

The GLYCOL bank of interaction parameters for the SRKM method has been created for these systems. This bank is a sub-section of the general SRKM interaction bank, and the data have been fitted over a narrow range of typical temperatures and pressures for TEG, and, to a lesser extent, EG, and DEG dehydration systems. Invoking the GLYCOL system automatically retrieves the GLYCOL interaction parameters. Recommended Methods
GLYCOL

Comments
The program includes special interaction coefficients for typical TEG, and, to a lesser extent, EG, and DEG dehydration systems.

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Application Guidelines

Sour Water Systems

There are two methods available for the prediction of vapor-liquid equilibrium. They are identified on the METHODS statement as SOUR and GPSWATER. SOUR This method is based on a combination of the API/EPA SWEQ (Sour Water EQuilibrium) model for sour water components (H2O, H2S, CO2 and NH3) and SRKM for all other components. The recommended range of application is:
Temperature (F) Pressure Composition 68 < T < 300 F P < 1500 psia xwtNH3 + xwtCO2+ xwtH2S< 0.30

where xi is the weight fraction in the aqueous phase.

In general, this method is recommended over the GPSWATER when CPU time is a consideration. GPSWATER This method is based on the GPSWAT program for calculating sour water equilibrium. The GPSWAT method is used for generating Kvalues for sour water components (H2O, H2S, CO2, NH3, CO, CS2, COS, MeSH and EtSH). All other components are calculated using SRKM. The recommended range of application is:
Temperature (F) Pressure Composition Sour gas partial pressure 68 < T < 600 F P < 2000 psia xwtNH3 < 0.40 PCO2+ PH2S < 1200 psia

The GPSWATER method is valid for a broader range of applications than the SOUR method, but requires significantly more computation time.

Amine Systems
The AMINE package is used for generating K-values for aqueous amine systems and sour gases including H2S, CO2, H2O, MEA, DEA, DGA, DIPA, and MDEA. All other component K-values are calculated using SRKM. Water and exactly one amine must be present when using the package.

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Data for the equilibrium constants are provided for MEA, DEA, DGA, DIPA, and MDEA. However, the DIPA data are not recommended for use in final designs. For MDEA, the model is modified to include composition effects. Dimensionless residence time corrections to amine K-value calculations may be specified by the user. These corrections are only appropriate for systems involving MDEA or DGA. For all other amines, the entry is ignored if it appears. The user can override the default value of 0.3 under the KVALUE keyword in the THERMO DATA section in order to better fit the plant data. A RESI value of 1.0 corresponds to an equilibrium model. The data package may be used over the ranges of concentrations and acid gas loadings typically encountered in gas processing. This includes the temperatures and pressures for the contactor and regenerator. MEA processes have been successfully applied in the 25-100 psig operating range. However, DEA does not perform well under these conditions and is generally used at higher pressures. Typically, contactor pressures for MEA contactors may range from 100 to 500 psig, with DEA systems ranging from 100 to 1000 psig. The amine regenerators are generally operated at temperatures less than 275 F, with a typical temperature being 255 F. Amine solution strengths for MEA and DEA are generally within 15-25 wt% and 25-35 wt%, respectively. The AMINE package accounts for heats of reactions by applying a correction to IDEAL saturated liquid enthalpies. SRKM is also used for actual vapor densities and IDEAL values are used for liquid densities.

Petrochemical Applications
Light Hydrocarbon Systems
SRK, PR, or BWRS is recommended for most light-hydrocarbon, petrochemical applications. When solubility of water in hydrocarbon and hydrocarbon in water becomes important, as it would at high pressure, SRKKD(VLLE) is recommended. Use the COSTALD method for liquid density. This option is not the default and must be requested specifically.

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Application Guidelines

Recommended Methods
SRK / PR / BWRS SRKKD

Comments
Good for systems containing only similar hydrocarbon types (e.g., all paraffins). Water may be decanted as a pure aqueous phase. Use SRKKD for more accurate results with hydrocarbon-water systems. SRKKD uses more CPU time than SRK.

Aromatic Systems
For systems containing all aromatic components, use the ideal method at low pressures as these systems are very close to ideal. For systems at pressures above 2 atmospheres, use GS, SRK, or PR for a more accurate result. The liquid density can be calculated using the ideal, the default API, or the COSTALD methods. The COSTALD method has data for many aromatic components, will give good results at higher temperatures, and is better than API if any light components such as methane are present. For systems at high temperatures with all aromatic components, the API method is as good and uses less CPU time. The ideal method is best at lower temperatures and should not be used if the temperature is significantly higher than the boiling point of any one component. Recommended Methods
IDEAL GS / SRK/ PR IDEAL / API / COSTALD

Comments
Recommended for systems at low pressures below 2 atm. Recommended for systems at pressures above 2 atm. Recommended for liquid density.

Aromatic/Non-aromatic Systems
Traditionally, these systems are difficult to model accurately.However, new equation-of-state mixing rules and alpha formulations can give excellent results when appropriate interaction parameters and alpha parameters are available. The SIMSCI databank includes a large number of interaction parameters, but the user should verify
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the availability of all critical parameters to ensure getting good results. It is not necessary to use the VLLE option unless polar components, such as water, are present. For aromatic / non-aromatic extraction systems (e.g., DMF extraction of butadiene), use a liquid activity method such as NRTL. Equations of state using the advanced mixing rules can model this system as well but require more CPU time to obtain the same results. As with all systems of this type, the results are only as good as the supplied data. The SIMSCI databank has a large amount of interaction data stored for the advanced mixing rules and the NRTL and UNIQUAC liquid activity methods. However, the user must ensure that all important interactions are covered in order to get good results. The liquid activity methods have an advantage over equations of state, since they can use the UNIFAC FILL option to estimate any missing binary interaction parameters. Systems that include light gases can be modeled using the HENRY option in conjunction with the liquid activity methods. This is acceptable when the light gases are present in small quantities. However, if the gases are present in large quantities, it is better to employ an equation of state using one of the advanced mixing rule methods. These calculate the solubilities of the gases more rigorously. Recommended Methods
SRKM / PRM / SRKH / PRH

Comments
Use any of these methods for aromatic / non-aromatic systems. Also use them for extraction systems at high pressure, or when large quantities of supercritical gases are present. Use these liquid activity methods for extraction systems, such as the extraction of butadiene using DMF. Use the Henry option to model any supercritical gases present in small quantities. Use the UNIFAC FILL option to estimate missing binary pairs.

NRTL / UNIQUAC

Non-hydrocarbon Systems
These systems typically contain oxygen, halogen, or nitrogen derivatives of hydrocarbon components and tend to be highly non-ideal. For low pressure systems, use a liquid activity coefficient method. For single phase systems, the WILSON, NRTL, and UNIQUAC methods are equally good. The Wilson method is the simplest and
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requires the least amount of computer time. Simpler methods, such as VANLAAR and MARGULES, are not as good, since they often do not model the more non-ideal systems accurately. For systems containing two liquid phases, the NRTL or UNIQUAC method should be used. The SIMSCI databank contains a large number of binary interaction coefficients for both VLE and LLE systems. In order to get good results, the user must ensure that all significant binaries are supplied in the input. The UNIFAC FILL option can be used to fill in any missing binary data, but should be used only if interaction data are available for most of the binary pairs. If the user has no data, the SYSTEM= UNIFAC option can be used, since it has group interaction data available for both VLE and LLE applications. For high pressure systems, the program offers several methods for modeling the vapor phase fugacity. These methods should be used only if the system pressure is significantly higher than the pressure at which the interaction coefficients were regressed. Interaction coefficients regressed from high pressure data may already include any vapor phase non-ideality in the liquid phase interaction coefficients. The user should always determine whether or not any usersupplied interaction parameters include vapor phase fugacity. All of the parameters in the SIMSCI databank except for components such as carboxylic acids were regressed without a vapor phase fugacity method. For systems with carboxylic acids such as acetic acid, it would therefore be appropriate to use PHI=HOCV. Supercritical gases present in small quantities can be modeled using the Henry option. If they are present in large quantities, or if the system is at high pressures (usually greater than 10 atmospheres), an equation of state using one of the advanced mixing rules should be selected. These are the SRKH, PRH, SRKM, PRM, SRKS, SRKP and PRP methods. The SRKM, SRKS or PRM methods are recommended for the non-hydrocarbon systems discussed here.

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Recommended Methods
WILSON

Comments
Use WILSON for slightly non-ideal systems. Use the HENRY option to model small amounts of noncondensible gases. Use the UNIFAC FILL option to fill in missing binary interaction data.Do not use WILSON for VLLE systems. Use either of these methods for all non-ideal systems. Use the Henry option to model small amounts of non-condensible gases. Both methods model VLLE systems as well as VLE systems. Use the UNIFAC FILL option to fill in missing binary interaction data. Use for systems at higher pressure or when large quantities of non-condensible gases are present. Can be used for VLE and VLLE systems. Can be used as comparable alternatives to SRKS, SRKM and PRM. SRKS / SRKH / PRH / SRKM / PRM normally yield better results than SRKP and PRP in these applications.

NRTL / UNIQUAC

SRKM / PRM / SRKS SRKH / PRH SRKP / PRP

Alcohol Dehydration Systems

A special bank of interaction coefficients for the NRTL method has been created for alcohol dehydration systems. The coefficients are applicable over a much narrower range than the general NRTL bank coefficients. The user may specify either BANK=ALCOHOL on the KVALUE statement or SYSTEM=ALCOHOL on the METHOD statement. The SYSTEM=ALCOHOL option calculates the vapor enthalpy and density using the SRKM method. Recommended Methods
ALCOHOL NRTL / UNIQUAC

Comments
Use for all alcohol dehydration systems. Use when valid user-supplied interaction data are available.

HF Systems
A special equation of state, HEXAMER, has been created for systems containing molecules that hexamerize in the vapor phase. This
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method is recommended for HF systems such as the HF alkylation process, and for the manufacture of refrigerants and other halogenated compounds using HF.

Chemical and Environmental Applications

Non-Ionic Systems
Non-ionic systems typically contain oxygen, halogen, or nitrogen derivatives of hydrocarbon components and tend to be highly nonideal. For low pressure systems, use a liquid activity coefficient method. For single liquid phase systems, the WILSON, NRTL, and UNIQUAC methods are equally good. The Wilson method is the simplest and requires the least amount of computer time. Simpler methods such as VANLAAR and MARGULES are less applicable, since they often do not model the more non-ideal systems accurately. The NRTL or UNIQUAC method should be used for systems containing two liquid phases. The SIMSCI bank contains a large number of binary interaction coefficients for both VLE and LLE systems. In order to get good results, the user must ensure that all significant binaries are included in the input. The UNIFAC FILL option can be used to estimate any missing binary data but should be used only if interaction data are available for most of the binary pairs. If the user has no data, the SYSTEM=UNIFAC option can be used, since it has group interaction data available for both VLE and LLE systems. The program offers several methods for modeling the vapor phase fugacity in high pressure systems. These should be used only if the system pressure is significantly higher than the pressure at which the interaction coefficients were regressed. Interaction coefficients regressed from high pressure data may already include any vapor phase non-ideality in the liquid phase interaction coefficients. Supercritical gases present in small quantities may be modeled using the Henry option. If they are present in large quantities or if the system is at high pressures, an advanced equation of state such as SRKH, PRH, SRKM, PRM, SRKS SRKP, and PRP should be selected

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. Recommended Methods
WILSON

Comments
Use WILSON for slightly non-ideal systems. Use the Henry option to model small quantities of noncondensible gases.Do not use WILSON for VLLE systems. Use either of these methods for all non-ideal systems. Use the Henry option to model small quantities of non-condensible gases. Both methods model VLLE systems as well as VLE systems. Use the UNIFAC FILL option to estimate missing binary interaction data. Use at higher pressures or when large quantities of non-condensible gases are present. All three of these methods can be used for VLE and VLLE systems. These methods often yield less satisfactory results than the SRKH, PRH, SRKM, SRKS, and PRM methods in these applications.

NRTL / UNIQUAC

SRKM / PRM / SRKS SRKP / PRP

Carboxylic Acid Systems

Carboxylic acids form dimers in the vapor phase. To obtain accurate values for vapor fugacity, enthalpy, and density, use the Hayden-O'Connell method to calculate the vapor phase properties. Note that HOCV vapor phase fugacities must be used in conjunction with a liquid activity method. Recommended Methods
HOCV

Comments
The Hayden-O'Connell method produces the best values for vapor phase properties in these applications. Use the PHI=HOCV, ENTHALPY(V)=HOCV, DENSITY(V)=HOCV options on the METHOD statement.

Environmental Applications
These systems usually involve stripping dilute pollutants out of water. The normal liquid activity methods, such as NRTL, do not usually model these very dilute systems with sufficient accuracy. A better approach is to use Henry's Law data for the components in water. The Henry's Law data can be obtained from data sources,
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such as the U.S. Environmental Protection Agency( EPA), or are often available in the SIMSCI databank. In order to model the systems accurately, the user should supply temperature-dependent values for the Henry data whenever possible. Non-temperature dependent data often over-predict the required amount of stripping steam.

Solid Applications
Solid-liquid equilibria for most systems can be represented by the van't Hoff (ideal) solubility method or by using user-supplied solubility data. In general, for those systems where the solute and solvent components are chemically similar and form a near ideal solution, the van't Hoff method is appropriate. For non-ideal systems, solubility data should be supplied. For most organic crystallization systems, which are very near ideal in behavior, the van't Hoff SLE method provides good results. The VLE behavior can usually be adequately represented by IDEAL or VANLAAR methods.

Examples
E-2.1: This example models a hydrocarbon-water mixture that contains less than 10% of water. The SRK method is chosen.

TITLE PROB=HC-WATER PRINT INPUT=ALL COMP DATA LlBID 1,H2O/2,C2/3,NC4/4,NC5/5,NC6 THERMO DATA METHOD SYSTEM=SRK WATER DECANT=ON STREAM DATA PROP STREAM=1,TEMP=100,PRES=100, & COMP=40/100/100/100/100 UNIT OPERATIONS FLASH FEED 1 PROD V=2,L=3,W=4 ISOT TEMP=100,PRES=100 END

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E-2.2

Refinery Application: A mixture of topped crude and dissolved steam is to be modeled. The BK10 method gives satisfactory results for this low pressure crude application.

TITLE PROB=VACUUM DIMEN METRIC, PRES=MMHG COMP DATA LIBID 1,H2O/ 2,C2/ 3,C3 THERMO DATA METHOD SYSTEM=BK10 STREAM DATA PROP STREAM=1, TEMP=330, PRES=8000, RATE(V)=99.37, & ASSAY=LV TBP STREAM=1, PRES(MMHG)=760, & DATA=0,257/ 5,324/ 10,380/ 20,399/ 30,435/ 40,455/ & 50,505/ 60,541/ 70,596/ 75,634 SPGR AVERAGE=0.9833, STREAM=1 PROP STREAM=2, TEMP=30, PRES=8000, RATE(V)=3.0, & COMP=2,75/ 3,25 PROP STREAM=3, TEMP=330, PRES=8000, RATE(W)=318, & COMP=1,100 PROP STREAM=4, TEMP=355, PRES=8500, PHASE=V, & RATE(W)=908, COMP=1,100 UNIT OPERATIONS MIXER FEED 1,2,3 PROD L=5 COLUMN PARA TRAY=2 FEED 5,1/ 4,2 PROD OVHD=6, BTMS=7,100 VAPOR 1,300/ 2,50 TEMP 1,355/ 2,371 HEAT 1,1 PRES 1,98/ 2,115 SPEC STREAM=7, RATE(V), VALUE=50.88 VARY HEAT=1 END

E-2.3

Sour Water Application: A sour water stream containing CO2, H2S, NH3 and HCN is to be modeled. The amount of HCN in the feed is small, and its distribution between the liquid and vapor phases is not important. Either the SOUR or GPSWAT methods could be used. However, an examination of the feed shows that the sum of the weight fractions of the sour gases exceeds 0.30. The GPSWAT method is therefore preferred over the SOUR method.
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TITLE PROB=SOUR PRINT INPUT=ALL COMPONENT DATA LIBID 1,N2/ 2,CH4/ 3,H2S/ 4,NH3/ & 5,CO2/6,HCN/7,H2O THERMODYNAMIC DATA METHODS SYSTEM=GPSWAT STREAM DATA PROP STREAM=1, TEMP=120, PRES=25, PHASE=L, & COMP(W)=1,2/ 2,3/3,8000/4,4000/ & 5,1200/6,0.238/7,25584.7 PROP STREAM=2, PRES=50, PHASE=V, COMP(M)=7,2000 UNIT OPERATIONS COLUMN PARA TRAY=7, IO=25, DAMP=0.5 FEED 1,1/ 2,7, NOTSEP PROD OVHD=3, BTMS=4,24446 PSPEC TOP=20.8, DPCOL=2.1678 ESTI MODEL=CONV END

E-2.4

Natural Gas Application: You wish to study a natural gas stream that contains less than 1 percent of N2. Therefore, the SRK equation of state method is used along with the COSTALD liquid density method to model this application.

TITLE PROB=LNG PRINT INPUT=ALL COMPONENT DATA LIBID 1,N2/ 2,CH4/ 3,C2/ 4,C3/ & 5,NC4/ 6,NC5/ 7,NC6 THERMODYNAMIC DATA METHODS SYSTEM=SRK, DENSITY(L)=COSTALD STREAM DATA PROP STREAM=1, TEMP=10, PRES=50, PHASE=V, & COMP(M)=1,2.6/2,93.7/3,1.94/4,0.95/ & 5,0.38/6,0.23/7,0.2 UNIT OPERATIONS PHASE ENVELOPE EVALUATE STREAM=1, LFRAC=0.90, IPLOT=OFF END

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E-2.5

Petrochemical Application: A binary aromatic mixture of n-methyl-formamide (NMF) and tert-butylformamide (TBUTFORM) is to be modeled at a pressure of 3 atmospheres. The SRK K-value method provides good results for aromatic systems above 2 atmospheres. The COSTALD liquid density method provides good results for aromatic systems at low temperatures.

TITLE PROB=AROM PRINT INPUT=ALL COMP DATA LIBID 1,NMF/ 2,TBUTFORM THERMO DATA METHOD SYSTEM=SRK, DENS(L)=COSTALD STREAM DATA PROP STREAM=1, TEMP=80, PRES(ATM)=1, RATE(W)=1000, & COMP=1,25/ 2,75 UNIT OPERATIONS COLUMN PARA TRAY=10, CHEM=40, DAMP=0.6 FEED 1,5 PROD OVHD=2, BTMS=3,700 COND TYPE=BUBB, PRES(ATM)=3 PSPEC PTOP(ATM)=3, DPCOL=0.5 DUTY 1,1,10/ 2,10,10 SPEC RRATIO, VALUE=5 SPEC STREAM=3, COMP=2, FRAC, VALUE=0.9 VARY DUTY=1,2 ESTI MODEL=CONV END

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Application Guidelines

E-2.6

Chemical and Environmental Application: A waterhydrocarbon stream is to be flashed at 1 atmosphere. The presence of acetic and acrylic acids in the stream necessitates the use of the Hayden-O'Connell vapor fugacity method to account for the vapor phase dimer formation. The NRTL method will be used to calculate VLE equilibria. The HENRY option is selected to model the supercritical components.

TITLE PROB=ACIDS PRINT INPUT=ALL COMP DATA LIBID 1,H2O/ 2,O2/ 3,N2/ 4,C3/ 5,IC4/ 6,NC4/ & 7,NC5/ 8,ACETIC/ 9,ACRYLIC THERMO DATA METHOD SYSTEM=NRTL, PHI=HOCV, ENTH(V)=HOCV , & DENS(V)=HOCV, HENRY KVALUE BANK=SIMSCI, POYNTING=YES, FILL=IDEAL HENRY BANK=SIMSCI SOLUTE 2,3 STREAM DATA PROP STREAM=1, TEMP=80, PRES(ATM)=1, RATE(W)=1000, & COMP=1,0.80/ 2,2.0E-02/ 3,0.04/ 4,2E-02/ 5,5.0E-02/ & 6,0.05/ 7,1.0E-03/ 8,0.01/ 9,0.01 UNIT OPERATIONS FLASH FEED 1 PROD L=2, V=3 ISOT TEMP(C)=90, DP=0.0 END

E-2.7

Solid Application: Urea is to be precipitated from an aqueous solution. Some library properties for urea and water such as vapor pressure and heat capacity are overridden with user-supplied values. The urea-water mixture is non-ideal and so user solubility data are supplied.

PRO/II Thermodynamic Data Keyword Manual

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TITLE PROB=SOLIDS PRINT INPUT=ALL COMP DATA LIBID 1,UREA/ 2,H2O PHASE VLS=1 ATTR COMP=1, PSD(MIC)=147,208,295,417,589,833,1168 TTP(K) 1,4.0585E+02 PTP(PA) 1,9.31306E+01 FORMATION(V,J/KG,MOLE) 1,-2.458E+08,-1.582E+08 HFUS(J/KG,MOLE) 1,1.479E+07 VP(L,PA,K) CORR=20, LN, DATA=1, & 3.6805E+02,2.981E+02,2.8209E+01,-1.05E+04, & 1.0272E-01,0.0,0.0,0.0 LATENT(J,KG/K,MOLE) CORR=1, DATA=1, & 2.981E+02,2.981E+02,8.7864E+07,0.0, & 0.0,0.0,0.0,0.0 CP(S,J/KG,K,MOLE) CORR=1, DATA=1, & 4.0E+02,8.0E+01,1.725E+04,2.318E+02, & 7.9E-02,0.0,0.0,0.0 DENS(S,K,KG/M3,WT) CORR=1, DATA=1, & 300.0,20.0,1335.036 SVTB 1,-7.701601E-03 SLTB 1,1.889548E+02 SLTM 1,1.639447E+01 HVTB 1,-9.317743E-03 HLTB 1,8.7864E+04 HLTM 1,7.127574E+03 THERMO DATA METHOD SYSTEM(VLE)=VANLAAR, KVALUE(SLE)=SOLDATA KVALUE(VLE) VANLAAR 1,2,0.8255,100.0 KVALUE(SLE) SOLUTE 1 SOLDATA(K) 1,2,0.0,-1310.37,0.533619 STREAM DATA PROP STREAM=1, TEMP=80, PRES(ATM)=1, RATE(W)=1000, & COMP=1,25/ 2,75 UNIT OPERATIONS CRYSTALLIZER FEED 1 PROD OVHD=2, BTMS=3 RATING VOLUME=200 OPER SOLU=1, SOLVENT=2, TEMP=20, DP=0.0 GROWTH KG(M/S)=1.0E-07, GEXP=0.2 NUCLEATION KB=8.0E+13, RPM=100 END

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Application Guidelines