Duhok Polytechnic University

Technical College of Engineering

Petrochemical Departments
Fourth stage
Plant design
-Group-A
Student name : shavang khoshavi
Lecturer name:mr.abdulsalam
Peng-Robinson EOS
The Peng-Robinson EOS has become the most popular equation of state for natural gas systems
in the petroleum industry. During the decade of the 1970’s, D. Peng was a PhD student of Prof.
D.B. Robinson at the University of University of Alberta (Edmonton, Canada). The Canadian
Energy Board sponsored them to develop an EOS specifically focused on natural gas systems.
When you compare the performance of the PR EOS and the SRK EOS, they are pretty close to a
tie; they are “neck to neck,” except for a slightly better behavior by the PR EOS at the critical
point. A slightly better performance around critical conditions makes the PR EOS somewhat
better suited to gas/condensate systems.The Peng-Robinson equation describes the state of the
gas under given conditions, relating pressure, temperature and volume of the constituent matter.
The Peng-Robinson equation of state has the basic form:

p=R⋅T/Vm−b−a⋅α/Vm2+2⋅b⋅Vm−b2

Description
The Peng-Robinson equation of state (named after D.-Y. Peng and D. B. Robinson) can model
some liquids as well as real gases.

Peng-Robinson is most enhanced in Hysys, highest T & P range, has special treatment for key
components, largest binary interaction database: good standard for hydrocarbons

It is easy to see in the first term of the Peng-Robinson equation that this state equation had its
origins in the Ideal gas law: pV = nRT, since VnVn gives you molar volume.   To apply the Ideal
gas law to real gases, correction terms have been included that are composed of empirically
derived offsets.
The Peng-Robinson equation was specifically deigned to meet the following criteria:

1. The parameters should be expressible in terms of the critical properties and the acentric

factor.
2. The model should provide reasonable accuracy near the critical point, particularly for
calculations of the compressibility factor and liquid density.
3. The mixing rules should not employ more than a single binary interaction parameter,
which should be independent of temperature pressure and composition.
4. The equation should be applicable to all calculations of all fluid properties in natural gas
processes.

Usage
This equation is popular for us with natural gas systems found in petroleum industries. Equations
of state are useful in describing the physical properties of fluids, solids, and even the interior of
stars.
The PR property package rigorously solves any single-, two-, or three-phase system with a high
:degree of efficiency and reliability and is applicable over a wide range of conditions

temperature range >-271∁ or 456F-

pressure range <100,000kpa or 15,000psia-

For oil gas or Petrochemical applications, the PR EOS is the generally recommended
property package The PR property package is generally used for the following simulations

TEG dehydration-

TEG dehydration with aromatics -

cryogenic gas processing-

air separation-

Atm crude tower-

vacuum towers-

high H2 systems-

reservior systems-

hydrate inhibition-

crude system-

:Peng robinson
– Most enhanced model in Aspen HYSYS
– Largest applicability range in terms of T and P
– Special treatments for some key components
– Largest binary interaction parameter database

What is the SRK ?

The parameter mixing rules of the Soave–Redlich–Kwong (SRK) equation of state are rewritten
as Huron–Vidal mixing rules, where infinite-pressure activity coefficients are predicted by group
contributions. Alkanes are treated as composed by one group type and aromatics by two types,
aliphatic and aromatic. Hydrocarbon mixtures can be treated using one universal interaction
parameter. Light compounds like methane, N2, CO2, H2S, etc. are treated as separate groups; each
one requires a pair of parameters for its interactions with aliphatic and aromatic groups. Group
interaction parameters were determined from experimental VLE data. From them, binary
interaction constants of the classical quadratic mixing rules can directly be derived

SRK
in many cases, the Soave--Redlich-kwong SRKmodel provides comparable results to Peng-
:Robinson, but its range of application is significantly more limited

temperature range>-143 C or -225 F-

-pressure range<5,000 psia or 35,000kpa

The SRK EOS should not be used for non-ideal chemicals such as alcohols, acids or other
components. These chemicals are more accurately handled by the activity models (highly non-
ideal) or the PRSV EOS (moderately non-ideal)

:The SRK property package is generally used for the following simulations

TEG dehydration-

sour water-

cryogenic gas processing-

air separation-

Atm crude tower-

vacuum tower-

high H2 system-

reservior system-

hydrate inhibition-

chemical system-

HF alkylation-

TEG dehydration with aromatic-

SRK
– Modified RK model
– Can provide comparable results to PR in many cases, but
with a lot less enhancement in Aspen HYSYS
-SRK: modified Redlich Kwong model. Similar accuracy/use as Peng Rob, but in Hysys SRK
has less enhancements than PR.

 Sour PR model and Sour SRK

The Sour PR model combines the Peng-Robinson equation of state and wilson’s API-Sour
:modelfor handling sour water systems and can be applied to

sour water strippers-

hydrotreter loops-

crude columns-

any process containing hydrocarbons acid gases and H2O-

In the sour PR model, the K-values for the aqueous phase are calculated using Wilson’s API-
Sour method. This option uses Wilson’s model to account for the ionization of the H2S and co2
and NH3 in the aqueous water phase.The original model is applicable for temperatures between

C (68F)and 140C (285F)and pressure up to 50psia 20

The acceptable pressure ranges for the HYSYS model vary depending upon the concentration of
the acid gases and H2O. The method performs well when theH2O partial pressure is below
100psi

? What is the NRTL

The nonrandom two-liquid (NRTL) model is an activity coefficient model used widely in phase
equilibria calculations. The NRTL model has three adjustable parameters that are determined
through regression of experimental data for a specific system. A generalization for the model
parameters would reduce the time, money and effort expended on the collection of experimental
data. This work focuses on the application of a theory-framed quantitative structure–property
relationship (QSPR) modeling approach for the estimation of NRTL parameters. A database of
342 low-temperature binary (10–40 °C) liquid–liquid equilibria (LLE) systems was employed in
this work. Data regression analyses were performed to determine the NRTL model parameters.
Structural descriptors of the molecules were generated and used in developing a QSPR model to
estimate the regressed NRTL parameters. The newly developed QSPR model uses 30 significant
descriptors as inputs. The model yielded binary predictions with 8, 38, 51 and 44% absolute
average deviation for the mole fractions (x1 in 1-rich phase and x1 in 2-rich phase) and partition
coefficients (K1 and K2), respectively. These errors are approximately 3 to 4 times the errors
found from the regression analyses. Further, we observed an 11% prediction failure rate, in
which cases the model fails to converge to an equilibrium solution. The application of the
popular and often employed UNIFAC-1981-LLE model resulted in 3 to 7 times the errors
obtained through regression analyses and a prediction failure rate of 36%. These results
demonstrate the efficacy of our QSPR model in providing improved predictions and an increased
.range of applicability when compared to the UNIFAC-1981-LLE model for LLE systems

:Parameter determination
The NRTL parameters are fitted to activity coefficients that have been derived from
experimentally determined phase equilibrium data (vapor–liquid, liquid–liquid, solid–liquid) as
well as from heats of mixing. The source of the experimental data are often factual data banks
like the Dortmund Data Bank. Other options are direct experimental work and predicted activity
coefficients with UNIFAC and similar models. Noteworthy is that for the same liquid mixture
several NRTL parameter sets might exist. The NRTL parameter set to use depends on the kind of
phase equilibrium (i.e. solid–liquid (SL), liquid–liquid (LL), vapor–liquid (VL)). In the case of
the description of a vapor–liquid equilibria it is necessary to know which saturated vapor
pressure of the pure components was used and whether the gas phase was treated as an ideal or a
real gas. Accurate saturated vapor pressure values are important in the determination or the
description of an azeotrope. The gas fugacitycoefficients are mostly set to unity (ideal gas
assumption), but for vapor-liquid equilibria at high pressures (i.e. > 10 bar) an equation of
.state is needed to calculate the gas fugacity coefficient for a real gas description

Extended NRTL
The extended NRTL is a variation of NRTL model allowing you to input values for the
Aij,Bij,Cij,AIP1ij and AIP2ij parameter used in defining the component activity coefficients

:Apply this model to systems

with a wide boiling point range between components-

where you require simulations solution of VLE and LLE and there exists wide boiling point -
range or concentration range between component

:Extended NRTL uses the following calculation methods

:For liquid

NRTL method for VLE-

cavett method for enthalpy and entropy-

:For vapour

ideal gas ,RK,virial,peng robinson, and SRK method for VLE-

ideal gas,RK,virial,peng robinson, and SRK method for enthalpy and entropy-

:General NRTL
This variation of the NRTL model allows you to select the equation format for
:equation parameters t and x apply this model to systems

with a wide boiling point range between components-

where you require simultaneous solution of VAE and AAE, and there exists a wide boiling point-
or concentration range between components

:General NRTA uses the following calculation methods

:for liquid

NRTL method for VLE- 

cavett method for Enthalpy and Entropy-

:For vapour

ideal gas, RK, Virial, Peng Robinson, and SRK methods for VLE-

Ideal Gas, RK, Virial, Peng Robinson, and SRK methods for Enthalpy and Entropy-

NRTL

The NRTL on-Random-Two-Liquid (NRTL) equation is an extension of the wilson equation. it

uses statistical mechanics and the liquid cell theory to represent the liquid structure. it is capable
of representing VLE, LLE, and VLLE phase behavior.The NRTL property package is used
for chemical systems and HF Alkylation with highly non-ideal chemicals. NRTL uses the
:following calculation methods

:for liquid

NRTL method for VLE- 

cavett method for Enthalpy and Entropy-

:For vapour

ideal gas, RK, Virial, Peng Robinson, and SRK methods for VLE-

Ideal Gas, RK, Virial, Peng Robinson, and SRK methods for Enthalpy and Entropy-
Like the Wilson equation, the NRTL is thermodynamically consistent and can be applied to
ternary and higher order systems using parameters regressed from binary equilibrium data. It has
accuracy comparable to the Wilson equation for VLE systems.The NRTL equation in HYSYS
contains five adjustable parameters (temperature dependent and independent)) for fitting
.per binary pair. The NRTL combines the advantages of the Wilson and van Laar equations

like the van laar equation , NRTL is not extremely CPU intensive and can represent LLE quite -
well

unlike the van laar equation NRTL can be used for dilute system and hydrocarbon-alcohol -
mixture ,although it may not be used as a good for alcohol –hydrocarbon system as the Wilson
equation

the five adjustment parameter for the NRTL equation in HYSYS are the aij,aji,bil,bji,and αij -
terms

?We can use two fluid package together

Yes we can
There are many times when a user wishes to use a traditional fluid package (such and Peng-
Robinson) in one part of the HYSYS flowsheet and then to use the OLI fluid package in another
part of the flowsheet. The user may not care to use the rigorous electrolytes (and the potentially
large computational overhead) in all of the flowsheet but needs the rigor in only a portion. There
are two major issues when attempting to do this in HYSYS.
The first issue is that HYSYS permits only one fluid package per flowsheet section. If you need
to use a second fluid package, you must create a sub-flowsheet. The second issue is that the
component names between fluid packages may not be the same.