16 views

Uploaded by elizabethchemestry

ucalgary

- distillation project
- Compositional Hydrocarbon Reservoirs. Continuous Thermodynamics
- Section 3 Well Performance
- TDA 301T-8c - Thermodynamic Properties Real Substances
- Equation of State
- Tutorial Sheet 04 Answers 2014
- Physical Principles of Food Preservation
- Basic(2)
- lle
- rpi_physics1_lec01
- Topic 4. Binary Distillation V2
- soal matekkim.pdf
- Calypso_07_OVCMM.pdf
- Distillation PostLab Final
- Distillation
- Equotip Uncertainty Clarification Short E 2014.01.10
- 03 Reliability of Generation Systems[1]
- 43072296 HTFS Presentation 2
- SPE Phase Behavior Monograph Ch 5
- 1_5024240515088908344

You are on page 1of 178

Properties and Thermodynamic Models

by

Samaneh Hajipour

A THESIS

SUBMITTED TO THE FACULTY OF GRADUATE STUDIES

IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE

DEGREE OF DOCTOR OF PHILOSOPHY

CALGARY, ALBERTA

JANUARY, 2014

Abstract

The issues related to error propagation from uncertainties in physical properties and

thermodynamic models involved in process modelling and simulation are examined.

Traditionally, the effect of these basic parameters are ignored in chemical and process

engineering and designers make the final decision on determining equipment parameters such as

sizing and residence time in an ad-hoc manner based on their prior experience with similar

problems. The objective of this dissertation is to develop a self-contained and consistent

mathematical procedure to quantify the effect of uncertainties related to thermodynamic models

on process design calculations for flow sheets of any complexity. The methodology is based on

the Monte Carlo technique along with Latin Hypercube Sampling (LHS) method.

The development of such an error propagation algorithm requires that the uncertainty

information of physical properties of pure compounds and vapour-liquid equilibrium (VLE) data

of binary mixtures be readily available. A pure component database was developed for 176 pure

hydrocarbons in the range of C5 to C36 based on NISTs ThermoData Engine (TDE) system. Two

generalized correlations for the calculation of critical properties and acentric factors

parameterized by the normal boiling point and specific gravity were re-parameterized. The

PengRobinson (PR) equation of state was re-parameterized against the pure component

database using a weighted nonlinear least squares method for the determination of its

dependency on acentric factors and the definition of the uncertainty of its generalized

parameters. The variance-covariance matrices for error propagation calculations were also

determined for each model.

Binary mixture database was also developed containing experimental VLE data and their

uncertainties taken from TDE for 87 binary mixtures present in natural gas processing. The

ii

quality of each isothermal VLE dataset was investigated using a thermodynamic consistency test.

The binary interaction parameters associated with their uncertainties for the re-parameterized PR

equation of state along with the van der Waals quadratic mixing rules were evaluated against the

consistent VLE data using nonlinear optimization coupled with the Monte Carlo method taking

into account the uncertainties of input parameters.

Using the databases developed in this study, a simple and general error propagation algorithm

based on the Monte Carlo technique combined with the LHS sampling method was developed

and coupled with the VMGSim process simulator to analyze the effect of uncertainties on

chemical process design and simulation. The method was applied to simplified cases of industrial

interest such as gasoline blending and injection of liquid hydrocarbon to the existing natural gas

pipeline. The results show how the new approach can guide process engineers in revisiting

process design decisions affected by uncertainties related to thermodynamics.

iii

Preface

This paper-based Ph.D. thesis includes the results of studies conducted at the Department of

Chemical and Petroleum Engineering of the University of Calgary and funded by Shell Canada

Ltd. The main chapters of this thesis have been published in reputable peer-reviewed journals in

the field of chemical engineering. All papers have been reused with the permission of copyright

owners and reformatted to conform to the University of Calgary formatting requirements.

A version of Chapter 2, along with Appendices A and B, has been published as S.

Hajipour, M.A. Satyro, Uncertainty Analysis Applied to Thermodynamic Models and Process

Design - 1. Pure Components, Fluid Phase Equilibria 307 (2011) 78-94.

A version of Chapter 3, along with Appendices C and D, has been published as S.

Hajipour, M.A. Satyro, M.W. Foley, Uncertainty Analysis Applied to Thermodynamic Models

and Process Design - 2. Binary Mixtures, Fluid Phase Equilibria 364 (2013) 15-30.

A version of Chapter 4 has been published online as S. Hajipour, M.A. Satyro, M.W.

Foley, Uncertainty Analysis Applied to Thermodynamic Models and Fuel Properties - Natural

Gas Dew Points and Gasoline Reid Vapour Pressures, Energy Fuels (2013), DOI:

10.1021/ef4019838.

For all three papers, I was the lead investigator and intellectually responsible for concept

formation, literature review, data collection and analysis, mathematical modelling, simulation

and optimization, graphical and tabular results preparation, as well as manuscript composition.

The first paper was written under supervision of Dr. Satyro and two others were supervised by

Dr. Foley. Dr. Satyro was involved throughout the research in forming concepts, identifying the

research questions, reviewing the research findings, and editing the manuscripts. Dr. Foley was

involved in this project as a supervisor and contributed in discussions and manuscript edits.

iv

Acknowledgements

The accomplishment of a doctoral research is fundamentally a collaborative process and it has

happened because of those who supported and encouraged me on this path, emotionally,

academically, and financially. My expressions and feeling of gratitude to compensate their

efforts are not bounded by these brief remarks in these pages.

Above all, I would like to express my sincerest gratitude and appreciation to my

supervisor, Dr. Michael W. Foley, and my ex-supervisor, Dr. Marco A. Satyro, for their

continuous encouragement and unconditional support during these challenging years with both

ups and downs. This work would not have been possible without Dr. Foleys kind support and

agreement to take me on as a Ph.D. student in the middle of my research, despite the tenuous

connection between his research and my own. I am grateful to him for always being believing

me and letting me pursue my ideas and being available for guidance whenever required. My

most important coach and advisor, Dr. Satyro, deserves very special thanks for the initiation of

this study and continuous technical and emotional support at all times. I can never express my

gratitude to him for eagerly sharing his valuable knowledge and ideas with me, and being always

ready to take time out from his busy schedule to guide me and keep me on the right track.

Working with him was a dream come true and I am very proud of being his student.

I am very grateful to my supervisory committee members, Dr. William Y. Svrcek and Dr.

Harvey W. Yarranton, for their precious time and constructive feedback and suggestions.

Furthermore, I would like to acknowledge Dr. Laurence R. Lines for his time to review this

thesis and being my examiner and Dr. Vladimir V. Diky from National Institute of Standards and

Technology (NIST) for agreeing to act as an external examiner and sharing his insights on

TDEs uncertainty evaluation.

v

Thanks go to my previous teachers from the University of Tehran, Dr. Mohsen Edalat for

providing me with a strong background in Thermodynamics and Dr. Rahmat Sotudeh-Garebagh

for introducing me to Dr. Satyro and motivating me to continue my graduate studies at the

University of Calgary. My appreciation goes Dr. Jos O. Valderrama from the Universidad de la

Serena for valuable discussions on his proposed thermodynamic consistency test method. I also

gratefully acknowledge Virtual Materials Group Inc. for providing access to NISTs TDE

software and a copy of the VMGSim process simulator.

I would like to acknowledge Shell Canada Ltd. For funding this research and offer many

thanks towards the Ursula and Herbert Zandmer Graduate Scholarship, the Graduate Students

Association and the Department of Chemical and Petroleum Engineering at the University of

Calgary for their scholarships and financial support. I would also like to thank the administrative

staff of the department specially Dolly Parmar and Arlene Wallwork for their help.

Great appreciation goes to my officemates for providing an extraordinary working

environment in our office and close friends of many years in Iran and Canada for their

friendship, good humor, faith, understanding, respect, and emotional support.

At last but definitely not least, I owe the deepest gratitude to my parents, my brother,

Meisam, and my sister in law, Behnaz, in Iran who have always believed in me and understood

my desire to study abroad and being by my side virtually with full encouragement, compassion

and love. I would like to extend my thanks to my two-year-old niece, Tina, for putting a smile on

my face from miles apart. Their memories and their support from long distance by emails and

phone calls kept me focused on my goals and provided me with hope and confidence.

vi

Dedication

for their endless support and unconditional love.

vii

Table of Contents

Abstract ........................................................................................................................................... ii

Preface............................................................................................................................................ iv

Acknowledgements ..........................................................................................................................v

Table of Contents ......................................................................................................................... viii

List of Tables ...................................................................................................................................x

List of Figures and Illustrations .................................................................................................... xii

List of Symbols, Abbreviations and Nomenclature .......................................................................xv

CHAPTER ONE: INTRODUCTION ..............................................................................................1

1.1 Overview ................................................................................................................................1

1.2 Research Objectives ...............................................................................................................6

1.3 Thesis Structure .....................................................................................................................9

CHAPTER TWO: UNCERTAINTY ANALYSIS APPLIED TO THERMODYNAMIC

MODELS AND PROCESS DESIGN 1. PURE COMPONENTS ...................................11

2.1 Abstract ................................................................................................................................11

2.2 Introduction ..........................................................................................................................11

2.3 Pure Component Database Development ............................................................................17

2.3.1 Uncertainty on Standard Specific Gravity ...................................................................18

2.3.2 Uncertainty on Pitzer Acentric Factor .........................................................................19

2.4 Development of A New Correlation for Critical Temperature, Critical Pressure and

Acentric Factor Using Uncertainties in Physical Property Data ........................................21

2.4.1 Computational Approach.............................................................................................23

2.4.1.1 Linear Regression ..............................................................................................28

2.4.1.2 Nonlinear Regression .........................................................................................30

2.4.2 Results and Discussion ................................................................................................32

2.4.2.1 Examples ............................................................................................................41

2.5 Effect of Uncertainties in Thermodynamic Data on Calculated Thermo-physical

Properties ...........................................................................................................................42

2.5.1 Notes on the Uncertainty of Input Variables ...............................................................42

2.5.2 The Monte Carlo Technique and Sampling.................................................................42

2.6 Re-parameterization of the PengRobinson Equation of State ...........................................46

2.7 Natural Gas Processing Examples .......................................................................................49

2.8 Conclusions ..........................................................................................................................53

CHAPTER THREE: UNCERTAINTY ANALYSIS APPLIED TO THERMODYNAMIC

MODELS AND PROCESS DESIGN 2. BINARY MIXTURES .....................................55

3.1 Abstract ................................................................................................................................55

3.2 Introduction ..........................................................................................................................56

3.3 Thermodynamic Consistency Test.......................................................................................66

3.3.1 Computational Approach for Modelling of VLE Data................................................70

3.4 Binary VLE Database Development....................................................................................72

3.4.1 Application of the Selected Consistency Test in This Study ......................................74

viii

3.5.1 Input Variables and Their Uncertainties......................................................................80

3.5.2 The Monte Carlo Technique and Sampling Method ...................................................81

3.6 Results and Discussion ........................................................................................................87

3.6.1 Saturation Point Calculation ........................................................................................87

3.6.2 De-ethanizer Example .................................................................................................92

3.6.3 Natural Gas Processing Example ................................................................................94

3.7 Conclusions ..........................................................................................................................97

CHAPTER FOUR: UNCERTAINTY ANALYSIS APPLIED TO THERMODYNAMIC

MODELS AND FUEL PROPERTIES NATURAL GAS DEW POINTS AND

GASOLINE REID VAPOUR PRESSURES .......................................................................99

4.1 Abstract ................................................................................................................................99

4.2 Introduction ........................................................................................................................100

4.2.1 Liquid Hydrocarbon Injection into an Existing Natural Gas Pipeline ......................100

4.2.2 Gasoline Blending .....................................................................................................102

4.3 Development of the Error Propagation Algorithm ............................................................103

4.4 Case Study Problems .........................................................................................................106

4.4.1 Injection of Liquid n-Butane into an Existing Natural Gas Pipeline .........................106

4.4.2 Gasoline Blending .....................................................................................................111

4.5 Uncertainty Analysis Results and Discussion ...................................................................114

4.6 Conclusions ........................................................................................................................128

CHAPTER FIVE: CONCLUSIONS AND RECOMMENDATIONS ........................................130

5.1 Conclusions ........................................................................................................................130

5.2 Recommendations ..............................................................................................................133

APPENDIX A: DATABASE FOR PURE HYDROCARBONS FROM C5 TO C36 ..................135

APPENDIX B: CALCULATED UNCERTAINTY OF VAPOUR PRESSURE USING NEW

3-PARAMETER PENG-ROBINSON EQUATION OF STATE BY COVARIANCE

APPROACH .......................................................................................................................143

APPENDIX C: DETAILS ON THE DEVELOPED VLE DATABASE ...................................145

APPENDIX

D:

BINARY

INTERACTION

PARAMETERS

AND

THEIR

UNCERTAINTIES ............................................................................................................149

REFERENCES ............................................................................................................................153

ix

List of Tables

Table 2.1. General forms of correlations. ..................................................................................... 24

Table 2.2. Fitted parameters and covariance matrices for new RiaziDaubert correlations

obtained from nonlinear regression....................................................................................... 33

Table 2.3. Fitted parameters and covariance matrix for the re-parameterized LeeKesler

correlation for critical temperature. ...................................................................................... 33

Table 2.4. Fitted parameters and covariance matrix for the re-parameterized LeeKesler

correlation for critical pressure. ............................................................................................ 34

Table 2.5. Fitted parameters and covariance matrix for the re-parameterized LeeKesler

correlation for acentric factor. ............................................................................................... 35

Table 2.6. Comparison of re-evaluated correlations using weighted deviation. ........................... 36

Table 2.7. Comparison of the experimental and calculated critical properties and acentric

factors of n-hexane and n-dodecane...................................................................................... 41

Table 2.8. Monte Carlo sampling for normal boiling point. ......................................................... 45

Table 2.9. Peng-Robinson equation of state refitted parameters and covariance matrix. ............. 47

Table 2.10. Comparison results of the original PR equation and the refitted equations............... 47

Table 2.11. Comparison of vapour pressure and its uncertainty calculated using the

covariance-based approach and the Monte Carlo simulation. .............................................. 49

Table 2.12. Critical point, cricondenbar and cricondentherm coordinates when compressing

lean natural gas prototype mixtures. ..................................................................................... 50

Table 2.13. Basic equipment performance data estimated using uncertainty information. .......... 51

Table 3.1. Sample of developed VLE database for the ethane/propane mixture. ......................... 73

Table 3.2. Range of VLE data used for the consistency test. ....................................................... 74

Table 3.3. Critical properties and acentric factors of pure components. ...................................... 75

Table 3.4. Thermodynamic consistency data for ethane/propane and methane/H2S. ................... 76

Table 3.5. Input variables for estimation of a binary interaction parameter. ................................ 81

Table 3.6. Temperature and pressure ranges of consistent VLE data for ethane/propane and

methane/H2S binary mixtures. .............................................................................................. 83

x

Table 3.7. Monte Carlo simulation results for binary interaction parameters (k12) with

different sample sizes. ........................................................................................................... 86

Table 3.8. Calculated VLE data and their uncertainties for ethane/propane mixture at P=2758

kPa using the technique developed in this work. .................................................................. 89

Table 3.9. The de-ethanizer product specifications (ethane(1)/propane(2)) at P=2758 kPa. ....... 92

Table 3.10. Comparison of the minimum number of stages using different approaches applied

in this work. .......................................................................................................................... 94

Table 3.11. Basic equipment performance data and their uncertainties revisited in this work. ... 95

Table 3.12. Positions of the cricondenbar, cricondentherm and critical point calculated using

the Monte Carlo simulation. ................................................................................................. 96

Table 4.1. Composition of natural gas used in this study. .......................................................... 108

Table 4.2. Existing natural gas pipeline specifications used in this work. ................................. 108

Table 4.3. Existing pipeline equipment performance data. ........................................................ 110

Table 4.4. Low RVP gasoline blend chemical composition. ...................................................... 112

Table 4.5. Properties of pure components. ................................................................................. 113

Table 4.6. Results of the phase envelopes uncertainty analysis. ................................................ 116

Table 4.7. Physical properties of the gas and the pipeline equipment performance data before

and after the injection. ......................................................................................................... 121

Table 4.8. Vapour pressures and uncertainties calculated using the Monte Carlo simulation

for the gasoline before and after n-butane blending at different temperatures. .................. 124

Table 4.9. Results of uncertainty analysis of RVP calculation depending on the volume ratio

of the blended n-butane to gasoline at standard conditions. ............................................... 126

Table C.1. Detailed information about the developed binary VLE database. ............................ 145

Table D.1. Binary interaction parameters associated uncertainties. ........................................... 149

xi

Figure 2.1. Effect of error in the critical temperature on the predicted vapour pressure using

the PengRobinson equation of state for simple paraffins. .................................................. 13

Figure 2.2. Calculated acentric factor associated with uncertainty as a function of vapour

pressure @ Tr=0.7. ................................................................................................................ 20

Figure 2.3. Calculated acentric factor associated with uncertainty as a function of critical

pressure. ................................................................................................................................ 20

Figure 2.4. Calculated acentric factor associated with uncertainty as a function of critical

temperature. .......................................................................................................................... 21

Figure 2.5. Uncertainties of normal boiling point and specific gravity. ....................................... 37

Figure 2.6. Critical temperature versus normal boiling point. ...................................................... 39

Figure 2.7. Critical pressure versus normal boiling point. ............................................................ 39

Figure 2.8. Acentric factor versus normal boiling point. .............................................................. 40

Figure 2.9. Critical temperature normal distributions for (a) n-hexane (b) n-dodecane. .............. 44

Figure 2.10. Comparison of vapour pressure calculated using the original and the improved

PengRobinson equations of state. ....................................................................................... 48

Figure 2.11. Pressuretemperature envelope for Composition 1 (methane and n-hexane). ......... 52

Figure 2.12. Pressuretemperature envelope for Composition 2 (methane and n-dodecane). ..... 52

Figure 3.1. Temperature-composition diagram for ethane/propane system at 2758 kPa. Note

that the thickness of the TXY curves actually represents the uncertainties associated

with the bubble and dew points curves. ................................................................................ 59

Figure 3.2. Effect of uncertainties in compositions on (a) vapourliquid equilibrium constant

(Ki), and (b) relative volatility () for ethane/propane system at pressure of 2758 kPa. ...... 61

Figure 3.3. Illustration for the calculation of AP between two consecutive points of r and s. ...... 68

Figure 3.4. System ethane/propane, (a-c) Pressure-composition diagrams at 270.00, 310.93,

and 273.20 K, (d-f) Deviations in the individual areas ( %Ai ) for liquid phase () and

vapour phase ( ). ................................................................................................................... 77

xii

Figure 3.5. System methane/H2S, (a-c) Pressure-composition diagrams at 273.20, 277.59, and

310.93 K, (d-f) Deviations in the individual areas ( %Ai ) for liquid phase () and

vapour phase ( ). ................................................................................................................... 78

Figure 3.6. Conceptual scheme of the approach used for uncertainty estimation of the fitted

parameter............................................................................................................................... 82

Figure 3.7. Histogram of calculated binary interaction parameters by different sample sizes

(a) ethane/propane, (b) methane /H2S. .................................................................................. 84

Figure 3.8. Binary interaction parameter distribution for ethane/propane with sample size

100......................................................................................................................................... 85

Figure 3.9. Temperature-composition diagram for (a) ethane/propane at 2758 kPa, and (b)

methane/H2S at 6894.8 kPa................................................................................................... 88

Figure 3.10. Pressure-composition diagram for (a) ethane/propane at 310 K, and (b)

methane/H2S at 320 K. .......................................................................................................... 91

Figure 3.11. Schematic diagram of natural gas processing example. ........................................... 95

Figure 3.12. Pressure-temperature envelope for Composition 2 (methane/n-decane).................. 96

Figure 4.1. Sequence of overall error propagation evaluation process. ...................................... 105

Figure 4.2. Pressure-temperature (PT) envelope for a natural gas and thermodynamic

positions of the pipeline with temperatures of higher (T1) and lower (T2) than dew point

temperature at pressure of P................................................................................................ 107

Figure 4.3. Schematic view of the existing natural gas pipeline used in this work. ................... 109

Figure 4.4. Pressure-temperature envelopes for a natural gas before and after the liquid nbutane injection. .................................................................................................................. 115

Figure 4.5. (a) The zoomed-in version of Figure 4.4 for pressure-temperature envelope of gas

after the injection of 137.52 m3/hr, and (b) Monte Carlo simulation results for dew point

calculation at 5515.8 kPa. ................................................................................................... 117

Figure 4.6. (a) Calculated dew point and associated uncertainty at 5515.8 kPa against the

injected liquid/gas standard volume ratio, and (b) zoomed-in version of (a) in the

vicinity of maximum dew point. ......................................................................................... 119

Figure 4.7. Monte Carlo simulation results for the dew point calculation at 5515.8 kPa after

the injection of 135.45 m3/hr n-butane................................................................................ 120

Figure 4.8. Pressure-temperature envelopes for the gasoline before and after n-butane

blending............................................................................................................................... 123

xiii

Figure 4.9. Monte Carlo simulation results for the RVP calculation of the final gasoline blend

with 7.17 volume percent of blended n-butane. .................................................................. 125

Figure 4.10. Calculated RVP and associated uncertainty against the blended nbutane/gasoline standard volume ratio. ............................................................................... 126

Figure 4.11. Monte Carlo simulation results for RVP calculation of the final gasoline blend

with 6.86 volume percent of blended n-butane. .................................................................. 128

xiv

Abbreviation

Definition

AAD

AD

Absolute Deviation

APR

Advanced PengRobinson

ASTM

CI

Confidence Interval

DIPPR

EOS

Equation of State

EPS

LHS

LK

LeeKesler

LNG

LPG

MAOP

Max.

Maximum

MC

Monte Carlo

MCS

MCSE

Min.

Minimum

NFC

NIST

NPS

PR

PengRobinson

RD

RiaziDaubert

RK

RedlichKwong

RVP

SHS

SRK

SoaveRedlichKwong

xv

TC

Thermodynamically Consistent

TDE

ThermoData Engine

TI

Thermodynamically Inconsistent

TRC

VLE

VapourLiquid Equilibria

WS

WongSandler

A

molar Helmholtz energy in Chapter 3, kJ/kmol

area deviation

calculated area

AP

experimental area

attraction parameter in Chapter 3, kPa.(m3/kmol)2

variance-covariance matrix

element of matrix C

Fobj

objective function

independent variable

Kw

kij

interval identification

MW

xvi

m'

n'

sample size

NC

number of components

Nmin

NP

NT=cte.

Psat

weighting factor

standard deviation

SG

specific gravity

Tb

U'

U'

compressibility factor

xvii

Greek letters

PR

PR alpha function

element of matrix

'

'

activity coefficient

ij

element of matrix

12

21

mean value

uncertainty

fugacity coefficient

acentric factor

Subscript

avg.

average

bottom product

critical property

xviii

distillate

mixture

reduced property

tra.

transferred

Superscript

cal.

calculated

excess property

exp.

experimental

liquid phase

residual property

vapour phase

xix

1.1 Overview

Physical and thermo-physical property data for pure components and mixtures are essential in

the field of chemical engineering for the simulation, design, optimization, and debottlenecking of

industrial facilities. Vapour pressure, for example, is required for the design of almost all

equipment and processes in which both liquid and vapour phases are present. Vapourliquid

equilibrium data are used for the simulation and design of separation equipment and used

throughout the design of a plant or a fluid transportation facility. Critical properties and acentric

factors are essential for vapourliquid processes simulated using equations of state. The

reliability and accuracy of these properties are essential for the proper understanding and

modelling of processes. Physical properties are invariably derived from experimental

measurements and therefore subject to uncertainties associated with measured values. The errors

associated with physical properties can have costly consequences such as unnecessarily large

overdesign with corresponding high capital or operating costs or, at its worst, designs that cannot

be made to provide products within desired specifications.

Today, commercial process simulation software such as VMGSim and Aspen

HYSYS are routinely used to quickly simulate, design, develop and optimize processes.

Physical and thermo-physical property data are the most important ingredients for the

development of thermodynamic models used in such simulators. These mathematical models and

correlations are used to estimate the physical properties of pure components and oil fractions

and/or to predict phase equilibria and physical properties of mixtures such as activity and

fugacity coefficients. These models contain undefined parameters that are determined from

1

experimental data used to determine the model parameters propagate and hence simulation

results are also subject to errors inherited from the original data used to develop the

thermodynamic models.

Currently the basic input properties such as critical properties and acentric factors of pure

components are used in simulators without statistical uncertainty information. These properties

are commonly used as input parameters in thermodynamic models, such as cubic equations of

state, and are extensively used in process and reservoir engineering for the prediction of phase

equilibrium and thermo-physical properties of material streams. Although reliable prediction of

thermodynamic properties relies on the regressed model parameters, the uncertainties of

estimated parameters propagated from the uncertainties in experimental data are traditionally

overlooked in simulators.

In addition to pure components and thermodynamic models, the quality of the binary

interaction parameters used in equations of state to improve their ability to predict the fluid phase

behaviour of mixtures is a key component for the development of statistically meaningful VLE

data. Interaction parameters greatly affect the accuracy of VLE calculations and therefore

estimated equipment performance of separators and distillation columns. Binary interaction

parameters are estimated by data regression using the available experimental binary VLE data.

While uncertainties in VLE data propagate through the estimation procedure to the adjusted

parameters, they are defined in simulators as deterministic inputs and their uncertainties are also

not taken into account.

Avoiding uncertainties in simulators due to lack of statistical information can have

serious consequences, since no qualification of the accuracy of input parameters is known and no

2

information on the way errors in parameters propagate through the computations is provided to

users. Consequently, experience-based risk assessment and safety measures have to be used

without the benefit of a tool to assist in the critical analysis of the quality of the results.

The availability of the uncertainty information associated with the basic properties and all

thermodynamic model parameters was the main reason for the development of a computational

procedure for uncertainty analysis. The final result is an increase in the knowledge of how these

uncertainties propagate through common process calculations, how they affect the estimated

performance and, most important, assist designers in defining equipment overdesign consistently

thus optimizing the process design.

Several previous studies on the uncertainty analysis in the field of process engineering

did not provide a general way to quantitatively determine the associated uncertainties of physical

properties and model parameters but rather determined the uncertainties in an ad-hoc manner

based on the estimated average errors frequently considered as a percentage of the reported

values. Using sources for critically evaluated thermophysical property data developed during the

last decades, some studies were done to quantify the effect of physical property uncertainties on

process design using limited uncertainty information available at that time, such as through the

DIPPR 801 database where pure component uncertainties were roughly estimated based on the

average absolute deviation between reported and calculated physical properties.

Traditionally, critical evaluation of data for a particular chemical system or property

group is a time and resource-consuming process and must be performed far in advance of need.

As a result, a significant part of the existing data has never been evaluated. Moreover, since it is

quite common that significant new data have become available during the data evaluation

project, data analysis and fitting model parameters, such as equations of state models, must be

3

updated in order to provide up-to-date predictions. This type of data evaluation is slow and

inflexible [1].

Recently, the National Institute of Standards and Technology (NIST) developed the first

software in the form of ThermoData Engine (TDE) [2] to: (1) automatically generate

recommended data based on all available, up-to-date experimental data with assigned

uncertainties for pure compounds, binary and ternary mixtures, and reaction systems stored in

the SOURCE electronic database [3, 4]; (2) produce critically evaluated data dynamically or in

order using an automated system when information is required. Dynamic data evaluation

contrasts with the traditional evaluation of data which must be initiated in advance of anticipated

need. The unique feature of this software is that all calculated numerical values include estimates

of uncertainties. In this study, TDE is used as the most comprehensive source of experimental

data and their uncertainties in the "world" for both pure components and binary and ternary

mixtures and allows the determination of not only the model parameters but rather statistically

significant model parameters weighted based on the quality of the physical property data as well

as model parameter uncertainties. The most important aspect of this software and fundamental to

this work is the estimation of uncertainty based on the normal (Gaussian) distribution density

function with a level of confidence of approximately 95%.

After recognizing the uncertainty in the various input variables, a practical method to deal

with the uncertainty propagation arising from complex models is required to analyze and

quantify uncertainty induced from errors in input variables. The Monte Carlo simulation

technique coupled with a sampling method is the most popular and useful computer-based

approach and has been commonly applied in the uncertainty propagation analysis of chemical

plants. This kind of analysis corresponds to the probabilistic approach where all the input

4

variables are characterized by probability distributions representing the full range of possible

values and the uncertainties propagate in the model prediction such that the result is also a

probability distribution. The normal distribution is the most popular probability density function

used for characterized the uncertain variables to represent the uncertainty resulting from

unbiased measurement errors. It is recognized that errors in physical properties are not

necessarily distributed according to a normal distribution since other sources of errors such as

equipment systematic deviations may be present in the data. These are usually not available to

the modeller and therefore considered outside the scope of this study.

In this study, the Monte Carlo simulation was used for the uncertainty propagation

calculations for complex flow sheets. A sample set from the probability distribution of all

uncertain input parameters is generated using an appropriate sampling technique and the values

of the desired equipment or process parameters are repeatedly calculated using different sampled

values of each input variable. The number of samples and the sampling technique are the two

main factors in the sampling process in order to get reliable samples for estimation of output

variables. Examples of these techniques are random Monte Carlo Sampling (MCS) [5] and Latin

Hypercube Sampling (LHS) [6] which are used in this research and will be discussed in the

following chapters.

Several studies of uncertainty analysis applied to the chemical industry emphasized its

importance in process design. However, a comprehensive computational procedure has not yet

been presented to systematically analyze the effect of thermodynamic model parameter

uncertainties on the results of process simulation/design. In this study, this procedure is

developed through the linkage between the TDE derived evaluated physical property database

and the VMGSim process simulator [7] for quantification and analysis of process uncertainties

5

via the Monte Carlo method coupled with nonlinear regression algorithms and sampling

techniques.

1.2 Research Objectives

The main objective of this dissertation is the development a self-contained and consistent

computational procedure to quantify the uncertainties in basic physical properties,

thermodynamic model parameters, and binary interaction parameters and how these uncertainties

affect the calculated thermo-physical properties, material and energy balances, equipment

parameters, and product properties. To achieve this goal, the following specific challenges were

overcome:

and predicted data with associated uncertainties. The database contains the physical

properties (molecular weight, normal boiling temperature, standard liquid density,

standard liquid specific gravity, and vapour pressure), critical properties (critical

temperature and critical pressure) and acentric factor for pure components commonly

present in natural gas. The experimental values and their relevant uncertainties were

taken from TDE version 5.0 [2] , while the predicted values of acentric factor and

standard specific gravity were calculated as part of this work and their uncertainties were

predicted using the principles of error propagation based on the first order Taylor series

linearization.

pseudo-components. The majority of naturally occurring hydrocarbon systems contain

some undefined heavy fractions that are lumped together and identified as the plus

fraction, or are determined using oil assays using distillation curves. In order to predict

the phase behaviour of hydrocarbon systems using a thermodynamic model, the acentric

factor and critical properties of these undefined fractions are required together with

estimated uncertainties. Estimation methods were re-parameterized by taking into

account the uncertainties of both dependent and independent variables, and their

associated variance-covariance matrices of model parameters were provided. These

newly developed estimation methods allow the rigorous estimation of uncertainties in

physical properties of undefined oil fractions.

Re-parameterize equation of state models and provide the uncertainty information related

to model parameters. The availability of uncertainties in the necessary input parameters

required for developing a thermodynamic model makes it possible to re-parameterize the

model and provide variance-covariance matrix of its parameters. While the objective of

this thesis is to provide a method generally applicable to any thermodynamic model,

specific examples will used. A re-parameterized version of the Peng-Robinson equation

of state where its parameters were determined using statistically meaningful vapour

pressures, critical pressures, critical temperatures, and acentric factors will be developed.

The parameters of the corresponding equation of state were determined with their

associated uncertainties.

equilibrium (VLE) data and their uncertainties and perform the thermodynamic

consistency test to check the reliability of the experimental data. The first step in

expanding the thermodynamic model for mixtures is providing the database including the

experimental data of pressures, temperatures, and both liquid and vapour phase

7

consistency of VLE data was checked through the use of the Gibbs-Duhem equation.

Estimate binary interaction parameters and their associated uncertainties. The prediction

of phase and volumetric behaviour of mixtures using equations of state is done through

the use of mixing rules for model parameters. Since the binary interaction parameters are

traditionally determined using the VLE data regression, the uncertainties in the original

data necessarily affect the quality of the estimated parameters. Therefore, the binary

interaction parameters and associated uncertainties have to be determined to meet the

research objective. The re-parameterized Peng-Robinson equation of state was used along

with van der Waals mixing rules with a single adjustable binary interaction parameter and

the interaction parameter associated with its uncertainty was obtained by simultaneously

taking into account the uncertainties in the binary vapourliquid equilibrium data,

physical properties of pure components, and the Peng-Robinson model parameters.

generic flow sheets. The algorithm must be able to propagate the uncertainties from pure

component physical properties and thermodynamic model parameters through all

material balances, energy balances, and equilibrium relationships and provide uncertainty

estimations for the quantities resulting from these process calculations. The computerbased error propagation algorithm must be coupled with chemical plants flow sheets of

any complexity.

This is a paper-based dissertation consisting of five chapters structured as follows. The main

findings of this research study are presented in the next three chapters consisting of published

papers in peer-reviewed journals. There is, therefore, some repetition such as introduction,

mathematical models, and numerical methods. Each chapter presents background information

and a literature review of the principal subjects as well as brief reviews of the pertinent methods.

Chapter 2 focuses on the uncertainties in physical property data of pure components and

their effect on thermodynamic models and process simulation/design. Two estimation models for

characterization of undefined oil fractions and a cubic equation of state are re-parameterized

based on the data and associated uncertainties taken from the developed database for pure

components. In addition, the variance-covariance matrices of model parameters are evaluated. A

version of this chapter was published in the Fluid Phase Equilibria journal [8].

Chapter 3 deals with the binary mixtures and quantification of the uncertainties in

estimated binary interaction parameters propagated from uncertainties in pure components

physical properties, VLE data, and thermodynamic model parameters. The thermodynamic

consistency test is performed for each isothermal VLE dataset in order to determine the quality

of the associated data. A version of this chapter was published in the Fluid Phase Equilibria

journal [9].

Chapter 4 presents the methodology used for the development of a consistent and selfcontained error propagation algorithm and the application of the proposed algorithm is illustrated

through two case studies related to hydrocarbon processing. The first case study is related to

liquid hydrocarbon injection into an existing natural gas pipeline and the second case study is a

gasoline blending process. In both cases, the process conditions are revisited and the safety

9

factors are determined in light of the uncertainty analysis. A version of this chapter has been

published online in the Energy & Fuels journal [10].

Finally, general conclusions and recommendations and suggestions for future studies are

presented in Chapter 5.

10

Design 1. Pure Components 1

2.1 Abstract

A simple model is proposed to estimate the critical temperature and critical pressure of

hydrocarbons in the range of C5C36 with parameters determined using weighted linear least

squares and weighted nonlinear least squares taking into consideration the experimental

uncertainty in the data as well as in the correlating parameters. The correlation model was

parameterized using the normal boiling point and specific gravity at 60 F. The uncertainties of

parameters and associated covariance matrix necessary for error propagation calculations are

reported and a comprehensive evaluation of acentric factors uncertainties based on the

experimental vapour pressures was conducted. In addition, a simple sensitivity analysis designed

to determine how the uncertainty of properties used for calculations based on equations of state

propagate thorough the model and affect the final results. The normal boiling points of two pure

components, n-hexane and n-dodecane were calculated using an equation of state and the

estimated error in the calculations is presented together with estimated uncertainties for the

prototype pressure-temperature envelopes for two binary mixtures of methane/n-hexane and

methane/n-dodecane.

2.2 Introduction

Critical properties and acentric factors are important for prediction of thermodynamic and

physical properties of fluids and commonly used as input parameters in cubic equations of state

Reprinted from Fluid Phase Equilibria, Vol. 307, S. Hajipour, M.A. Satyro, Uncertainty Analysis Applied to

Thermodynamic Models and Process Design 1. Pure Components, 78-94, Copyright (2011), with permission from

Elsevier. It should be noted that the content of this chapter includes the extensions beyond the cited journal paper.

11

such as SoaveRedlichKwong (SRK) [11] and PengRobinson (PR) [12]. These equations of

state are extensively used in process and reservoir engineering and routinely used for the design,

optimization and debottlenecking of industrial facilities via process simulators. Currently

equation of state input values such as critical temperatures and pressures are used in simulators

without statistical uncertainty information. Therefore safety measures such as equipment

overdesign have to be applied in an ad-hoc manner.

The objective of this work is to expand on ideas put forth by Whiting and co-workers

[13-18] in uncertainty analysis of chemical processes through the development of a

comprehensive database of critical parameters, acentric factors, interaction parameters, and

estimation techniques for pure component physical properties and binary interaction parameters,

taking advantage of new uncertainty on fundamental physical property data available now

through NISTs ThermoData Engine (TDE) [2]. A unique feature of this development is related

to the uncertainty information encoded in this new database as well as in estimation methods

necessary for the modelling of pseudo-components used to model complex hydrocarbon fluids.

The availability of uncertainty information associated with all the model parameters

allows us to estimate in a rigorous way what is the uncertainty in values calculated from the

model and put the analysis of the quality of results from a thermodynamic model on solid footing

thus making this important information available to process engineers and assist them in

determining if critical parts of a process being designed require more information before

significant investment is committed or if process conditions must be revisited due to

uncertainties on the state of the process fluid at certain process conditions such as proximity to

the dew point line at the inlet of a compressor.

12

It is well known that small errors in the critical properties used in equations of state affect

the quality of final results, sometimes in a dramatic fashion. For example, the effect of errors in

the critical temperature of different compounds using the PengRobinson equation of state is

shown in Figure 2.1. If the critical temperature is under-estimated by 2% from its accepted value,

errors in vapour pressure between 20 and 60% for several evaluated compounds are obtained.

Note, the deviation curves do not go through the zero-zero point due to the inherent inaccuracy

of the model used for the calculations.

180

n-Hexane

n-Dodecane

140

n-Eicosane

n-Tetracosane

100

60

20

-20

-60

-6

-4

-2

Figure 2.1. Effect of error in the critical temperature on the predicted vapour pressure

using the PengRobinson equation of state for simple paraffins.

There are several studies reported in the literature, for example, Zudkevitch [19],

Zudkevitch and Gray [20], Larsen [21], and Zeck [22], that illustrated the effects of uncertain

thermodynamic data and corresponding effects in the accuracy of models in several specific

13

cases, but these studies did not provide a way to quantitatively determine the uncertainties but

rather associated uncertainties of physical property data in an ad-hoc manner based on the

estimated average errors. Uncertainty analysis in the field of process engineering was studied by

Halemane and Grossmann [23], Diwekar and Rubin [24], Pistikopoulos and Ierapetritou [25] and

Chaudhuri and Diwekar [26].

Notably Whiting and co-workers [13-18] showed the importance of the effect of physical

property inaccuracies on process design. At the time, little quantitative information related to

uncertainty was available and these earlier studies were performed using average uncertainties

estimated for different physical properties such as the evaluations performed by DIPPR (Design

Institute for

collection and correlation by the National Institute of Standards and Technology (NIST) in the

form of the ThermoData Engine (TDE) and the SOURCE database allow now for the

development of databases and correlations that reflect the uncertainty of physical properties and

the determination of not only model parameters but also model parameters weighted based on the

quality of physical property data as well as model parameter uncertainties.

TDE is the first software that implements the concept of dynamic data evaluation to

thermo-physical property data. TDE uses experimental data stored in the TDESOURCE

database, predicted data (obtained through application of several predictive methods), and usersupplied property values for dynamic evaluation process. All experimental properties archived in

the TDESOURCE originate from journals, articles, reports, and theses and it is a subset of the

Thermodynamic Research Centre (TRC) SOURCE, an extensive relational data archival system

for thermo-physical and thermo-chemical properties reported in the scientific literature. The

artificial intelligence (expert-system) software built into TDE automatically generates critically

14

evaluated data on demand through assessment of available experimental and predicted data. The

estimation of uncertainties with a confidence level of 95% for all numerical property values used

in TDE is the most important aspect of this software [1] and is fundamental to this thesis work.

In TDE, it is assumed that the uncertainty of each property of a pure component is

characterized by a normal (Gaussian) distribution. For a confidence level of 95% with the

evaluated true value set as the mean value (), the standard deviation (S) is half of the evaluated

uncertainty. The range of values that each property can take in the 95% confidence interval

would lie in the interval 2S . In this work, the estimated uncertainties are used in a weighted

least squares regression procedure as weighting factors of data points and in the error

propagation procedure. This ensures that the best possible models are developed from statistical

and data quality points of view.

The objective is to develop a carefully evaluated database of pure component properties,

interaction parameters, and parameters used to estimate pure component properties and

interaction parameters for mixtures of interest to the natural gas processing industry together

with the necessary statistical uncertainty information for each piece of information present in the

database. With this information, Monte Carlo techniques are used to evaluate the effect of

physical property uncertainties in process simulation, with the final goal of providing a sound

background for the re-evaluation of process equipment design parameters such as heat transfer

correlations thus bringing us closer to the goal of providing process engineers with better tools to

access the feasibility, quality and safety of new industrial processes or processes being modified

or revamped.

There are dozens of correlations available in the literature to estimate critical properties

[28-40]. These properties often depend on some easily measurable physical properties such as

15

molecular weight, normal boiling point, and standard liquid density (or specific gravity). Lee and

Kesler [35, 36] and Riazi and Daubert [37] proposed models dependent on normal boiling

temperature (used as a crude energy parameter) and specific gravity (used as a crude size

parameter). These simple two-parameter correlations can be applied only to hydrocarbon and

non-polar compounds. Wilson et al. [38] and Brule et al. [39] suggested two-parameter

correlations for coal liquids. Another two-parameter correlation was developed by Twu [40] both

for petroleum and coal liquids. All these correlations involve only the boiling point and the

specific gravity as input parameters. The parameterization using normal boiling point and

specific gravity is of particular importance to the oil industry, since usually only these properties

are available, as a result of an oil characterization procedure and if critical properties, acentric

factors and ideal gas heat capacities can be reliably estimated from these basic properties then a

complete simulation model can be constructed.

The parameters used in these models were obtained from regressions using independent

and dependent variables experimental values. Notwithstanding the usefulness of these estimation

methods, they were presented without uncertainty information, such as uncertainty related to the

dependent variables (in this case critical pressure and temperature), independent variables

(normal boiling point and specific gravity) and model parameter uncertainties. Due to the need to

deal with undefined components present in refining and natural gas systems, there is the need to

redevelop the estimation methods taking into account errors in the dependent and independent

variables, and to present the associated covariance matrix of model parameters for error

propagation calculations.

In this work, the Riazi and Dauberts model [37] and Lee and Keslers model [35, 36]

were chosen to re-evaluate a wide variety of hydrocarbons in the range of C5C36, although the

16

procedure is entirely general and other methods could be used. These models depend on the

normal boiling point and the specific gravity, readily available properties from oil

characterization, for prediction of critical temperature, critical pressure and acentric factor. We

chose the Riazi and Dauberts model due to its simplicity and accuracy in prediction of critical

properties and Lee and Keslers model because of its accuracy in prediction of critical properties

and acentric factors. Both methods are widely used in the hydrocarbon industry. The uncertainty

on normal boiling point and specific gravity were taken into account together with the

uncertainty of critical pressures or temperatures while developing the correlation. To support this

effort a database containing critical temperature (Tc), critical pressure (Pc), normal boiling point

(Tb), and specific gravity (SG) for hydrocarbons associated with their uncertainties was prepared.

2.3 Pure Component Database Development

Re-evaluation of estimation models taking into account the uncertainties required the

development of a database capable of storing all relevant experimental and predicted data

associated with uncertainties. The database contains physical properties (molecular weight,

normal boiling point, standard liquid density, standard liquid specific gravity, and vapour

pressure), critical properties (critical temperature, critical pressure) and acentric factor for 176

pure hydrocarbons in the range of C5C36. The selection of hydrocarbons is based on compounds

commonly present in natural gas with normal boiling points above 290 K. These are necessary to

redevelop estimation models for characterization of undefined oil fraction such as C 7+. The

experimental values of molecular weight (MW), normal boiling point (Tb), standard liquid

density (l), critical temperature (Tc), critical pressure (Pc) and vapour pressure data (Psat) at

reduced temperature (Tr) of 0.7 and their relevant uncertainties were taken from TDE version 5.0

17

[2]. After selecting a compound, TDE was used to gather the experimental data for each property

from the TDESOURCE database and to evaluate these data dynamically using an internal

algorithm [1]. To redevelop the estimation methods, standard specific gravity and acentric factor

data and their uncertainties were required. Since this type of information is not available directly

in TDE, they were specially calculated as part of this work and their predicted values are listed in

the database presented in Appendix A.

2.3.1 Uncertainty on Standard Specific Gravity

The standard specific gravity is defined in Equation 2.1:

SGi

i

H O

2.1

where i and H 2O are the standard liquid density of the selected compound and water at 60 F.

The uncertainty on specific gravity was determined using the standard error propagation

equations, Equations 2.2 and 2.3 [41]:

2

SGi

SGi

i

SG

i

SGi

i

i

2 SGi

i

H O

H 2O

H 2O

2

2

H 2O

2.2

2.3

where SGi is the standard specific gravity uncertainty of the selected component, and i and

H 2O

are the standard liquid density uncertainties of the selected component and water,

respectively.

18

The Pitzer correlation [42], Equation 2.4, was used for calculation of the acentric factor ():

2.4

where Pr and Tr are the reduced pressure and temperature. The acentric factor uncertainty was

calculated from the propagation of the vapour pressure uncertainty using Equation 2.5:

sat Pc

sat P

P ln 10

P

ln

10

2.5

Vapour pressures and critical pressures data associated with their uncertainties are taken

from TDE Version 5.0 [2] in the form of a 5-parameter Wagner equation [43], Equation 2.6:

ln P sat ln Pc

Tc

( A1 A2 1.5 A3 2.5 A4 5 )

T

2.6

where 1 (T Tc ) .

Figures 2.2 to 2.4 show the uncertainty of acentric factor versus vapour pressure at

reduced temperature of 0.7, critical pressure, and critical temperature. The values of the

parameters and their uncertainties were obtained from TDE Version 5.0. In Figures 2.2 and 2.3,

all of the data follow a common trend; however, Figure 2.4 does show three distinct trends for

the acentric factor as a function of the critical temperature. The lower trend line shows the

uncertainty of compounds with two rings in their structures such as naphthalene and 1,1bicyclopentyl, the middle trend line shows the trend for compounds which have one ring in their

structure (aromatic and/or naphthenic) such as benzene and cyclohexene, and the upper trend line

is the trend for the other compounds in the database. This figure indicates that the acentric factor

of a hydrocarbon is a function of its structure. This relationship could be further explored for the

development of better acentric factor correlations.

19

1.8

1.6

1.4

Acentric Factor

1.2

1.0

0.8

0.6

0.4

0.2

0.0

0

40

80

120

160

200

240

Vapour Pressure @ Tr=0.7 (kPa)

280

320

Figure 2.2. Calculated acentric factor associated with uncertainty as a function of vapour

pressure @ Tr=0.7.

1.8

1.6

1.4

Acentric Factor

1.2

1.0

0.8

0.6

0.4

0.2

0.0

0

500

1000

1500

Critical Pressure (kPa)

4000

4500

5000

Figure 2.3. Calculated acentric factor associated with uncertainty as a function of critical

pressure.

20

1.8

1.6

1.4

Acentric Factor

1.2

1.0

0.8

0.6

0.4

0.2

0.0

450

500

550

600

650

700

750

800

850

900

950

Figure 2.4. Calculated acentric factor associated with uncertainty as a function of critical

temperature.

2.4 Development of A New Correlation for Critical Temperature, Critical Pressure and

Acentric Factor Using Uncertainties in Physical Property Data

In this study, the Riazi and Dauberts model (RD) [37] and Lee and Keslers model (LK) [35,

36] were re-evaluated. The Riazi and Daubert method is a simple correlation expressed by the

multiplication of two power functions. Voulgaris et al. [44] did a comparative study of the

accuracy of several calculation methods and recommended the Riazi and Daubert method for the

critical properties and Lee and Kesler method for acentric factor estimation.

Riazi and Daubert [37] proposed a simple two-parameter equations to correlate the critical

temperatures and critical pressures of hydrocarbons in the C5C20 range, Equations 2.7 and 2.8.

Tc 19.06232 Tb0.58848 SG 0.3596

2.7

21

2.8

where Tc is the critical temperature in K, Pc is the critical pressure in kPa, Tb is the normal

boiling point in K, and SG is specific gravity of the liquid at 60 F.

The original Lee and Kesler [35, 36] correlations for critical temperatures, critical

pressures, and acentric factors are as follows:

105

Tc 341.7 811SG (0.4244 0.1174SG)Tb (0.4669 3.2623SG)

Tb

ln Pc 8.3634

0.566

2.2898 0.11857

3

0.24244

10 Tb

2

SG

SG

SG

3.648 0.47227

1.6977

7 2

1.4685

10 10Tb3

10 Tb 0.42019

2

2

SG

SG

SG

2.9

2.10

15.2518 15.6875 Tbr 13.4721ln Tbr 0.4357Tbr6

2.11

1.408 0.01063K w

Tbr

2.12

is the normal boiling point in Rankine, SG is specific gravity of the liquid at 60 F, Tbr and Pbr are

the reduced normal boiling temperature and pressure, respectively, and Kw is the Watson

characterization factor which is a function of the normal boiling point in Rankine and standard

specific gravity, Equation 2.13:

Kw

(1.8 Tb )1 3

SG

2.13

22

In this study, new parameters for the RiaziDaubert (RD) and LeeKesler (LK) models

were recalculated using new data to extend them into the C5C36 range. These correlations can

be written in the general forms shown in Table 2.1. In this table, the dependent variable (a

function of the critical property or acentric factor) is expressed as a function of independent

variables f and a vector of model parameters a . The numerical values of model parameters are

unknown and to be determined using the experimental data of dependent and independent

variables. Linear and nonlinear regressions using the LevenbergMarquardt [45] method were

used to determine the parameters for the different models. In this procedure the uncertainties in

dependent (Tc, Pc or ) and independent variables (Tb and SG) were taken into account.

2.4.1 Computational Approach

The model parameters were estimated using the weighted least squares method, a special case of

the more general maximum likelihood estimation procedure [46]. The method essentially

involves the minimization of an objective function based on the model, model parameters,

experimental data and associated uncertainties of experimental data, Equation 2.14.

n

(a )

2

i 1

1

2

i

i ( f i ; a)2

2.14

where n is the number of selected compounds from the experimental database, i are the

experimental values of dependent variables, ( f i ; a ) are the model variables calculated using the

true parameter values a . i represents the value of the total uncertainty calculated using both

dependent and independent variable uncertainties.

23

Model

General Form

Correlation Structure

RD

Nonlinear form:

( f ; a) a1 f1a f 2a

Tc or Pc

Linear form:

ln Tc or ln Pc

RD

f Tb

( f ; a ) ak f k

6

( f ; a ) ak f k

k 1

10

( f ; a ) ak f k

4

( f ; a)

c ak f k

k 1

a

k 1

k 4

6

( f ; a ) ak f k

k 1

a a1

a2

a3

a a1

a2

... a5

a a1

k 1

LK

SG

a3

ln SG

f 1 SG Tb

ln Pc

24

LK

a2

f 1 ln Tb

Tc

k 1

LK

a a1

fk

a6

a2 ... a9

a2

10 5 SG

Tb

a10

1

f 1

10 3 Tb

SG

c ln Pbr

a a1

10 5

Tb

SG. Tb

... a 7

10 3 Tb

SG

10 3 Tb

SG 2

a8

1

f 1

ln Tbr Tbr6

Tbr

a a1 a 2 ... a5 a6

f 1 K w

K w2 Tbr

1

Tbr

Kw

Tbr

10 7 Tb2

10 7 Tb2

SG

10 7 Tb2

SG 2

10 10 Tb3

10 10 Tb3

SG 2

independent variables are neglected. Since we want to determine model parameters that encode

uncertainty information of dependent and independent variables, this simplification is not

warranted and the procedure proposed by Fornasini [47] is used and briefly described below:

1. As a first step, only the uncertainty of the dependent variable (or the experimental

uncertainty ( i ) exp. ) is taken into account and the approximate values of parameters are

2

obtained by the least squares method with weighting factors set equal to 1 ( i ) exp

. .

2

i2 ( ) exp

.

2.15

uncertainty of the dependent variable of the model by the propagation procedure for each

point. The squared uncertainty of the dependent variable calculated using the error

propagation procedure is shown in Equation 2.16:

m

( i )

2

tra.

j 1

( f ; a )

f

j

f

2.16

where m' is the number of independent variables and ( i ) tra. is the transferred contribution

to the uncertainty of the dependent variable.

3. The squared experimental uncertainty and the squared transferred contributions to the

uncertainty of the dependent variable are then summed for each point.

2

2

i2 ( ) exp

. ( ) tra.

i

2.17

4. The least squares method is again used to estimate the vector of model parameters (a), but in

this step the weighting factors are equal to 1 i2 . Weighting factors are updated using

25

Equations 2.16 and 2.17 with the values of a re-estimated at each iteration. The procedure is

repeated until the sum of the absolute differences between two values of total uncertainties

( i ) in two successive iterations is less than the specified tolerance of 10-8 or some fractional

amount like 10-6.

5. Once acceptable parameters were found using Fornasinis iterative procedure, the probable

uncertainties in the fitted parameters must be estimated. The covariance between two

parameters aj and al, or variance for j=l, is the sum of the variances of each of the data points

( i2 ) multiplied by the effect of each data point has on the determination of each parameter

and by assuming that there are no correlations between uncertainties in the measured

variables i , is given by Equation 2.18.

n

2

a j al

i 1

2

i

a j al

C jl

i i

2.18

The m m symmetric matrix C is commonly known as the covariance matrix or error matrix

where m is the number of fitted parameters. The diagonal elements of matrix C are the

variances (squared uncertainties) associated with estimates of fitted parameters and its offdiagonal elements are covariances between aj and al, Equation 2.19:

a21

C a2l a1

2

ama1

a21al

a2

2

am al

a21am

a2l am

a2m

2.19

6. The parameters associated with their uncertainties are shown in Equation 2.20:

ak Ckk

2.20

26

Now, knowing the uncertainties of all input properties, available model parameters, and

covariance matrix, the squared uncertainty of the calculated dependent variable can be

calculated, Equation 2.21:

2

( )

2

i

( f ; a )

f

j

f

j

j 1

m 1

k 1

( f ; a )

C kk

a

k

2.21

( f ; a ) ( f ; a )

C kl

ak i al i

l k 1

m

k 1

The first term shows the effect of uncertainties of all input properties, the second term

models the influence of the variances of estimated parameters, and the third term indicates

the impact of covariances between two parameters on the uncertainty of the calculated

dependent variable.

An important result of this detailed regression procedure is including input parameter

uncertainties and the ability to estimate the uncertainty of estimated critical properties or acentric

factor as a function of the input variables.

The weighted bias, the percentage weighted average bias, the weighted absolute deviation

(AD), and the percentage weighted average absolute deviation (AAD%) were also calculated in

order to compare the updated models and the original correlations, Equations 2.22 to 2.25.

1

Bias

n

1

AD

n

i 1

i 1

100

Bias %

n

( ( f i ; a ) i )

2.22

( f i ; a) i

2.23

1 ( f i ; a) i

i

i

i 1

2.24

27

100

n

AAD%

1 ( f i ; a) i

i 1

2.25

where i are experimental values of critical properties and acentric factors, ( f i ; a ) are

calculated values of critical properties or acentric factors using the models and the parameter

values developed in this work and i are the corresponding experimental uncertainties.

2.4.1.1 Linear Regression

The general form of the linear functions is shown as Equation 2.26 [41]:

m

a f

( f ; a)

2.26

k 1

of a vector of independent variables as functions of the normal boiling point (Tb) and standard

specific gravity (SG), and a is a vector of unknown model parameters, Table 2.1.

The minimum of the objective function (Equation 2.14) is determined by taking partial

derivatives with respect to each parameter and setting them to zero, Equation 2.27:

2

2

ak

i 1

1

2

j 1

a j ( f j ) i ( f k ) i 0

2.27

n

i 1

( f k )i

2 i

a j

j 1

i 1

(

f

)

(

f

)

j i

k i

2

i

2.28

A set of simultaneous linear equations for parameters al can then be expressed in matrix

form, Equation 2.29:

28

aU

2.29

where the matrix a is a row matrix of parameters to fit and the elements of matrix and

symmetric matrix U are defined by Equations 2.30 and 2.31:

i 1

U jk

i 1

2

i

i ( f k )i

2.30

1

1 2 2

(

f

)

(

f

)

2 j i k i

i

2 a j a k

2.31

By multiplying both sides of the Equation 2.29 by the inverse of matrix U ( U 1 ), the

parameter matrix a is obtained as:

m

aj

( k kj )

k 1

jk

k 1

i 1

2 i ( f k )i

i

2.32

The covariance of two parameters a j and al , or variance for j l , using Equation 2.18 is

given by:

n

2

a j al

2

i

i 1

k 1

1

jk 2 ( f k ) i

i

p 1

(

f

)

lp 2 p i jl

i

2.33

The covariance matrix C in a linear regression is the inverse of the symmetric matrix U .

The squared uncertainty of the calculated dependent variable can be calculated using

Equation 2.21 and can be expressed as Equation 2.34:

a f

m

( )

2

i

k 1

m 1

2

k i

fk i

k 1

kk

f f

k i

k 1 l k 1

29

l i

kl

2.34

In this study, the procedure was repeated using a nonlinear regression. The Levenberg

Marquardt [45], as suggested by Press et al. [48], used a general nonlinear form of each model

for each property, Table 2.1. With a nonlinear model the minimization must proceed iteratively

using a selected minimization algorithm. In this study, the LevenbergMarquardt [45]

minimization method was used. It is an elegant technique that combines advantages of the

GaussNewton [46] method for solving a set of linear system of equations and the steepest

descent method [46]. This method inherits its accelerated convergence near the minimum from

the GaussNewton iteration method and derives its stability from the steepest descent method.

Given an initial guess for the parameter vector a , a procedure is developed that improves

the trial solution. The procedure is then repeated until 2 , Equation 2.14, stops decreasing. The

total uncertainty for each point is updated in each iteration using Equation 2.17.

The gradient of 2 with respect to the parameters a will be zero at the 2 minimum. In

the Levenberg-Marquardt method, described by Press et al. [48], the following formulae are

used to define the components of matrix , equal to minus one-half times the Gradient matrix,

and matrix U whose components are equal to one-half times the first-derivative terms of the

components of the Hessian matrix, Equations 2.35 and 2.36:

U jk

1 2

2 ak

i 1

1 2 2

2 a j ak

2

i

i 1

i ( f i ;a) ( f i ;a)

ak

2 ( f i ;a )

1 ( f i ;a ) ( f i ;a )

(

f

;

a

)

i

i

ak

a j ak

i2 a j

30

2.35

2.36

Equation 2.36 can be written as Equation 2.37 by ignoring the second partial derivative.

Firstly, this term is small enough to be negligible when compared to the first derivative term.

Secondly, the factor in the second derivative term representing the error of measured value from

the calculated value, i ( f i ;a), can have either sign, so the second term tends to cancel when

summed over i.

1 ( f i ;a ) ( f i ;a )

j

k

i

U jk

i 1

2.37

The basis of the method to find the parameters a is that when the current estimated

parameter vector ( a current ) is far from the a next , then the steepest descent method is best and when

a current is close to a next , then Gauss-Newton method is best. So, a new matrix, U , is defined by

Equation 2.38:

U jj U jj (1 )

U jk U jk

2.38

( j k)

two methods, steepest descent and Gauss-Newton. When is very large the diagonal elements of

the matrix U dominate, so the method becomes identical to the steepest descent method. On the

other hand, if is very small, the method becomes more Gauss-Newton like. A value equal to

0.001 was assumed for the first iteration for . To determine the parameters, the following set of

linear equations must be solved for the increments a j that, added to the current approximation,

provide the next approximation ( a a next acurrent ) , Equations 2.39 and 2.40:

m

a U

j

jk

2.39

i 1

31

a (U ) 1

2.40

value of is increased by a factor of 10 to follow the gradient more closely and Equation 2.40 is

solved and the procedure is repeated. On the other hand, if 2 (a a) 2 (a) , the value of

is decreased by a factor of 10 to reduce the influence of gradient and the trial solution for the

parameters is updated, ( a next acurrent a ), and the procedure is repeated by solving the

Equation 2.40. The iterative procedure stops when 2 decreases by a negligible amount, say10-6.

When the minimum of 2 was determined, the inverse of matrix U is computed by

setting 0 . As approaches zero, U U and U 1 is the estimated covariance matrix of the

errors in the fitted parameters a :

C U 1

2.41

After determining the parameters and covariance matrix of the errors for the fitted

parameters, the squared uncertainty associated with the calculated dependent variable is given

by Equation 2.21.

2.4.2 Results and Discussion

Table 2.2 shows the fitted parameters for critical temperature, critical pressure, acentric factor,

their uncertainties, and their covariance matrices for the re-evaluated RiaziDaubert correlations.

Tables 2.3 to 2.5 show the estimated parameters and the uncertainties for the re-parameterized

LeeKesler correlations and the covariance matrices for the critical temperature, critical

pressure, and acentric factor, respectively.

32

Table 2.2. Fitted parameters and covariance matrices for new RiaziDaubert correlations

obtained from nonlinear regression.

( f ; a) a1Tba SG a

Parameters

Covariance matrix

Critical Pressure (kPa)

Parameters

2.6209 10 3

C 2.6077 10 5

1.6977 10 5

9.7184 10

C 6.5273 10 5

5.3041 10 5

15

Covariance matrix

2.6077 10 5

2.5991 10 7

1.5933 10 7

1.6977 10 5

1.5933 10 7

3.3350 10 7

6.5273 10 5

4.3968 10 5

3.3286 10 5

5.3041 10 5

3.3286 10 5

7.6218 10 5

Table 2.3. Fitted parameters and covariance matrix for the re-parameterized LeeKesler

correlation for critical temperature.

Critical Temperature (R)

Parameters, a :

377.31 125.00 1788.12 165.04 1.05 0.09 0.73 0.12 2.30 0.43 5.74 0.57

Covariance matrix, C :

1.5625 10 4

4

2.0535 10

1.1350 10 1

1

1.4860 10

5.3167 10 1

1

7.0143 10

2.0535 10 4

2.7238 10 4

1.4866 10 1

1.9638 10 1

7.0132 10 1

9.3411 10 1

1.1350 10 1

1.4866 10 1

8.2964 10 3

1.0825 10 2

3.8387 10 2

5.0468 10 2

1.4860 10 1

1.9638 10 1

1.0825 10 2

1.4249 10 2

5.0438 10 2

6.6928 10 2

33

5.3167 10 1

7.0132 10 1

3.8387 10 2

5.0438 10 2

1.8203 10 1

2.4108 10 1

7.0143 10 1

9.3411 10 1

5.0468 10 2

6.6928 10 2

2.4108 10 1

3.2242 10 1

Table 2.4. Fitted parameters and covariance matrix for the re-parameterized LeeKesler correlation for critical pressure.

Critical Pressure (psia)

Parameters, a :

25.9 30.5

27.3 23.6 98.9 101.5 54.99 63.03 20.9 14.5 989.5 1098.5 242.5 460.2 434.7 356.8 350.4 371.9 221.6 230.4

Covariance matrix, C :

34

2

5.5803 10 2

2.3736 10 3

7.1847 10

3.0594 10 3

2.3736 10 3

1.0307 10 4

3

1.4260 10 3 6.2893 10 3

1.8172 10

2

4.2371 10

3.2734 10 2 1.3389 10 3

4

2.5137 10 4 1.1075 10 5

3.2277 10

1.1143 10 4

8.8646 10 3

4.0981 10 4

1.0733 10 4

8.3627 10 3

3.5262 10 4

4

3

8.5349 10

3.7490 10 4

1.0970 10

6.6075 10 3 5.2059 10 3 2.2835 10 4

1.8172 103

1.4260 10 3

4.2371 102

3.2277 104

2

3.2734 10

2.5137 10 4

6.2893 10 3

3.9729 10 3

7.6370 10 2

1.3389 10 3

7.6370 10 2

2.1030 10 2

1.1143 104

8.8646 10 3

1.0733 104

8.3627 10 3

1.0970 104

8.5349 10 3

1.1075 10 5

4.0981 10 4

3.5262 10 4

3.7490 10 4

6.8823 10 4 2.7449 10 4 2.1071 10 4 2.3155 10 4

1.3729 10 4 4.1391 10 3 5.0310 10 3 4.7312 10 3

6.8823 10 4

1.3729 10 4

1.2066 10 6 4.6722 10 5 3.7232 10 5 4.0774 10 5

2.7449 10 4 4.1391 10 3 4.6722 10 5

2.1177 10 5

1.2824 10 5

1.5555 10 5

2.1071 10 4 5.0310 10 3 3.7232 10 5

1.2824 10 5

1.2729 10 5

1.2723 10 5

4

3

5

5

5

2.3155 10

4.7312 10

4.0774 10

1.5555 10

1.2723 10

1.3829 10 5

1.4412 10 4

2.8482 10 3

2.5023 10 5

9.9061 10 4

7.8054 10 4 8.4684 10 4

6.6075 103

5.2059 10 3

2.2835 10 4

1.4412 10 4

2.8482 10 3

2.5023 10 5

9.9061 10 4

7.8054 10 4

8.4684 10 4

5.3081 10 4

Table 2.5. Fitted parameters and covariance matrix for the re-parameterized LeeKesler correlation for acentric factor.

Acentric Factor

Parameters, a :

25.7 141.9

34.7 209.4 54.3 393.5 18.9 151.1 54.8 507.5 65.0 593.4 88.9 927.4 3.4 101.1

Covariance matrix, C :

35

2.0135 10 4

4

2.9640 10

5.5504 10 4

4

2.0667 10

4.4496 10 4

4

4.985110

7.4655 10 4

3.6115 10 2

2.9640 10 4

4.3826 10 4

8.2299 10 4

5.5504 10 4

8.2299 10 4

1.5483 10 5

2.0667 10 4

3.0978 10 4

5.8667 10 4

4.4496 10 4

7.0750 10 4

1.3891 10 5

4.9851 10 4

7.9689 10 4

1.5694 10 5

7.4655 10 4

1.2000 10 5

2.3704 10 5

3.0978 10 4

7.0750 10 4

7.9689 10 4

5.8667 10 4

1.3891 10 5

1.5694 10 5

2.2836 10 4

6.0162 10 4

6.8613 10 4

6.0162 10 4

2.5758 10 5

3.0097 10 5

6.8613 10 4

3.0097 10 5

3.5212 10 5

1.0465 10 5

4.6952 10 5

5.4999 10 5

1.2000 10 5

1.8325 10 3

2.3704 10 5

5.0198 10 3

1.0465 10 5

3.9865 10 3

4.6952 10 5

4.0693 10 4

5.4999 10 5

4.8802 10 4

8.6014 10 5

7.7987 10 4

3.6115 10 2

1.8325 10 3

5.0198 10 3

3.9865 10 3

4.0693 10 4

4.8802 10 4

7.7987 10 4

1.0225 10 4

Parameters, a :

458.1 78937.6

Covariance matrix, C :

68.5 11551.2 1.6 292.1 94.2 14347.0 217.5 33724.7 21.9 3303.2

6.2312 10 9 9.0931 10 8

2.3000 10 7

1.0414 10 9 2.6397 10 9

2.5656 10 8

8

1.3343 10 8 3.3674 10 6 1.5657 10 8

3.8698 10 8 3.7820 10 7

9.0931 10

2.3000 10 7 3.3674 10 6

8.5350 10 4

3.8838 10 6 9.7048 10 6

9.4617 10 5

9

1.5657 10 8

3.8838 10 6

2.0584 10 8 4.5885 10 8

4.5935 10 7

1.0414 10

2.6397 10 9

3.8698 10 8 9.7048 10 6 4.5885 10 8

1.1374 10 9 1.1109 10 8

8

3.7820 10 7

9.4617 10 5

4.5935 10 7 1.1109 10 8

1.0911 10 7

2.5656 10

Table 2.6 shows the values of the weighted bias, the percentage weighted average bias,

the weighted absolute deviation (AD), and the percentage weighted average absolute deviation

(AAD %) for each model and each property when the uncertainties of the independent variables

(functions of normal boiling point and specific gravity) are taken into account.

Property

Acentric factor ()

Model

Bias

AD

Bias%

AAD%

RD

8.62 (K)

15.29 (K)

1.56

2.63

New RD

2.39 (K)

13.37 (K)

0.47

2.28

LK

7.84 (K)

13.70 (K)

1.35

2.32

New LK

3.76 (K)

13.62 (K)

0.67

2.27

RD

0.16 (kPa)

3.42 (kPa)

0.03

0.14

New RD

0.04 (kPa)

3.25 (kPa)

0.04

0.14

LK

1.53 (kPa)

3.23 (kPa)

0.07

0.13

New LK

2.03 (kPa)

3.52 (kPa)

0.11

0.16

LK

0.18

0.37

78.18

110.29

New LK

0.03

0.13

7.88

34.58

For critical temperature, the new and original versions of the RiaziDaubert and Lee

Kesler models show approximately similar AAD% values while for critical pressure, the reparameterized LeeKesler model presents a greater AAD% value in comparison with the other

correlations. Since the uncertainties of critical pressures and also independent variables, which

are functions of normal boiling point and specific gravity, are taken into account in the least

square method as weighting factors, the greater uncertainty leads to smaller weighting factor for

some points. This data with greater uncertainty had a decreased importance in model parameters

determination.

36

For the acentric factor, the new LeeKesler model had a smaller AAD% value than the

original LeeKesler correlation. The re-parameterized models for critical properties and acentric

factors are of similar quality when compared to the original models but now encode the

uncertainty of each independent variable and can be used for more advanced statistical analyses.

It is useful to note the uncertainties of specific gravity and normal boiling point as shown

in Figure 2.5. This figure shows the uncertainties in specific gravity using vertical error bars and

uncertainties in the normal boiling point using horizontal error bars for each hydrocarbon.

1.3

1.2

Specific Gravity

1.1

1.0

0.9

0.8

0.7

0.6

0.5

250

300

350

400

450

500

550

600

650

700

750

800

Tb=59235 K and SG=0.990.03, 1-nonadecene (C19H38) with Tb=60416 K and

SG=0.7950.004, and 1-eicosene (C20H40) with Tb=62015 K and SG=0.8270.025 have the

highest uncertainties in the experimental values of the normal boiling point, respectively. On the

37

(C12H18) with SG=0.9110.091 and Tb=540.93.2 K, and 1,2,4,5-tetrakis(1-methylethyl)benzene

(C18H30) with SG=0.8560.085 and Tb=533.950.02 K have the highest uncertainties in the

experimental values of their standard specific gravity. This figure is a complementary figure for

Figures 2.6 to 2.8.

The comparison between the results of the re-evaluated Riazi and Dauberts model with

original one is shown in Figure 2.6 for the critical temperatures and in Figure 2.7 for the critical

pressures. The figures show the critical properties as a function of the normal boiling point. The

horizontal error bar refers to normal boiling point uncertainty and the vertical error bar indicates

the uncertainty of experimental value of the critical property. As shown in the figures for both

critical temperatures and pressures, the new correlations estimate the critical values very well,

specifically for hydrocarbons with normal boiling points up to about 660 K. Note, the results of

the updated correlation are similar to RiaziDauberts model and the deviation between predicted

value and experimental data are negligible for the entire range, but for high boiling point

components the deviation did increase. This occurs because a more rigorous regression takes

place for the lower boiling point compounds due to the smaller uncertainties.

Figure

2.6

shows

that

3,7,7-trimethyl-bicyclo[4.1.0]hep-3-ene

(C10H16)

with

Tb=657.011.39 K have the largest uncertainties for experimental values of critical temperature.

Similarly, as shown in Figure 2.7, 3,7,7-trimethyl-bicyclo[4.1.0]hep-3-ene (C10H16) with

Pc=2967876 kPa, and 2,3-dimethyl-1-pentene (C7H14) with Pc=2856795 kPa and

Tb=357.41.5 K have the highest values of critical pressure uncertainties.

38

1000

Exp.

New RD

900

RD

800

700

600

500

400

250

300

350

400

450

500

550

600

650

700

750

800

6000

Exp.

New RD

5000

RD

4000

3000

2000

1000

0

250

300

350

400

450

500

550

600

650

700

39

750

800

To compare the re-evaluated Lee and Kesler correlation for acentric factor with the

original one, the calculated acentric factor values were plotted against the normal boiling points

in Figure 2.8. Figure 2.8 shows that the updated model and original one predict approximately

the same values for compounds with lower boiling points, while the updated model estimates the

acentric factor of higher boilers more accurately than the original LeeKesler correlation. As

shown in Figure 2.8, 1,1-methylenebis[(1-methylethyl)benzene] (C19H24) with =0.5000.435,

1-eicosene (C20H40) with =0.8810.222, and 1-nonadecene (C19H38) with =0.8770.217 have

the largest acentric factor uncertainties.

1.8

Exp.

1.6

New LK

1.4

LK

Acentric Factor

1.2

1.0

0.8

0.6

0.4

0.2

0.0

250

300

350

400

450

500

550

600

650

700

40

750

800

2.4.2.1 Examples

The application of the updated correlations for the calculation of critical properties and acentric

factors and their associated uncertainties is illustrated through two examples. In the first

example, the critical temperature of a C7+ fraction with a normal boiling point of 508.20.5 K

and specific gravity of 0.82590.001 was calculated using the Riazi and Daubert nonlinear

model, as described in Table 2.1, with the fitted parameters from Table 2.2. The critical

temperature uncertainty can be determined by using the covariance matrix for this model, also

shown in Table 2.2 and in Equation 2.21. The critical temperature for this oil fraction was

calculated to be 696.50.5 K.

In the second example, the critical temperatures, critical pressures and acentric factors of

n-hexane and n-dodecane and their associated uncertainties were calculated using the updated

Lee and Kesler correlations. Note, for components with available experimental data and

uncertainties, the experimental values of critical properties were used to calculate the acentric

factor using the Lee and Kesler correlation, Table 2.1. For oil fractions usually only the normal

boiling point and standard gravity are available from oil characterization and all properties are

functions of these two parameters. The results were summarized in Table 2.7.

Table 2.7. Comparison of the experimental and calculated critical properties and acentric

factors of n-hexane and n-dodecane.

Tc (K)

Pc (kPa)

n-Hexane

Experimental

Calculated

507.53 0.14

509.08 0.33

3031.18 32.39

2861.50 182.27

0.301 0.005

0.301 0.020

n-Dodecane

Experimental

Calculated

658.28 0.59

658.69 0.47

1812.40 87.20

1787.4 186.0

0.572 0.021

0.571 0.072

Compound

41

Properties

The uncertainties associated with basic thermo-physical properties such as critical temperatures,

critical pressures, and acentric factors affect the quality of results calculated using equations of

state for boiling points, densities, enthalpies, and phase equilibria. To quantify thermodynamic

model uncertainties, Monte Carlo type techniques [16] can be used to propagate input

uncertainties into result uncertainties. In order to use this method and estimate the effect of input

uncertainties on the thermo-physical property of interest, specifying uncertain inputs, the Monte

Carlo technique and sampling method will be explained in following sections. Then, one simple

example was chosen to illustrate how this method works.

2.5.1 Notes on the Uncertainty of Input Variables

Critical temperature, critical pressure and vapour pressure data and their associated uncertainties

are taken from the developed database. It is assumed that the pure component uncertainty values

used in the model development are characterized by normal (Gaussian) distributions, the same

assumption that is used to develop the uncertainties in TDE. The mean values ( ) for a certain

physical property would be equal to the evaluated true values in TDE and the 95% confidence

level used in TDE corresponds to a confidence interval bound by 2S. The standard deviation

(S) is then one half of calculated uncertainties.

2.5.2 The Monte Carlo Technique and Sampling

Monte Carlo methods are useful tools for uncertainty propagation analysis by performing

random sampling from probability distributions [5] for complex models. In our case we are

interested in determining the uncertainties of variables derived from process flow sheeting

42

calculations. The use of Taylor based linearization is cumbersome to say the least, except for the

simplest models.

Thus a lottery is constructed where the values of the physical property of interest are

calculated using the process model, for example saturation temperatures or compressor horse

power are repeatedly calculated using different values for the input thermodynamic model such

as critical temperature, critical pressure, and acentric factor, assuming that they are randomly

distributed over the range of their uncertainties. This is a significant assumption since the

distribution of experimental data does not necessarily have to be Gaussian, but it is the most

reasonable assumption that can be made.

Commonly used sampling techniques associated with the Monte Carlo method are

random Monte Carlo sampling (MCS) [5], Latin Hypercube sampling (LHS) [6], Shifted

Hammersley sampling (SHS) [49], and Equal Probability sampling (EPS) [16]. In this study, the

traditional random Monte Carlo sampling, in which the samples are taken at random within the

whole range of distribution of variables, was used to determine the effect of sample size on the

estimation of property uncertainty. The development of guidelines for sampling size is an

important feature for the use of this technique in process quality assurance and is explored

briefly using the calculation of the normal boiling point of simple compounds using the Peng

Robinson equation of state [12].

Three sets of numerical experiments were selected, with 100, 1,000, and 10,000 samples.

For each sample set, the results for the calculated normal boiling point are the mean value and

the quantified uncertainty. Finally, the results obtained for each set are compared.

The PengRobinson equation of state was used for the calculation of normal boiling point

for n-hexane and n-dodecane with physical properties and uncertainties shown in Table 2.7. The

43

input variables are critical temperature, critical pressure, and acentric factor for each component

and the assumed random values based on the Gaussian distribution with defined average and

standard deviation (half of the associated uncertainty) as shown in Table 2.7. Figure 2.9 shows

the assumed probability distributions for the critical temperature for the two components. The

same distribution was also used for the critical pressures and acentric factors.

1.6

(a)

6.0

4.0

2.0

0.0

507.35

(b)

1.2

0.8

0.4

0.0

657.6

507.45

507.55

507.65

Critical Temperature (K)

658

658.4

658.8

Critical Temperature (K)

Figure 2.9. Critical temperature normal distributions for (a) n-hexane (b) n-dodecane.

Three sets of samples with 100, 1,000, and 10,000 random values for each of the three

parameters were prepared. For each of these values the normal boiling point is calculated using

the PengRobinson equation of state and Soaves iteration free saturation calculation method

[50]. The mean value and the standard deviation were calculated using Equations 2.42 and 2.43

where n' is the size of the sample.

1

Tb

n

2.42

bi

i 1

1

STb

n 1

bi

Tb

2.43

i 1

44

Results for each sample size and each component are presented in Table 2.8 along with

their standard deviations. The results can be analyzed in two different views: compare with the

experimental values and compare the results calculated for each sample size. Firstly, comparison

the results with the values from the prepared database (Appendix A) shows that the calculated

mean values using the PengRobinson equation of state are close to the experimental values

(341.850.11 K for n-Hexane and 489.450.12 K for n-Dodecane), but the estimated

uncertainties are greater than the experimental ones.

Secondly, based on this sampling study it seems that relatively small samples can be used

to provide acceptable uncertainty estimates for values calculated from complex models. This

issue is can be further investigated to develop a more comprehensive set of sample size criteria

using a rigorous statistical approach.

No. of Samples

Mean Value

(K)

Range (Min-Max)

(K)

(K)

(K)

n' = 100

341.930

341.253 342.529

0.297

0.594

n' = 1,000

341.938

341.146 342.710

0.318

0.636

n' = 10,000

341.940

341.136 342.779

0.316

0.633

n' = 100

488.886

485.648 491.610

1.366

2.732

n' = 1,000

488.930

485.291 492.445

1.476

2.952

n' = 10,000

488.946

485.233 492.824

1.476

2.952

n-Hexane

n-Dodecane

45

With available uncertainties for the necessary input parameters required to develop a cubic

equation of state, namely critical temperature, critical pressure, vapour pressure and acentric

factor combined with the necessary uncertainties for the physical properties, it is now possible to

re-parameterize an equation of state that will then provide uncertainty information when used in

process simulations. Note, in order to develop an equation of state suitable for technical

applications in the hydrocarbon industry, it is necessary to provide estimation methods for

pseudo-components or plus fractions as presented earlier in this study. Due to its popularity,

the PengRobinson equation of state was chosen, although any other equation could have been

selected.

The most important physical property from a process simulation point of view is the

vapour pressure, and the same formulation as proposed in the original Peng and Robinson paper

was used, based on Soaves form, Equation 2.37:

PR 1 f 1 Tr

2.44

where f was defined as an equation with three parameters in the original form of Peng

Robinson equation of state and presented as equation with four parameters in their improved

version of the equation of state for a pure component with acentric factor above 0.491 in 1978

[51].

The parameters were determined by minimizing the error between the estimated and

experimental vapour pressures, calculated by Soave method [50] from the normal boiling point

to the critical temperature using twenty equally spaced points. All input parameters critical

temperature, critical pressure and vapour pressure are used in the regression taking into account

46

their uncertainties. The same procedure was used to find the parameters and their uncertainties

for both of these equations for all the hydrocarbons in the database. Table 2.9 shows the

equations and results for the original and the improved PengRobinson equations of state.

Table 2.9. Peng-Robinson equation of state refitted parameters and covariance matrix.

f a1 a2 a3 2

Parameters

Covariance matrix

1.2268 10 5

C 6.8363 10 5

8.8538 10 5

6.8363 10 5

3.9476 10 4

5.3088 10 4

8.8538 10 5

5.3088 10 4

7.4825 10 4

f a1 a2 a3 2 a4 3

Parameters

Covariance matrix

4.2173 10 5

3.0845 10 4

C

6.8038 10 4

4

4.3979 10

3.0845 10 4

2.3231 10 3

5.2871 10 3

6.8038 10 4

5.2871 10 3

1.2486 10 2

3.5364 10 3

8.7336 10 3

4.3979 10 4

3.5364 10 3

8.7336 10 3

6.5048 10 3

In order to compare the three-parameter equation and four-parameter equation with the

original PR equation of state, the values of the weighted bias, the percentage weighted average

bias, the weighted absolute deviation (AD), and the percentage weighted average absolute

deviation (AAD %) for vapour pressure were calculated. The results are presented in Table 2.10.

Table 2.10. Comparison results of the original PR equation and the refitted equations.

Model

Original three-parameter PR

0.51

1.59

0.12

0.68

Re-parameterized three-parameter PR

0.15

1.26

0.31

0.52

Re-parameterized four-parameter PR

0.14

1.26

0.30

0.52

47

The original and the improved PengRobinson equation of state show similar values for

the calculated vapour pressures; however, the AAD% values for the re-parameterized equations

are lower than those of the original equation. Both of the re-parameterized equations can be used

to calculate the vapour pressure and associated uncertainty. Figure 2.10 demonstrates the quality

of the predictions of the vapour pressure.

5000

Experimental

4500

Methane

= 0.0116

4000

From four-parameter equation

3500

n-Hexane

= 0.3009

3000

2500

n-Dodecane

= 0.5715

2000

1500

1000

500

0

100

200

300

400

500

Temperature (K)

600

700

Figure 2.10. Comparison of vapour pressure calculated using the original and the

improved PengRobinson equations of state.

The uncertainty values calculated using the covariance-based approach for the 3parameter PengRobinson equation of state are shown in Appendix B for methane, n-hexane,

and n-dodecane. Typical uncertainty values calculated using both versions of the reparameterized equation of state for each of the components at one temperature are shown in

Table 2.11.

48

In order to compare the covariance-based approach with the Monte Carlo simulation, the

vapour pressure calculation was performed using the Monte Carlo method with a sample of

1,000 points which are selected using Latin Hypercube Sampling (LHS) technique [6]. Each data

set contains critical temperature, critical pressure, acentric factor and the calculated parameters

of the re-parameterized PengRobinson equation of state. Table 2.11 shows that the results of

covariance-based approach and the Monte Carlo simulation are basically the same. So, the

Monte Carlo simulation was selected for this study as an efficient error propagation algorithm to

evaluate the uncertainty in physical properties calculations.

Table 2.11. Comparison of vapour pressure and its uncertainty calculated using the

covariance-based approach and the Monte Carlo simulation.

Model

Covariance-Based

Monte Carlo

Component @ T(K)

Three-parameter PR

Methane @ 153 K

1183.3 4.8

1183.3 4.4

n-Hexane @ 432.4 K

902.1 10.6

902.1 10.2

n-Dodecane @ 580.94 K

601.3 30.5

601.4 27.5

Methane @ 153 K

1195.1 7.1

1195.1 6.6

n-Hexane @ 432.4 K

901.9 10.6

901.9 13.0

n-Dodecane @ 580.94 K

601.8 30.5

601.9 28.7

Four-parameter PR

In this section we examine the use of the data and techniques developed in this study using two

simple but representative examples in natural gas processing. In both cases we wish to compress

10 Million Standard Cubic Feet per Day (MMSCFD) lean natural gas from 2068.43 kPa (300

49

psia) to 6205.28 kPa (900 psia) using a single stage ideal compressor. The gas enters the

compressor at 25 C and the intercooler has a pressure drop of 68.95 kPa (10 psia) with a

specified outlet temperature of 48.9 C.

Two gas compositions were used, one with 0.999 methane and 0.001 n-hexane

(Composition 1) and another with 0.99999 methane and 0.00001 n-dodecane (Composition 2).

The results are summarized in Tables 2.12 and show the locations of the critical point,

cricondenbar, and cricondentherm on the pressure-temperature envelope for each composition.

The cricondenbar indicates the maximum pressure on the two-phase boundary at which liquid

and vapour can coexist in equilibrium and is located on the on the highest point of the phase

envelope. The farthest point to the right on the pressure-temperature envelope indicates the

cricondentherm that is the lowest temperature above which hydrocarbon can exist in a vapour

phase alone.

compressing lean natural gas prototype mixtures.

Critical Point

Cricondenbar

Cricondentherm

4777 9 (kPa)

6530 43 (kPa)

2710 11 (kPa)

4620 20 (kPa)

1930 40 (kPa)

Composition 1

Composition 2

Table 2.13 shows the basic information for the compressor and intercooler and

corresponding uncertainties propagated from the uncertainties of pure component critical

properties and acentric factors.

50

Table 2.13. Basic equipment performance data estimated using uncertainty information.

Temperature after

Compressor, K

Compressor Horse

Power, HP

Intercooler Duty,

kJ/h

Composition 1

383.55 0.01

553.2 0.1

1,325,500 400

Composition 2

383.78 0.01

553.7 0.1

1,325,800 400

The gas compositions were chosen to illustrate the effect of a heavy trace component that

may be present in the natural gas. In this case, the uncertainty introduced in the basic energy and

entropy balances as demonstrated by the intercooler duty, compressor horse power and

compressor outlet temperature are negligible, while the position of the cricondenbar and

cricondentherm present significantly more uncertainty as the model component for the natural

gas heavy fraction moves from n-hexane to n-dodecane. Of particular importance is the

uncertainty of the position of the cricondentherm and its effect on the selection of intercooler

operating temperatures to ensure proper compressor operation. It is important to stress that these

uncertainties are related to thermodynamics alone and a complete picture of the problem can

only be established by taking into account the uncertainties of measured inputs such as flows,

temperatures and pressures as well as uncertainties related to equipment such as heat transfer

coefficients and compressor efficiencies.

Figures 2.11 and 2.12 show the pressuretemperature envelopes for two compositions

(Composition 1 and Composition 2) with the uncertainty region calculated using the Monte

Carlo technique. The position of the cricondenbar and cricondentherm present significantly more

uncertainty as the natural gas heavy fraction moves from n-hexane to n-dodecane. The presented

uncertainties are related only the critical pressure, critical temperature and acentric factor

uncertainties.

51

7000

6000

Pressure (kPa)

5000

4000

3000

2000

1000

0

120

140

160

180

200

Temperature (K)

220

240

9000

8000

Pressure (kPa)

7000

6000

5000

4000

3000

2000

1000

0

120

140

160

180

200

220

Temperature (K)

240

260

280

300

52

2.8 Conclusions

A comprehensive database for physical properties of simple hydrocarbons with uncertainties was

developed based on NISTs TDE dynamic evaluation system. The database includes data and

uncertainties for critical properties and acentric factors, fundamental to the development of

models important for the hydrocarbon industry and the estimation of uncertainties related to oil

fractions.

The Riazi and Daubert, and Lee and Kesler correlations were re-evaluated using the

database developed in this work and new correlations were presented to predict the critical

temperature, critical pressure, and acentric factor of pure hydrocarbons in the C5C36 range.

Model parameters were determined using linear and nonlinear regression methods. The main

advantage of these correlations over the original correlations is their ability to estimate the

uncertainties of critical properties and acentric factors based on the uncertainty of the input

variables (normal boiling point and specific gravity). The parameters of these models were

obtained using the weighted least squares method taking into account the uncertainties of both

dependent and independent variables. The covariance matrix or error matrix was reported for

each model. Using this matrix and the standard error propagation procedures, the critical

properties and acentric factor uncertainties can be predicted for individual compounds or oil

fractions. These re-parameterized correlations can be used in thermodynamic models developed

for the natural gas and refining industries with minimal modifications to existing computer code

and provide estimates for the uncertainty of calculated physical properties. In turn these

uncertainties can be used to estimate uncertainties in process equipment hardware such as sizes

of separators, number or diameter of distillation trays, heat exchanger areas, or compressor horse

power.

53

The Monte Carlo technique can be used to evaluate the error propagation from

uncertainties in input variables of an equation of state to an estimated thermo-physical property

of interest. The Monte Carlo method is general and although computer intensive, can be used to

estimate the uncertainty derived from physical properties and corresponding thermodynamic

models for simulations of unlimited complexity. This was illustrated through estimates of the

uncertainties for boiling point calculations using the PengRobinson equation of state, a PT

envelope for a model natural gas mixture and compressor horse power.

A brief study of sample size in the Monte Carlo method was conducted, suggesting that

relatively small sample sizes in the order of 100 randomly distributed inputs may be adequate,

thus placing the method in a favorable light for use in the analysis of uncertainty of chemical

plant simulations. The thermodynamic model developed in this chapter is extended in Chapter 3

to include the uncertainties in the original vapourliquid equilibrium data and a database of

interaction parameters with uncertainties will be developed.

54

Design 2. Binary Mixtures 2

3.1 Abstract

A simple procedure is proposed to evaluate the uncertainty of the binary interaction parameters

from the uncertainties present in the physical properties and equation parameters used for their

calculation using a cubic equation of state. A small but useful database containing 87 binary

mixtures present in natural gas was constructed through collection of available experimental

vapourliquid equilibrium (VLE) data and associated uncertainties.

A thermodynamic consistency test was performed on each isothermal dataset to

determine the quality of the VLE data. Upon acceptance of the VLE data based on its quality and

consistency, binary interaction parameters and associated uncertainties were determined using a

combination of nonlinear regression and Monte Carlo simulation, taking into account the

uncertainties of the pure components, equation of state parameters, and VLE data. The Monte

Carlo simulation was also used for the error propagation to estimate the uncertainty in the

calculated VLE. Sample calculations were presented illustrating the effect of uncertainties in the

PXY and TXY diagrams of ethane/propane and methane/hydrogen sulfide binary mixtures. The

required minimum number of stages for a simplified de-ethanizer was calculated taking into

account uncertainties in the basic input parameters. In addition the effect of uncertainties in the

position of calculated cricondenbar and cricondentherm was evaluated.

Reprinted from Fluid Phase Equilibria, Vol. 364, S. Hajipour, M.A. Satyro, M.W. Foley, Uncertainty Analysis

Applied to Thermodynamic Models and Process Design 2. Binary Mixtures, 15-30, Copyright (2013), with

permission from Elsevier. It should be noted that the content of this chapter includes the extensions beyond the

cited journal paper.

55

3.2 Introduction

In Chapter 2, a comprehensive database for physical properties of pure hydrocarbons commonly

present in natural gas and their associated uncertainties was developed. Two correlations were

re-parameterized to estimate the critical properties and acentric factors of pseudo-components,

and the PengRobinson (PR EOS) [12] equation of state was re-parameterized to reflect the

uncertainties of the underlining physical property data in its structure as represented by the

generalized alpha parameter. The covariance matrices of model parameters were also presented

which can then be used to provide uncertainty information when used in process simulation and

make it possible to estimate the uncertainties of physical properties and thermo-physical

properties of pure components through error propagation calculations. In this Chapter, the

applicability of the re-parameterized PR equation of state is extended to binary mixtures,

required in the evaluation of the uncertainties in process simulation.

Several studies in the area of uncertainty effect on process design emphasize the

importance of uncertainty analysis in the field of process engineering and most of them were

reviewed in Chapter 2. Recently, uncertainty analysis in design and operation of biochemical

processes has been performed by Sin and co-workers on a case study basis; for example,

antibiotic production [52] and biofuel production [53]. They analyzed the uncertainty of model

predictions for a cellulose hydrolysis process and calculated the mean values of the estimated

parameters as well as their variance-covariance matrix based on a 95% confidence interval [53]

using the Monte Carlo technique combined with Latin Hypercube Sampling (LHS) method.

Cinnella et al. [54] also presented error propagation from some common thermodynamic models,

such as the PR EOS, to the pure dense gas flow fields predicted by a computational fluid

dynamics (CFD) solver. They quantified the impact of such uncertainties on aerodynamic data

56

and concluded more complex models may be more sensitive to uncertainties of the fluid physical

properties due to the larger number of input parameters involved.

Most processes in the petroleum and chemical industries operate in liquid and/or vapour

phases. Therefore the proper modelling of VLE is a significant step for the proper design and

simulation of processes. Cubic equations of state are extensively used in process simulators as

reliable models for the prediction of thermodynamic properties and phase equilibria for

hydrocarbon systems due to their simplicity, robustness, and computational efficiency.

Mixing rules and binary interaction parameters are used to generalize the equations of

state from pure fluids to mixtures and to improve the quality of VLE predictions. There is a large

body of work on mixing rules for cubic equations of state and will not be reviewed here because

it is beyond the scope of this study. Suffice it to say that commonly used mixing rules to

represent the behaviour of hydrocarbon mixtures will be used, and a more advanced mixing rule

for thermodynamic consistency calculations will be used when necessary. The procedures and

methods proposed in this Chapter are completely general and can be used with any equation of

state and associated mixing rules.

Optimum values of binary interaction parameters are determined by regression using

screened VLE data. Critical properties and acentric factors of pure components, thermodynamic

model parameters and the VLE data including pressure (P), temperature (T) and both liquid and

vapour phase compositions (x, y), are considered as independent variables used to estimate

binary interaction parameters.

As previously discussed in Chapter 2, uncertainties in input variables propagate through

the model and do affect the accuracy of the final results. Therefore, the quality of the adjusted

model parameters depends on the quality of all dependent and independent variables. Presently

57

binary interaction parameters are used in process simulators without statistical uncertainty

information. This lack of uncertainty information precludes the critical analysis of processes and

associated equipment and consequently further process development is hampered by the use of

empirical rules of thumb for determination of an appropriate overdesign factor.

The experimental uncertainties in VLE data available in the ThermoData Engine (TDE)

[2] developed by the National Institute of Standards and Technology (NIST) are used for the

estimation of uncertainties in the binary interaction parameters together with the pure component

database and EOS developed in Chapter 1. NISTs ThermoData Engine (TDE) software and the

SOURCE database [3, 4] implement the concept of a dynamic data evaluation to thermo-physical

property data and this fact enables the development of databases and correlations not only for

pure components but also for binary mixtures that reflect the associated uncertainties. TDE

evaluates the uncertainties through the examination of the quality of experimental data originated

from the SOURCE database which combines the knowledge embodied in the scientific literature

with the expert knowledge of NISTs scientists about error propagation and statistical analysis

for the development of recommended uncertainties for the collected data [55]. In this study, the

uncertainties in physical properties of pure components and binary vapourliquid equilibrium

data evaluated by TDE are used for estimation of binary interaction parameters and their

uncertainties. The uncertainties of the VLE data were taken into account as weighting factors in

the objective function used in the parameter estimation and they are also considered, along with

the uncertainties related to pure components for the uncertainty estimation of the interaction

parameters using Monte Carlo simulation. This approach maximizes the chance that the best set

of model parameters are calculated for binary mixtures from a data quality point of view.

58

simulation, design, and performance. This is illustrated by a simple example where uncertainties

in the vapour and liquid compositions are introduced in the design of a simplified de-ethanizer

used to stabilize liquefied petroleum gas (LPG). It is assumed that the de-ethanizer operates at

2758 kPa with a distillate purity specification of 0.99 0.005 (C2) mole fraction and a bottoms

product with a purity specification of 0.98 0.005 (C3) mole fraction.

Figure 3.1 shows the TXY diagram for ethane/propane using the experimental VLE data

[56] and uncertainties of 0.11 K for temperature, 0.005 for liquid phase composition (x), and

0.005 for vapour phase composition (y).

350

Ethane/Propane System

P= 2758 kPa [56]

Temperature (K)

330

310

290

270

0.0

0.2

0.4

0.6

Ethane (Mole Fraction)

0.8

1.0

Note that the thickness of the TXY curves actually represents the uncertainties

associated with the bubble and dew points curves.

Figure 3.2(a) shows the K-value for each component (Ki=yi / xi) versus mole fraction of

ethane and the error bars indicate the effects of uncertainties in compositions on the calculated

59

equilibrium constants at each experimental point using the standard error propagation equation,

Equation 3.1:

x

i

Ki

xi

i

yi

yi

2

3.1

where Ki , xi , and yi are the uncertainties of the K-value, liquid phase composition and

vapour phase composition for component i, respectively. In this calculation, it was assumed that

there was no correlation between uncertainties in the measured compositions; therefore, the offdiagonal terms of the covariance matrix are zero. Note the error in equilibrium constant increases

as either ethane or propane approaches high dilution due to the inverse relation between the

uncertainty of K-value and the phase compositions.

The error bars in Figure 3.2(b) indicate the errors in relative volatility propagated from

the uncertainties in compositions at each experimental point against mole fraction of ethane. This

case study provides a compelling example of the effect of uncertainties in physical properties on

equipment design, in this case through the relative volatility. The effect of uncertainties on the

design of the de-ethanizer can be simply illustrated when the Fenske equation [57], Equation 3.2,

is used to calculate the minimum number of stages (Nmin) required for the separation.

N min

x (1 x B )

ln D

x B (1 x D )

ln avg.

3.2

where xD and xB are liquid mole fractions of ethane in distillate and bottoms products, and avg.

refers to the geometric average relative volatility of top-stage and bottom-stage values.

60

2.5

Vapour-Liquid Equilibrium Constant

(a)

2.0

1.5

Ethane

1.0

0.5

Propane

0.0

0.0

0.2

0.4

0.6

Ethane (Mole Fraction)

0.8

1.0

2.8

(b)

2.6

2.4

2.2

2.0

1.8

1.6

1.4

0.0

0.2

0.4

0.6

Ethane (Mole Fraction)

0.8

1.0

constant (Ki), and (b) relative volatility () for ethane/propane system at pressure of 2758

kPa.

61

Without considering the uncertainties in equilibrium data, the minimum number of stages

would be 12, while taking uncertainties into account the estimated number of minimum stages is

12 10 stages. The uncertainty in the minimum number of stages ( Nmin ) is calculated by

Equation 3.3:

N

min

N min

1

2 ln avg.

2 N min xD

xD (1 xD ) N min

yD N min 2 xB

y D (1 y D ) xB (1 xB ) N min

2

yB

y B (1 y B )

2

3.3

where yD and yB are vapour mole fractions of ethane in the distillate and bottom products.

This variability in the number of stages has a significant effect on the equipment capital

cost, its operational cost, and for its intended purpose. The results obtained in this example are in

agreement with results presented by Dohrn and Pfohl [58] and will be revisited at the end of this

chapter using a complete thermodynamic model with uncertainties.

The quality of the existing VLE data is important for development of binary interaction

parameters and it is important to have a general method, based on thermodynamic principles, to

screen the experimental data quality. When complete TPXY data is collected there is an intrinsic

redundancy as shown by the GibbsDuhem equation written for a binary mixture, Equation 3.4:

HE

VE

dT

dP 1d ln( 1 ) 2 d ln( 2 )

RT

RT 2

3.4

where i is the mole fraction of component i in the reference phase, and i is the activity

coefficient of component i in the reference phase. H E and V E are the molar excess enthalpy and

the molar excess volume, respectively. Unfortunately, these data are not always available nor are

they usually measured simultaneously and consistently with the VLE data.

It is well known that the GibbsDuhem can be used as the basis for thermodynamic

consistency tests [59]. Since most of the VLE data used in this study is at high pressure and

62

Thermodynamic consistency tests derived from the GibbsDuhem equation for high pressure

VLE data [60-66] use different equilibrium data and thermodynamic functions. In some cases

[63-65], the liquid phase composition is not used, and these methods can be used only if PTY

data are available. In this study, the Valderrama and Fandez [66] method was selected for

testing the VLE data because it not only uses all available PTXY data but also does not have the

complexity of the Won and Prausnitz [61] method which requires the definition of arbitrary

functions for activity coefficients and molar volumes of mixtures, or the Christiansen and

Fredenslund [62] approach which requires the calculation of several thermodynamic properties

such as standard state fugacity and Gibbs free energy. Although the Valderrama and Fandez do

also provide model parameters as part of the thermodynamic consistency procedure, this feature

of the method was not used in this study. In the Valderrama and Fandez method, the Gibbs

Duhem equation is expressed in terms of fugacity coefficients calculated in the VLE data

modelling procedure using the PR EOS [12] combined with the WongSandler mixing rules

[67]. The choice of mixing rules is somewhat arbitrary and is essentially determined by its

flexibility to fit data. This method fulfills our requirements for testing all the available PTXY

data for any range of concentration and pressure with calculated properties using the PR EOS.

Whenever possible, thermodynamically consistent sets are used for the determination of

binary interaction parameters and their associated uncertainties. It should be stressed that not all

VLE data is thermodynamically consistent and therefore the construction of a binary interaction

parameter database will almost certainly contain parameters that are based on tentative data.

Details of the data included in the parameter estimation are discussed in the following

section. The binary interaction parameter determination is a function of the objective function

63

[68-73] used in the data regression. Among the various types of objective functions reviewed by

Ashour and Aly [74], the one suggested by Anderson and Prausnitz [75] was used in this study.

This method was chosen because all the variables from binary VLE measurements and their

associated uncertainties are considered in evaluating parameters in Equation 3.5:

NP

Fobj (k12 )

n1

1

1

1

P

x1

y1

n

n

n

n

3.5

where s are the uncertainties of the measured variables and may vary from point to point. Pcal

and ycal are calculated using a bubble-point pressure calculation. Tcal and xcal are calculated using

a dew-point temperature calculation.

Arguably the most valuable contribution of this work is the uncertainty estimation of

binary interaction parameters obtained by minimization of the objective function, Equation 3.5.

Two useful approaches for the estimation of best guesses for the interaction parameters and their

uncertainties are described in the statistical literature Frequentist and Bayesian [76] and briefly

reviewed here.

Using the Frequentist approach, the unknown parameters are viewed as fixed values

which are usually determined using the maximum likelihood estimation method by minimizing

an objective function and their uncertainties are quantified under hypothetical repetition of

sampling of the observed data. In contrast, the Bayesian approach regards the unknown model

parameters as random variables with the prior postulated probability distributions based on the

prior knowledge of the analyst. The prior distribution represents beliefs for parameters before

observing the data. The Bayesian approach is based on the posterior probability distribution of

model parameters after observing data which is calculated using the prior distributions along

64

with a given set of observations based on Bayes theorem [76]. The Markov Chain Monte Carlo

method is often used for summarizing the posterior distribution in order to derive statistics such

as posterior mean and standard deviation. This approach is therefore useful when there is plenty

of prior information about the nature of the errors and their correlations and especially valuable

when the number of observations is limited [77].

The bootstrap technique proposed by Efron [78] is the main Frequentist tool used to deal

with complicated sampling distributions. It is a valuable approach that can be used when there is

a limited or no prior knowledge about the parameters and the nature of the measurement errors

[48]. In this method, the parameters are fitted to the actual observations by minimizing an

objective function and any number of random data sets is generated by replacement from the

residual error distribution. Each of these samples is analyzed to obtain the estimated parameters

and finally the Monte Carlo method is used to evaluate the expected values of the parameters.

Each of these approaches has their advantages and shortcomings. The strength of the

Bayesian method is its unified approach to all problems of uncertainty. However, it could not

solve complex problems due to computational difficulties as shown by Efron [79]. The prior

specification of parameter distribution is the other issue of this method, since improper posterior

may result from an improperly specified prior, especially for nonlinear models. The strength of

Frequentist methods is their ability to provide useful uncertainty estimates for model parameters

without the need to know the prior.

Since the objective of this study is to evaluate the fitted parameter uncertainty by taking

into account not only all the independent and dependent variable uncertainties but also model

input parameter uncertainties, none of the above-mentioned methods is entirely adequate as a

means to estimate the uncertainty of binary interaction parameters while taking into account all

65

the input uncertainties and the lack of detailed knowledge of how experiments were actually

performed, thus effectively making the use of Bayesian techniques very difficult.

Consequently, the Monte Carlo technique used in Chapter 1 is used to estimate the

uncertainties of the binary interaction parameters. This procedure is similar to the procedure used

in the bootstrap approach but now uses the Latin Hypercube Sampling (LHS) method [6] instead

of partial data replacement from the residual error distribution. The simultaneous use of the pure

components, VLE data, and equation of state allows for the development of a binary interaction

parameter database with uncertainties determined in a consistent and systematic manner. The

main four steps in using this technique are (1) specification of probability density functions for

the uncertainty of the input variables involved in the study based on the knowledge of their

uncertainty, (2) probabilistic sampling of the uncertainty space, (3) simulation and calculation of

output parameters by passing each sample set through the model, and (4) statistical analysis of

the results to evaluate the uncertainty of the model outputs.

3.3 Thermodynamic Consistency Test

The Valderrama and Fandez [66] thermodynamic consistency test, used in this study, is briefly

described in this section. The GibbsDuhem equation written in terms of residual properties and

fugacity coefficients, Equation 3.6, overcomes the problem of evaluation of the excess volume

and pressure effects on the activity coefficients for isothermal conditions. The fugacity

coefficients and the residual volume can both be calculated by a single equation of state [65].

VR

dP 1d ln(1 ) 2 d ln( 2 )

RT

3.6

66

where i and i are the mole fraction and fugacity coefficient of component i in the given phase

(liquid or vapour) and V R is the residual volume of the corresponding phase. Using

( Z 1)

dP (1 2 )d ln(1 ) 2 d ln( 2 )

P

3.7

For calculation of the fugacity coefficients and compressibility factor, a suitable

thermodynamic model must be selected to fit the given NP experimental VLE data points within

acceptable deviations. As suggested by Valderrama and Fandez [66], a model is appropriate if

the average absolute deviations of pressure and gas phase mole fractions of Component 1 defined

by Equations 3.8 and 3.9 are below 10%.

If the bubble point pressure and gas phase composition are not well correlated, it may

signify that the model is not appropriate for the binary system being studied or the data has

errors, and therefore the consistency test cannot be applied. Therefore, before using the

consistency test, these two criteria must be met.

AAD P

N P n1

P exp

100 N P y1 y1

AAD y

exp

N P n1

y1

cal

3.8

n

exp

3.9

n

After the model is found acceptable, the thermodynamic consistency test is performed

based on the Equation 3.7 integrated over an interval from data point r to an adjacent data point s

as expressed in Equation 3.10:

67

s

s

1

1 2

1

dP

d1

d 2

r ( Z 1)

r ( Z 1)

P 2

2

1

2

3.10

For a set of VLE data with NP data points, both sides of the Equation 3.10 must be

calculated for each ( N P 1) intervals for both liquid and vapour phases. The left hand side of

Equation 3.10 is denoted by AP, Equation 3.11, and the right hand side by A , Equation 3.12:

AP

1

dP

P 2

3.11

A A1 A2

s

1 2

1

d1

d 2

r ( Z 1)

2 ( Z 1)1

2

3.12

AP is determined using the experimental values of PX for liquid phase and PY for vapour

phase for each interval l using the trapezoidal rule and is considered as the experimental area,

since it is obtained from experimental data. Figure 3.3 shows a schematic view of the integrated

function in Equation 3.11 plotted against pressure at each data point. The hatched area indicates

AP for interval l.

( AP ) l

1 1 1

Ps Pr

2 P 2 s P 2 r

1/(P2)

s

(AP)

NP

Figure 3.3. Illustration for the calculation of AP between two consecutive points of r and s.

68

coefficients and compressibility factor from the thermodynamic model. The integration

procedure for evaluation of A1 and A2 is similar to that for AP. Since A is obtained from

calculated properties, it is considered to be the calculated area.

As an index for testing the consistency of VLE data, the individual absolute deviation

between experimental area (AP) and calculated area (A) is defined by Equation 3.13 for each

interval l ( l 1 to ( N P 1) ) and for a consistent dataset it should be within acceptable defined

deviations for both phases.

| %Al | 100

A AP

AP

3.13

l

thermodynamically consistent (TC), if all ( N P 1) individual area deviations are below 20% for

both phases, and considered as not fully consistent (NFC) if some of the area deviations (equal or

less than 25% of the areas) are more than 20%. The area test can conclude that the dataset is

thermodynamically inconsistent (TI), if most of the area deviations (more than 75% of the areas)

are outside the 20% limit. The defined margins of accepted errors applied in this method for

selection of the appropriate model (10% for average absolute deviations of pressure and vapour

phase composition) as well as for consistency test (20% for area deviations) were discussed in

detail by Valderrama and Alvarez [80].

In this study, if the model is inappropriate (IM) for modelling of an isothermal VLE

dataset or the dataset is TI, the dataset will be removed from the accepted VLE database used for

evaluation of binary interaction parameters. Only VLE data which are TC and NFC are used to

69

calculate the binary interaction parameters. However, in cases where there is no consistent and

not fully consistent data or there is no isothermal dataset, the available data are used for

estimation of binary interaction parameters. These data should be clearly marked as tentative

data and revisited when new data or new correlation methods become available to foster

permanent improvements in the thermodynamic database and associated process simulations and

equipment design.

3.3.1 Computational Approach for Modelling of VLE Data

Similar to the proposed thermodynamic consistency test method [66], the PR equation of state

[12] with the WongSandler mixing rule [67] along with the van Laar activity model was used in

this study as the default thermodynamic model to correlate VLE data for the system being

studied, although any other flexible and accurate thermodynamic model could be used.

As discussed by Brandani et al. [81] the WongSandler mixing rules have enough

flexibility and accuracy to fit high-pressure VLE data. These mixing rules can be accurately

applied for simple mixtures containing hydrocarbons and inorganic gases and mixtures

containing polar, aromatic, and associating species [67] over a wide range of temperature and

pressure using just a minimal number of adjustable binary parameters.

When using the WongSandler mixing rules, the PR EOS parameters for a mixture am

and bm, are calculated using Equation 3.14 through Equation 3.16:

a m bm

NC

i 1

ai AE ( i )

bi

3.14

70

bm

NC

NC

i 1

j 1

i j b

AE

1

RT

NC

i 1

RT ij

3.15

a

i i

bi RT

ai a j

a

1

(1 ij )

b

(bi b j )

RT ij 2

RT

3.16

of state, ai and bi are the PR equation of state parameters for pure component i, ij is a symmetric

binary interaction parameter, and AE is the molar excess Helmholtz energy at infinite pressure

obtained from the van Laar activity coefficient model, Equation 3.17, using the WongSandler

approximation G E (T , P 1 bar , i ) AE (T , high pressure, i ) .

G E AE

RT RT

121 2

1 12 2

21

3.17

Three adjustable parameters, 12, 12, and 21, were determined by fitting the bubble

point data from NP experimental VLE dataset using Equation 3.18:

Fobj (12 , 12 , 21)

NP

n 1

2

P cal P exp 2

y1cal y1exp

qn

exp

exp

y1

P

n

3.18

where y1 is the mole fraction of Component 1, superscript 'cal' and 'exp' denote the calculated

and experimental values, respectively, and qn are the weighting factors that are chosen such that

both terms are of the same order of magnitude at each point n. Therefore, it can be set as a power

of ten where the exponent is the order of magnitude difference between two terms at each point.

71

For instance, if the order of magnitude of the first term is 3 and one of the second term is 5,

the weighting factor would be 100. Since the order of magnitude difference may vary in different

points, the weighting factor may be different from one point to another one.

The error represented by Equation 3.18 is minimized using the LevenbergMarquardt

[45] nonlinear regression method to determine the thermodynamic model parameters. Since the

number of data points must be greater than the number of adjustable model parameters, only the

consistency of the isothermal VLE datasets containing more than three data points (NP > 3) can

be used in this method.

3.4 Binary VLE Database Development

The binary VLE database contains temperature (T), pressure (P), liquid phase composition (x),

and vapour phase composition (y) for all experimentally available binary mixtures based on a

pure component set comprised of 18 components including hydrocarbons from C1 to nC10,

nitrogen, oxygen, argon, helium, hydrogen sulfide, and carbon dioxide. The components were

selected based on their importance for natural gas processing. The experimental values of the

VLE and their relevant uncertainties are taken from TDE Version 5.0 [2]. Among 153 possible

binary combinations from the components of interest, experimental data for 87 binaries are

available in TDE.

Table 3.1 shows a small sample of the developed binary vapourliquid equilibrium

database for the ethane/propane binary mixture selected from 581 VLE data points available for

this mixture. The VLE information for the database of the 87 binaries is shown in Table C.1.

72

Table 3.1. Sample of developed VLE database for the ethane/propane mixture.

Pure Components Properties

Tc (K)

Pc (kPa)

Ethane

305.36 0.03

4879.4 22.3

0.100 0.002

Propane

364.95 0.26

4594.1 49.0

0.142 0.005

Component

T (K)

P (kPa)

x1

y1

T (K)

P (kPa)

Ref.

283.15

689.48

0.0236

0.0720

0.05

6.89

0.001

0.001

[82]

283.15

1379.0

0.3570

0.6120

0.05

13.8

0.001

0.001

[82]

283.15

2068.4

0.6510

0.8480

0.05

20.7

0.001

0.001

[82]

283.15

2757.9

0.9066

0.9616

0.05

27.6

0.001

0.001

[82]

344.26

2757.9

0.0253

0.0480

0.11

13.8

0.005

0.005

[56]

344.26

3102.6

0.1040

0.1760

0.11

13.8

0.005

0.005

[56]

344.26

3447.4

0.1740

0.2700

0.11

13.8

0.005

0.005

[56]

344.26

3792.1

0.2410

0.3430

0.11

13.8

0.005

0.005

[56]

344.26

4136.9

0.3050

0.4030

0.11

13.8

0.005

0.005

[56]

344.26

4481.6

0.3690

0.4570

0.11

13.8

0.005

0.005

[56]

344.26

4826.3

0.4320

0.5020

0.11

13.8

0.005

0.005

[56]

There are instances where uncertainties associated with VLE data are not fully reported

in TDE, for example, there are no uncertainties reported for the VLE data of n-decane/hydrogen

sulfide, methane/helium, and propane/n-pentane. Only uncertainties in pressure are reported for

n-octane/nitrogen, nitrogen/hydrogen sulfide, and n-hexane/carbon dioxide, and only

uncertainties in temperature and pressure are reported for n-heptane/n-octane, n-decane/n-octane,

and n-hexane/n-heptane. In order to access the missing uncertainties, the original literature cited

by TDE was reviewed which was a challenging and a time consuming effort. If the uncertainty

information of a binary system was not available, default uncertainties of 0.5 K, 50 kPa, 0.003

73

and 0.01 were assumed for temperature, pressure, liquid phase composition and vapour phase

composition, respectively [75].

To help ensure the accuracy of the data entered in the database, the VLE data reported by

TDE was checked against the data actually reported to eliminate typos and data duplication. For

instance, the composition of propane reported by Kahre [83] for the ethane/propane system was

reported as the composition of ethane in TDE. Both liquid and vapour phase composition of npentane/n-heptane published by Burova et al. [84] in mass fractions were reported as mole

fractions in TDE, and the isothermal VLE data at 169.81 K reported by Heck and Hiza [85] for

methane/helium mixture was reported in TDE at 124.85 K. There are also VLE data repetitions

for some mixtures such as carbon dioxide/nitrogen, n-decane/carbon dioxide, and nheptane/nitrogen. All errors were noted and communicated to NIST.

3.4.1 Application of the Selected Consistency Test in This Study

The application of the consistency test method explained in section 3.3 is illustrated for

ethane/propane and methane/hydrogen sulfide (H2S) mixtures.

Table 3.2. Range of VLE data used for the consistency test.

Mixture

T (K)

NP

Range P (kPa)

Range x1

Range y1

Ref.

270.00

23

496.00 1972.0

0.0469 0.8957

310.93

322.04

12

11

1379.0 4998.7

1723.7 4998.7

0.0313 0.9190

0.0130 0.7730

0.0300 0.826 [56]

273.20

277.59

310.93

344.26

12

23

21

12

1240.0 11820

1379.0 13100

2757.9 13100

5515.8 11376

0.0030 0.3560

0.0057 0.4401

0.0007 0.3578

0.0031 0.1830

0.1350 0.7380

0.1371 0.7321

0.0117 0.5255

0.0196 0.2811

Ethane/Propane

Methane/H2S

74

[87]

[88]

[88]

[88]

Three isotherms for the mixture of ethane (1)/propane (2) and four isotherms for the

mixture of methane (1)/H2S (2) from low to high pressures were selected from the VLE database

developed in this study to illustrate the use of the consistency test. The ranges of experimental

VLE data for isotherms are summarized in Table 3.2 and pure component properties are shown

in Table 3.1 for ethane and propane and in Table 3.3 for methane and H2S.

Component

Methane

Tc (K)

190.56 0.01

Pc (kPa)

4606.8 9.1

0.0116 0.0019

H2S

373.14 0.45

8950.0 21

0.0975 0.0013

The adjusted model parameters for thermodynamic consistency ( 12, 12 and 21),

average absolute deviations in pressure (AADP) and vapour phase compositions (AADy), average

absolute deviations of area in both liquid and vapour phases, and the consistency test results are

summarized in Table 3.4.

Before performing the consistency test, AADP and AADy must be checked to verify if they

are within the accepted error margins defined by the thermodynamic consistency method as

discussed above. Table 3.4 shows that these values are less than 10% for all isotherms except for

methane/H2S system at 344.26 K where AADy is greater than 10%. This means that the pressure

and vapour phase composition are not well correlated at this temperature due to either the model

limitations when fitting the VLE data or the VLE data may be of poor quality. In this case, the

model is classified as inappropriate (IM) and this particular consistency test cannot be applied for

this mixture at 344.26 K.

75

The ethane/propane mixture at 310.93 K was found to be TC, meaning that the individual

absolute deviations for all intervals (l=1 to11) in this dataset are less than 20%. At 322.04 K the

relevant VLE data was found NFC, meaning that the individual absolute deviations are greater

than 20% for less than 25% of all intervals (l=1 to10) in the dataset, and at 270 K it was found

TI, meaning that the individual absolute deviations are greater than 20% for more than 25% of

all intervals (l=1 to 22). For methane/H2S system, the VLE data was found to be TC at 310.93 K,

NFC at 277.59 K, TI at 273.20 K, hence the consistency test cannot be applied at 344.26 K since

the data were not well correlated (IM).

Mixture

%AADP

%AADy

|%AL|

|%AV|

Results

0.36

4.85

15.99

16.35

TI

0.81

4.54

6.00

5.60

TC

0.99

7.67

6.05

5.33

NFC

273.20 0.0613

1.7291

1.1824

2.66

5.88

33.89

32.44

TI

277.59 0.0730

1.4752

1.2026

3.19

3.95

9.67

9.57

NFC

310.93 0.1010

1.5713

0.8347

0.32

2.13

3.07

3.27

TC

344.26 0.0975

1.4145

0.7824

0.40

10.85

IM

T (K)

12

12

21

Ethane/Propane

Methane/H2S

The results are also shown in Figure 3.4 for ethane/propane and Figure 3.5 for

methane/H2S. The pressure-composition PXY diagrams for the binary systems are shown in

Figure 3.4(a) to (c) and Figure 3.5(a) to (c), and the calculated individual area deviations at each

interval are shown in Figure 3.4(d) to (f) and Figure 3.5(d) to (f).

76

2400

60

2000

Experimental

1600

Calculated

T = 270.00 K

(a)

1200

800

400

0

-20

-40

-80

0.0

0.2

0.4

0.6

0.8

Ethane Mole Fraction (x, y)

1.0

6000

10 12 14 16 18 20 22

Interval (l)

10

T = 310.93 K

(e)

T = 310.93 K

(b)

5

Area deviation (%)

5000

Pressure (kPa)

20

-60

4000

3000

2000

0

-5

-10

-15

1000

-20

0.0

0.2

0.4

0.6

0.8

Ethane Mole Fraction (x, y)

1.0

6000

5 6 7 8

Interval (l)

9 10 11 12

10

T = 322.04 K

T = 322.04 K

(c)

Area deviation (%)

5000

Pressure (kPa)

(d)

40

Area deviation (%)

Pressure (kPa)

T = 270.00 K

4000

3000

(f)

0

-10

-20

-30

2000

-40

1000

0.0

0.2

0.4

0.6

0.8

Ethane Mole Fraction (x, y)

1.0

5 6 7

Interval (l)

10 11

and 273.20 K, (d-f) Deviations in the individual areas ( %Ai ) for liquid phase () and

vapour phase ( ).

77

14000

80

T = 273.20 K

T = 273.20 K

(a)

Area deviation (%)

Pressure (kPa)

10000

8000

6000

4000

40

20

0

-20

-40

2000

-60

0

0.0

0.2

0.4

0.6

0.8

Methane Mole Fraction (x, y)

1.0

14000

5 6 7 8

Interval (l)

9 10 11 12

30

T = 277.59 K

T = 277.59 K

(b)

Area deviation (%)

12000

Pressure (kPa)

(d)

60

12000

10000

8000

6000

4000

(e)

20

10

0

-10

2000

-20

0

0.0

14000

0.2

0.4

0.6

0.8

Methane Mole Fraction (x, y)

1.0

10 12 14 16 18 20 22

Interval (l)

15

T = 310.93 K

T = 310.93 K

(c)

Area deviation (%)

12000

Pressure (kPa)

10000

8000

6000

Experimental

(f)

10

5

0

-5

4000

Calculated

-10

2000

0.0

0.2

0.4

0.6

0.8

Methane Mole Fraction (x, y)

1.0

8 10 12 14 16 18 20

Interval (l)

and 310.93 K, (d-f) Deviations in the individual areas ( %Ai ) for liquid phase () and

vapour phase ( ).

78

As shown in Figures 3.4(e) and 3.5(f), all the calculated individual area deviations at 310

K for systems ethane/propane and methane/H2S in both liquid and vapour phases are within the

20% to +20% and does indicate that the VLE datasets are TC.

Figure 3.4(f) at 322.04 K and Figure 3.5(e) at 277.59 K show only one area in the liquid

phase with high area deviation and outside the defined range. For the ethane/propane mixture the

high deviation occurred in the first interval (l=1) represents 10% of the total number of intervals

(one out of ten intervals), while for the methane/H2S mixture the high deviation interval seen in

l=19 represents 4.5% of the total number of intervals (one out of 22 intervals), so both systems at

the studied temperatures are determined to be NFC.

At 270.00 K the mixture of ethane/propane, considered to be TI, the area deviations are

not within the accepted range for five intervals (22.7% of the total intervals) in the liquid phase

and six intervals (27.2% of the total intervals) in the vapour phase, Figure 3.4(d). The same

pattern can be seen for methane/H2S at 273.20 K, Figure 3.5(d), where seven areas (63.6%) in

the liquid phase and six areas (54.6%) in the vapour phase represent high area deviations.

Among the isotherms studied in this section for these mixtures, isotherms at 310.93 and

322.04 K for the ethane/propane and isotherms at 310.93 and 277.59 K for the methane/H2S with

TC and NFC datasets are considered as acceptable VLE data for evaluation of the binary

interaction parameters. This same procedure was used to verify the thermodynamic consistency

for 87 binary mixtures included in the VLE database that was used for the determination of

binary interaction parameters.

79

Binary interaction parameters are commonly used in equations of state to improve the prediction

of vapourliquid equilibrium data, particularly in non-ideal fluid systems, and critical to the

ability of a thermodynamic model to accurately represent fluid phase behaviour. To quantify the

binary interaction parameter uncertainties, the Monte Carlo technique previously described in

Chapter 2 is used to propagate independent pure component, equation of state and VLE

uncertainties to the estimated parameter uncertainty.

In this chapter, the re-parameterized PR EOS with quadratic mixing rules, Equations 3.19

and 3.20, is used to model the phase behaviour of binary systems. Although more complicated

mixing rules are available, such as the WongSandler mixing rules used for the thermodynamic

consistency tests, quadratic mixing rules are widely used for modelling of natural gas mixtures

and for the simulation of many important industrial processes and as such is used in this study to

estimate the binary interaction parameter (kij).

2

am i j ai a j (1 kij )

3.19

i 1 j 1

bm i bi

3.20

i 1

In addition to experimental VLE data, the pure components properties including critical

temperatures (Tc), critical pressures (Pc), and acentric factors () are used as independent

variables in the calculation of the binary interaction parameters. Parameters of the

thermodynamic model also affect the quality of the estimated binary interaction parameter,

therefore, the total number of variables considered in this study for evaluation of a binary

80

interaction parameter and its uncertainty is thirteen, Table 3.5. Pure component properties and

the model parameters and their uncertainties are available in the pure component database

developed in Chapter 2, and the mixture data are taken from the database developed in this

chapter.

As in the TDE, it is assumed that the uncertainties are normally distributed. It should be

noted, distribution of the experimental data is not necessarily Gaussian, but it is the best

assumption that can be made at this time.

Table 3.5. Input variables for estimation of a binary interaction parameter.

Input Variables

Pure compounds

Tc Tc i

Pc Pc i

(i = 1,2)

Thermodynamic model [8]

( f m1 m2 m3 2 )

Vapourliquid equilibrium data

P P n

T T n

x1

y1

(n=1 to NP)

Monte Carlo techniques are useful statistical methods for uncertainty analysis and error

propagation in complex models. The objective of this study is to determine the uncertainties of

binary interaction parameters estimated from phase equilibrium calculations. Figure 3.6 shows

the conceptual scheme of the approach used for uncertainty evaluation of the estimated

parameters. Incorporating the mean values of all model input variables and uncertainty

information of VLE data shown in Table 3.5, the binary interaction parameter is estimated by

81

minimizing the AndersonPrausnitz objective function, Equation 3.5. In order to evaluate the

uncertainty of the fitted parameter, a sample set with size n' is randomly generated for each input

uncertain variable. Instead of replacement of the actual data based on the residual error

distribution which is used in the bootstrap approach to construct the sample dataset, due to lack

of uncertainty information of the observations, the LHS sampling method is used in this study.

Since the uncertainty of the experimental VLE data and also model parameters are available, the

LHS method was selected to select random data points from the normal distribution defined for

each input variable based on their uncertainty information.

Equation 3.5

Min.

Fitted parameter (k12)1

Dataset (2)

Dataset (n')

and their uncertainties

(Table 3.5)

Dataset (1)

Figure 3.6. Conceptual scheme of the approach used for uncertainty estimation of the fitted

parameter.

In this sampling method, the range of each input variable is divided into n' nonoverlapping intervals based on the equal probability of 1/ n' and one value from each interval is

taken at random. These obtained n' values for each variable are grouped in a random manner.

The LHS method ensures that the variables have been sampled over the full range of their

uncertainties and decreases the number of runs necessary to stabilize the Monte Carlo simulation,

when compared to the random sampling method.

82

For a mixture of interest, the binary interaction parameter is estimated for each sample set

with exactly the same procedure used for true mean values, and the resulting binary interaction

parameters are filed as data. The mean value and standard deviation of n' estimated binary

interaction parameters are then calculated and the associated uncertainty is estimated as two

times the standard deviation based on the selected 95% confidence level, consistent with the

uncertainty definition used in TDE. Finally, the resulting binary interaction parameter is

represented as an average value and a quantified uncertainty.

Since sample size determination is an important part of the Monte Carlo simulation a

brief study on the effect of sample size (n') on the estimated uncertainty of the binary interaction

parameter was performed. Three sets of binary interaction parameters are generated with 100,

1000, and 10,000 samples for two binary mixtures of ethane/propane (hydrocarbon/hydrocarbon)

and methane/H2S (hydrocarbon/polar compound).

The pure compounds properties and their uncertainties are shown in Table 3.1 and Table

3.3. Three parameters of the thermodynamic model (m) used for vapourliquid equilibrium

calculations and their uncertainties are presented in Table 3.5 and the number of VLE data point

used for the binary interaction parameter estimation and the range of variations in temperature

and pressure values are shown in Table 3.6.

Table 3.6. Temperature and pressure ranges of consistent VLE data for ethane/propane

and methane/H2S binary mixtures.

Binary

NP

T (K)

P (kPa)

Ethane/Propane

129

Methane/H2S

61

83

50

(a)

n' = 100

40

n' = 1000

Frequency (%)

n' = 10,000

30

20

10

60

(b)

n' = 100

50

n' = 1000

Frequency (%)

n' = 10,000

40

30

20

10

0

Figure 3.7. Histogram of calculated binary interaction parameters by different sample sizes

(a) ethane/propane, (b) methane /H2S.

84

As shown in Figures 3.7(a) and 3.7(b) the distribution of the estimated parameter values

are approximately the same for sample sets with 100, 1000, and 10,000 points, for both mixtures.

The distribution of the binary interaction parameters for the ethane/propane system estimated for

a sample size of 100 is shown in Figure 3.8. The dashed line in this figure shows the normal

(Gaussian) distribution with mean value of 0.0739 and standard deviation of 0.00335. The

values of estimated parameters are approximately distributed as a normal distribution and the

histograms are centred about the true mean value ( k12 0.0739 ), indicated by the arrow. The

hatched area in this figure indicates the range of uncertainty of the binary interaction parameter

( k12 0.0067) which is equal to two times the standard deviation based on the 95% confidence

level.

Frequency (%)

30

20

10

Figure 3.8. Binary interaction parameter distribution for ethane/propane with sample size

100.

85

True mean values of the estimated binary interaction parameters for the mixtures of

interest and associated uncertainties along with the standard deviations are listed in Table 3.7. In

order to measure the accuracy of the results estimated by the Monte Carlo simulation, the Monte

Carlo standard error (MCSE), S n

standard deviation estimated by the Monte Carlo technique for sample size of n'. Clearly if n'

increases, the MCSE goes to zero but the estimate is not necessarily more accurate as illustrated

by the uncertainty. Therefore, there is a practical limit for the determination of the sample size,

Table 3.7.

Based on this study, it appears that a relatively small sample size (n' = 100) can be used

to provide good uncertainty estimates for binary interaction parameters. Therefore, the sample

sets with 100 points generated by Latin Hypercube Sampling (LHS) were used. The study of

sample size can be explored in greater detail and could be the subject of future research studies.

Table 3.7. Monte Carlo simulation results for binary interaction parameters (k12) with

different sample sizes.

Sample Size

Mean Value

( k12 )

Standard Deviation

( S n )

Uncertainty

( k12 )

MCSE

(%)

n' = 100

0.0739

0.00335

0.0067

0.033

n' = 1000

n' = 10,000

0.0739

0.0739

0.00341

0.00335

0.0068

0.0067

0.011

0.003

n' = 100

n' = 1000

n' = 10,000

0.0503

0.0503

0.0503

0.00225

0.00224

0.00228

0.0045

0.0045

0.0046

0.022

0.007

0.002

86

The binary interaction parameters and their uncertainties for 87 binary mixtures are listed in

Table D.1 along with the number of VLE data points used to find the parameters and their

respective temperature and pressure ranges. The importance of the input uncertainties associated

with pure component physical properties (critical properties and acentric factors), reparameterized PR model parameters (m) and binary interaction parameters (kij) estimated in this

chapter is shown through two examples. In all the cases studied in this work, the uncertainty of

the property of interest was estimated using the Monte Carlo technique for an input sample

consisting of all these uncertain variables generated by the LHS method with the sampling size

of 100.

3.6.1 Saturation Point Calculation

In this example, the dew-points and bubble-points and associated uncertainties for two

binary mixtures of ethane/propane and methane/H2S are calculated using the VMGSim

simulation software [7] linked with the Monte Carlo technique. For the dew-point calculations at

known and fixed pressure and vapour composition, temperatures and liquid phase compositions

were calculated for each input sample set and their mean values associated with uncertainties

were estimated using the Monte Carlo technique. The same procedure was used for the bubblepoint calculation for the uncertainty calculation of the pressure and vapour phase composition at

a known temperature and liquid phase composition. Figure 3.9 shows the TXY diagrams for

ethane/propane system at pressure of 2758 kPa and methane/H2S system at 6894.8 kPa based on

the dew-point temperature calculations.

87

350

(a)

P = 2758 kPa

Temperature (K)

330

T-y

310

T-x

290

270

0

0.2

0.4

0.6

Ethane Mole Fraction (x, y)

0.8

370

(b)

P = 6894.8 kPa

Temperature (K)

330

T-y

290

T-x

250

210

0

0.2

0.4

0.6

Methane Mole Fraction (x, y)

0.8

Figure 3.9. Temperature-composition diagram for (a) ethane/propane at 2758 kPa, and (b)

methane/H2S at 6894.8 kPa.

88

Figure 3.9(a) shows the uncertainty propagation in both bubble curve and dew curve is

similar and the uncertainties of temperatures and vapour phase compositions on the dew curve

can be calculated based on the bubble-point temperature calculations at a known pressure and

corresponding liquid phase compositions. The calculated values of temperature and ethane

composition in both liquid and vapour phases and associated uncertainties are shown in Table

3.8. The uncertainty of the bubble point temperature is of the same order of magnitude as of the

dew point temperature at any equilibrium point; however, at temperatures below the critical

temperature of ethane (305.36 K) the uncertainty of bubble temperatures is slightly greater than

of dew temperatures whereas at higher temperatures this trend is inverted.

Table 3.8. Calculated VLE data and their uncertainties for ethane/propane mixture at

P=2758 kPa using the technique developed in this work.

Bubble Curve

T

Dew Curve

x

336.61 0.52

0.0200 0.0003

336.61 0.52

0.0286 0.0005

334.42 0.52

0.0700 0.0010

334.42 0.53

0.1000 0.0015

331.11 0.52

0.1404 0.0017

331.11 0.56

0.2000 0.0025

327.49 0.54

0.2120 0.0021

327.49 0.60

0.3000 0.0029

323.50 0.56

0.2856 0.0022

323.50 0.64

0.4000 0.0030

319.04 0.58

0.3625 0.0021

319.04 0.66

0.5000 0.0026

314.00 0.59

0.4447 0.0017

314.00 0.65

0.6000 0.0020

310.48 0.59

0.5000 0.0014

310.48 0.62

0.6623 0.0016

308.17 0.59

0.5356 0.0013

308.17 0.59

0.7000 0.0014

301.18 0.55

0.6415 0.0016

301.18 0.49

0.8000 0.0014

292.25 0.44

0.7776 0.0025

292.25 0.32

0.9000 0.0016

279.59 0.18

0.9900 0.0003

279.59 0.18

0.9968 0.0001

89

The same pattern can be seen between uncertainties in the liquid phase compositions and

vapour phase compositions. Moreover, the bubble point temperature at a liquid composition of

0.5 and the dew temperature at a vapour composition of 0.5 have the highest uncertainties. As

presented in Figure 3.9(a), both the bubble and dew curves are narrow near the boiling

temperature of ethane, which is indicates a smaller uncertainty in this region. On the other hand,

near the boiling point temperature of propane, the uncertainty in compositions is low while the

uncertainty of temperature is still high. Therefore, it can be concluded that the uncertainty

propagation for this binary mixture depends on temperature and compositions in both phases, as

one would expect.

The uncertainty propagation for methane/H2S TXY diagram, Figure 3.9(b), shows a

different pattern when compared to the ethane/propane mixture. The higher uncertainty can be

seen in bubble point curve in comparison with the dew point curve and does increase as

temperature is decreased. The PXY diagrams are also constructed using the bubble-point

pressure calculation at a known temperature and liquid phase compositions for these mixtures.

Figure 3.10 shows PXY diagrams for ethane/propane at 310 K and methane/H2S at 320 K. The

maximum uncertainty of the dew point pressure for methane/H2S mixture occurred around a

methane liquid composition of 0.33 which is the cricondenbar at this temperature. The

magnitude of the propagated uncertainty depends on the phase behaviour of the mixture at the

condition being examined and the specific location in the thermodynamic space.

90

5000

(a)

T = 310 K

Pressure (kPa)

4000

P-x

3000

P-y

2000

1000

0

0.2

0.4

0.6

Ethane Mole Fraction (x, y)

0.8

14000

(b)

T = 320 K

12000

P-x

Pressure (kPa)

10000

8000

P-y

6000

4000

2000

0

0.1

0.2

0.3

Methane Mole Fraction (x, y)

0.4

0.5

Figure 3.10. Pressure-composition diagram for (a) ethane/propane at 310 K, and (b)

methane/H2S at 320 K.

91

At the beginning of this chapter, the minimum number of stages required for a deethanizer was calculated using the Fenske equation, Eqution 3.2, and its uncertainty was

evaluated by the error propagation equation, Equation 3.3, using the experimental VLE data and

their uncertainties taken directly from the literature, labeled Approach I. In this section, the

minimum number of stages and their uncertainty for the de-ethanizer with the same

specifications are now calculated using the model and binary interaction parameters developed

for the ethane/propane mixture taking into account their uncertainties. It should be stressed that

since in this case study the product purity (x1) as an input variable required for calculation is

uncertain, its associated uncertainty must be considered for uncertainty evaluation of T and y1 for

both distillate and bottom products. Therefore, it is necessary to generate a sample set for x1D (or

x1B) over its range of uncertainty in addition to the other uncertainties for input variables. The

equilibrium temperatures and vapour phase compositions and their uncertainties for both top and

bottom products at known pressure and liquid phase compositions were calculated by the Monte

Carlo technique for each sample using the bubble-point temperature calculation as previously

discussed. Table 3.9 shows the equilibrium data for both the distillate and bottom products and

their uncertainties determined using the Monte Carlo technique.

Product

x1

Temperature

y1

Distillate (D)

0.9900 0.0050

279.59 0.30

0.9968 0.0014

Bottom (B)

0.0200 0.0050

336.61 0.56

0.0286 0.0064

92

Two approaches, Approach II and Approach III, were employed to calculate the

required minimum number of equilibrium stages and their uncertainty using the calculated VLE

shown in Table 3.9. In Approach II, the required minimum number of equilibrium stages is

calculated by Fenske equation, Equation 3.2, and its uncertainty is estimated by Equation 3.3 as

in Approach 1 but now using the calculated VLE data and their uncertainties. The result based

on this approach is 12 6.

Note, the error propagation equations, Equations 3.1 and 3.3, were derived using the

simplifying assumption that there is no correlation between compositions in both phases, while

any one of the compositions (in liquid or vapour phase) can be determined from the

thermodynamic model at a given pressure. Therefore, Approach III is proposed wherein the

Monte Carlo technique along with the LHS method is used to evaluate the uncertainty in the

minimum number of stages for the de-ethanizer. In this approach, an input sample consisting of

the pure component physical properties, model parameters, binary interaction parameters, and

both top and bottom product purities (x1) are generated and the corresponding vapour phase

compositions and the minimum number of stages are calculated by the thermodynamic model

and Equation 3.2 for each sample set. Finally, the mean value and the uncertainty of the Nmin are

evaluated as the Monte Carlo output variables. Based on this approach, the correlation between

liquid phase composition and vapour phase composition is part of the calculation.

The results of the three calculation approaches are summarized in Table 3.10. The results

show that ignoring the correlation between equilibrium compositions can significantly affect the

quality of the final results. It is interesting to note that the propagation calculations neglecting the

correlation between equilibrium compositions overestimate the uncertainty by a significant

number of stages, underlining the usefulness of the Monte Carlo technique.

93

It can be concluded that that Approach III is reasonable and the best in terms of the

uncertainty in the minimum number of stages, since the correlation between the liquid and

vapour phase compositions are taken into account in a natural and straightforward way. These

results suggest that if one is to obtain reliable estimates for the uncertainty of process variables

calculated using unit operation models that encoded thermodynamic uncertainty information,

Monte Carlo is a powerful technique for simulations of any degree of complexity. The trade-off

compared to a traditional analytical error propagation schemes based on differentials and

repeated use of chain rule is greater computer time.

Table 3.10. Comparison of the minimum number of stages using different approaches

applied in this work.

Calculation Method

Nmin

Approach I

12 10

Approach II

12 6

Approach III

12 1

In Chapter 2, a compressor/cooler example was used to estimate the uncertainties in the

process propagated from the uncertainties in pure component properties. The example is

revisited here, now by taking into account the uncertainties of the thermodynamic model and the

binary interaction parameters along with the uncertainties previously considered. Figure 3.11

shows the schematic for the process. Since, VLE data for n-dodecane is not reported in TDE and

it is also not in the database developed in this work, n-decane is considered instead as a heavy

trace component present in natural gas.

94

Q

T = 298.15 K

P = 2068.43 kPa

T = 322.05 K

P = 6136.33 kPa

P = 6205.28 kPa

Cooler

Compressor

The results for two gas compositions used, one with 0.999 methane and 0.001 n-hexane

(Composition 1) and another with 0.9999 methane and 0.0001 n-decane (Composition 2), are

summarized in Table 3.11. The pressure-temperature envelope for Composition 2 with

associated uncertainty region calculated using the Monte Carlo technique and the VMGSim

process simulator is shown in Figure 3.12. The uncertainty introduced in intercooler duty,

compressor horse power and compressor outlet temperature is negligible, while the positions of

the cricondenbar and cricondentherm present more uncertainty.

Table 3.11. Basic equipment performance data and their uncertainties revisited in this

work.

Temperature after

Compressor, K

Compressor Horse

Power, HP

Intercooler Duty,

kJ/h

Composition 1

383.53 0.01

549.7 0.2

1,325,900 400

Composition 2

383.72 0.01

550.1 0.2

1,326,100 400

95

10000

Pressure (kPa)

8000

6000

4000

2000

0

120

140

160

180

200

220

Temperature (K)

240

260

280

300

The uncertainty in the locations of the cricondenbar, cricondentherm and critical point for

both compositions are shown in Table 3.12. Of particular interest is the cricondentherm

uncertainty, calculated to be in the order of 2 K for Composition 2. The dew point of gas at the

compressor inlet pressure and output pressure is an important factor for the definition of the

compressor inlet temperature and the selection of intercooler operating temperature, which can

affect the operation of the compressor stations.

Table 3.12. Positions of the cricondenbar, cricondentherm and critical point calculated

using the Monte Carlo simulation.

Cricondenbar

Cricondentherm

Critical Point

6510.34 57.86

216.73 0.49

2675.59 14.74

243.32 0.73

4801.04 11.54

192.32 0.06

Composition 2

Pressure (kPa)

8703.67 215.23

Temperature (K)

236.98 1.05

2364.71 42.16

286.54 1.89

4663.68 8.71

191.04 0.02

Composition 1

Pressure (kPa)

Temperature (K)

96

3.7 Conclusions

In Chapter 2, a comprehensive database for pure components basic physical properties and

thermodynamic models was developed by taking into consideration the uncertainty information

of available data. In this chapter, the discussion was extended to mixtures and uncertainty

information of binary interaction parameters (kij) for the re-parameterized PR model along with

the simple quadratic mixing rules. The presented method is generally applicable and could be

employed with any other thermodynamic model and mixing rule.

A comprehensive database for vapourliquid equilibrium data of 87 binary mixtures with

their uncertainty information was developed based on the NISTs TDE software and reviewing

the original literature cited, therein. The database includes experimental values and uncertainties

of temperature, pressure, liquid phase compositions and vapour phase compositions which are

fundamental for the estimation of the binary interaction parameter and its uncertainty in a

thermodynamic model.

A thermodynamic consistency test was performed using the method suggested by

Valderrama and Fandez and the database developed in this study. The method determines the

consistency of an isothermal experimental VLE dataset that is well correlated by the PR/Wong

Sandler/ van Laar thermodynamic model. The optimal values of model parameters were found

by nonlinear regression. Isothermal VLE datasets which are thermodynamically inconsistent or

were not correlated by the defined model were removed from the accepted VLE database and

were not used for estimation of binary interaction parameters. Available data are considered as

tentative data if there is no consistent data or there is no isothermal dataset for a system. The

application of this method was illustrated through the performed consistency test for two binary

mixtures of ethane/propane and methane/H2S.

97

Binary interaction parameters were optimized using weighted least squares method,

taking into account the uncertainties of all process variables of VLE data through the objective

function suggested by Anderson and Prausnitz, and the uncertainty of the fitted parameters is

evaluated using the procedure similar to the bootstrap approach using the Monte Carlo

simulation along with the LHS method.

The Monte Carlo technique was used in this chapter to evaluate the error propagation in

saturation calculations, minimum number of stages calculations, compression duties, and phase

envelope calculations. A brief study of sample size was conducted through comparison of the

results obtained for three different sample sizes for two binary mixtures of ethane/propane and

methane/H2S. Since the results with different sample sizes are essentially the same, it is

suggested that relatively small sample sizes in the order of 100 are adequate, although no strict

proof is presented.

98

Properties Natural Gas Dew Points and Gasoline Reid Vapour Pressures 3

4.1 Abstract

A simple, consistent, and self-contained error propagation algorithm was developed using the

uncertainty information of pure component physical properties, binary interaction parameters,

and thermodynamic model parameters combined with the Monte Carlo simulation and the Latin

Hypercube Sampling (LHS) method. This algorithm can be used to simulate the error

propagation in process flow sheets of arbitrary complexity as long as the thermodynamic model

parameters encode uncertainty information. In this chapter, two significant problems related to

hydrocarbon processing are studied using uncertainty analysis. First, the injection of a valuable

liquid hydrocarbon , n-butane, into an existing natural gas pipeline was studied in order to find

the optimum injection rate of liquid n-butane that can be safely added to the flowing gas without

undesired condensation. The main factors considered in this calculation are the hydrocarbon dew

point, the natural gas physical properties, and conformity to pipeline specifications. Second,

uncertainties in Reid vapour pressure (RVP) calculations were taken into account for the

calculation of the optimal rate of liquid n-butane blending into gasoline. Gasoline blending is an

important operation in refineries where gasoline must be produced with enough volatility for the

proper operation of engines in cold climates.

Reprinted with permission from S. Hajipour, M.A. Satyro, M.W. Foley, Uncertainty Analysis Applied to

Thermodynamic Models and Fuel Properties Natural Gas Dew Points and Gasoline Reid Vapour Pressures,

Energy & Fuels, DOI: 10.1021/ef4019838. Copyright (2013) American Chemical Society. It should be noted that

the content of this chapter includes the extensions beyond the cited journal paper.

99

4.2 Introduction

In Chapter 2, a comprehensive database for pure hydrocarbons containing basic physical

properties and associated uncertainties, two correlations for estimation of pseudo-components

properties with required uncertainty information, and the variance-covariance matrix for the reparameterized PengRobinson equation of state parameters were developed. In Chapter 3, a

database for 87 binary mixtures containing the experimental values of vapourliquid equilibrium

(VLE) data and their uncertainties was developed and the re-parameterized PengRobinson

equation of state [8] was extended to mixtures using simple quadratic mixing rules. Binary

interaction parameters and their uncertainties were evaluated using a thermodynamically

consistent VLE database taking into account the uncertainties of measured binary data.

With the available uncertainty information for pure components, model parameters, and

binary interaction parameters, it is now possible to perform a rigorous uncertainty analysis for

process simulation/design through a self-contained and consistent computational procedure. In

this chapter, a simple error propagation algorithm integrated with an internally consistent

thermodynamic data set and correlations along with associated uncertainties was developed and

coupled with the VMGSim process simulation software [7] to evaluate the effect of

thermodynamic uncertainties on the simulation results.

4.2.1 Liquid Hydrocarbon Injection into an Existing Natural Gas Pipeline

In this process, liquid hydrocarbon is injected into the natural gas existing pipeline in order to

increase the pipeline capacity and/or heating value of the gas. This approach allows for the

transportation of high value hydrocarbon liquids in a gas pipeline. The amount of liquid

100

hydrocarbon that can be safely injected into the pipeline is controlled by the hydrocarbon dew

point of the gas and the existing pipeline specifications.

Commonly used cryogenic fluids such as liquefied natural gas (LNG) and liquefied

petroleum gas (LPG) or a mixture of hydrocarbons such as propane and butane with air are

added to the gas pipeline in the supply and distribution of natural gas to increase the capacity

during peak demand periods [89, 90]. A liquid hydrocarbon, normally butane, is sometimes

added to fuel gas to increase the heating value of the gas used to provide energy in refining

processes [91].

Stark et al. [89] presented an innovative method and apparatus for adding LNG or a

mixture of hydrocarbon/air to plant fuel gas pipelines using a Venturi jet. Different injection

possibilities were tested in which the kinetic energy of the flowing gas is used to aspire the

cryogenic liquid into the high pressure gas stream and the heat content of the flowing gas stream

is used to supply the latent heat of vaporization. The amount of injected liquid is determined by

the temperature of the pipeline or the gravity specification of the natural gas. They claimed that

using the Venturi system reduces the capital investment and required power by eliminating the

need for pumps or compressors to increase the pressure of the injected liquid and vaporizers to

supply the energy required for liquid vaporization.

On the other hand, Arenson [90] claimed that the liquefied cryogenic fluid must be

preheated, vaporized, and superheated prior to injection into the flowing gas, and therefore he

provided a new method to vaporize and inject the cryogenic gas. The possibility of condensation

and controlling the amount of liquid hydrocarbon added to the gas were not discussed by this

author. While Chin and co-workers [91] invented a device to control the amount of butane

injected into fuel gas that was based on monitoring the butane saturation temperature of the gas.

101

Regardless of the method used for the injection, the main objective of this study is to

investigate the effect of variation in the liquid hydrocarbon injection rate on the calculated dew

point. As previously discussed in Chapters 2 and 3, the uncertainty of input parameters affects

the calculation of the dew point of the natural gas and this effect would be significant in the

presence of a trace amount of heavy components. Therefore, uncertainty analysis using the error

propagation algorithm is performed to estimate the optimum amount of liquid hydrocarbon that

can be safely injected into the existing gas pipeline without liquid formation.

4.2.2 Gasoline Blending

Gasoline is a complex mixture of many different hydrocarbons and its composition varies

depending on the crude oil source, refining process, and additives. There are standard

specifications established by American Society for Testing of Materials (ASTM) for gasoline

dealing with the performance requirements such as volatility [92]. In order to meet the standard

specifications for a product, different gasoline cuts are blended together with additives and

lighter hydrocarbons.

The volatility of the gasoline blend is one of the most important properties affecting the

performance of engines and their ability to function properly independent of the weather.

Volatility is directly related to the Reid vapour pressure (RVP) [93] which is the vapour pressure

of the gasoline blend at 310.93 K (100 F) measured using a specific apparatus and vapour

fraction. The maximum allowable limit of the RVP varies with seasonal temperature changes and

geographical location.

In the summer and in high altitude regions, it is important to have a lower RVP gasoline

to reduce evaporation losses and prevent vapour lock. On the other hand, in the winter and in low

102

altitude areas, a higher RVP gasoline must be produced to improve engine starting characteristics

[93, 94]. As such, the RVP ranges from 49.64 kPa (7.2 psia) in the summer to 93.08 kPa (13.5

psia) in the winter [94]. Since n-butane is a relatively inexpensive, has a lower sales value than

gasoline on a volume basis, and has a high RVP equal to 358 kPa (52 psia), it is often used in

refineries as a blending component to produce gasolines with required RVP specifications.

In this section, the use of the error propagation algorithm to evaluate the amount of nbutane to be added to a gasoline to produce a desired RVP is demonstrated. Since the RVP of

the gasoline depends on the quantity and RVP of each component in the blend, the uncertainty in

vapour pressure of each individual component affects the quality of the overall RVP calculation.

As previously shown in Chapter 2, uncertainties of input parameters affect the quality of the

calculated vapour pressure of pure components. Therefore, physical property uncertainties

influence the quality of the overall RVP calculations and must be taken into account for reliable

calculation of the amounts added during blending.

4.3 Development of the Error Propagation Algorithm

When calculating any quantity of interest through mathematical relations, the uncertainties

associated with the independent variables are propagated into the final quantity. Evaluation of

the uncertainty in the final result using the principles of error propagation based on Taylor

linearization is an exceptionally tedious procedure [8] and difficult to generalize from a process

simulation point of view. Therefore, the error propagation equation is rarely used in evaluation of

uncertainties in complex calculations.

In Chapter 2, it was demonstrated that a novel version of the Monte Carlo method can be

used for the error propagation calculations for flow sheets of any complexity. This method is

103

simple, adaptable, and reasonably fast for complex computations. The basic requirements of a

self-contained and consistent error propagation algorithm for physical property calculations are

described in detail in Chapters 2 and 3. A very brief summary of its major points follows.

The sequence for the overall error propagation evaluation is shown in Figure 4.1 as a

block flow diagram. For pure components, critical temperature, critical pressure, and acentric

factor data and their associated uncertainties are taken from the pure component database

developed in Chapter 2. The re-parameterized RiaziDaubert or LeeKesler models [8] and their

variance-covariance matrices of model parameters are used for estimation of critical properties

and acentric factors for any undefined oil fractions or plus fractions and their uncertainties. The

re-parameterized PengRobinson equation of state and associated variance-covariance matrix [8]

along with the van der Waals quadratic mixing rules are used for thermodynamic calculations,

and binary interaction parameters and their uncertainties are taken from the database evaluated

for 87 binary mixtures and used for mixture calculations [9].

In order to use the Monte Carlo technique for error propagation, it is assumed that all

input uncertainty values are characterized by normal (Gaussian) distributions with standard

deviations equal to one half of their uncertainty values based on the 95% confidence interval

(CI). It should be stressed that the application of the proposed error propagation method rests

solidly on the applicability of a thermodynamic method for the modelling of the behaviour of

pure components and mixtures. In other words, the thermodynamic models should be devoid of

consistent bias when estimating relevant pure component properties such as vapour pressures and

mixture properties such as saturation pressures or vapour fractions. Thermodynamic models must

thereby be constructed using the best practices related to data regression and should be verified

before use for extensive error propagation calculations.

104

Internal Database

Pure Component Database [8]

Critical properties and uncertainties

Acentric factors and uncertainties

Characterization

models

for

undefined

oil

Binary Mixtures Database [9]

Vapour-liquid

equilibrium

(VLE)

data

and

uncertainties

Binary interaction parameters and uncertainties

Thermodynamic Models [8, 9]

Re-parameterized Peng-Robinson equation of

state and variance-covariance matrix

van der Waals quadratic mixing rules

Simulation

Monte Carlo

Process Simulation

Technique

by VMGSim [7]

Uncertainty Evaluation

The LHS method [6] is used to generate a sample set containing all input parameters

subject to uncertainty. The sample size (100) was determined from studies previously completed

in Chapters 2 and 3, and is used in this chapter without modification. The quantities of interest

105

and their associated uncertainties are calculated through multiple simulations. The distribution of

the calculated quantities shows the effect of the input uncertainties. The mean value of the

calculated quantities is reported as the true value with the uncertainty equal to two times of the

standard deviation. This approach is similar to Whiting et al.s method [15] for studying the

uncertainty of process performance, the main difference being the use of a comprehensive

database of thermodynamic parameters with associated uncertainties.

4.4 Case Study Problems

4.4.1 Injection of Liquid n-Butane into an Existing Natural Gas Pipeline

Although it is desirable to maximize the amount of liquid hydrocarbons in the natural gas in

order to maximize the hydrocarbon transport capacity and heating value of the gas, the injection

of liquid hydrocarbons is limited by the dew point of the components and the specifications for

the existing pipeline. With too much injection of liquid hydrocarbon into the pipeline, the gas

will be oversaturated, and some of the mixture will condense.

One of the essential factors in gas pipeline design is avoiding the condensation of liquid

hydrocarbons. Increased pressure drop, capacity reduction, and pipeline equipment problems

such as compressor damage are the main issues caused by hydrocarbon liquid dropout. In order

to prevent hydrocarbon condensation, the operating temperature of the pipeline must be kept

above the hydrocarbon dew point shown in the pressure-temperature (PT) envelope. Figure 4.2

represents a typical PT envelope of a natural gas that shows the effect of the operating

temperature of the pipeline on hydrocarbon condensation and indicates that the condensation

occurs at the temperatures (T2) lower than the dew point temperature.

106

Critical point

Vapour Phase

Pressure

Liquid Phase

T2,P

T1,P

Vapour-Liquid Phase

Dew Point

Temperature

Figure 4.2. Pressure-temperature (PT) envelope for a natural gas and thermodynamic

positions of the pipeline with temperatures of higher (T1) and lower (T2) than dew point

temperature at pressure of P.

The effect of uncertainty on the dew point calculation is illustrated through the injection

of liquid n-butane into an existing natural gas pipeline designed to transport a maximum natural

gas flow rate of 25.49 MMSCMD (900 MMSCFD) at 288.71 K (60 F) from a source (A) to a

delivery location (B), 130 km away, with a delivery pressure of 5515.8 kPa (800 psia). The

composition of the gas and the pipeline specifications are given in Table 4.1 and Table 4.2,

respectively.

107

Component

Mole Fraction

Oxygen

0.0002

Nitrogen

0.0149

Carbon dioxide

0.0070

Methane

0.9500

Ethane

0.0250

Propane

0.0020

i-Butane

0.0003

n-Butane

0.0003

i-Pentane

0.0001

n-Pentane

0.0001

n-Hexane

0.0001

Table 4.2. Existing natural gas pipeline specifications used in this work.

Specs

Nominal Pipe Size (NPS)

30 in

0.5 in

1.810-5 m (0.0007 in)

Roughness

Length

130 km

Pressure

Temperature

Max. 323.15 K

Min. 36 MJ/m3

Max. 41 MJ/m3

a

108

In order to calculate the number of compressor stations, the required mechanical work to

be supplied by the compressors, the compressor discharge temperature, and the intercooler duty,

the existing natural gas pipeline was simulated using VMGSim [7]. To simplify the simulation,

the number and location of the compressor stations required to transport the natural gas were

calculated by neglecting temperature and elevation differences along the pipeline. The reparameterized PengRobinson equation of state [8] was used for the process calculations, and the

pure component critical properties, acentric factors, and binary interaction parameters are

available in the databases developed in Chapters 2 and 3.

For the design of the pipeline, it was assumed that the first compressor station at point A

has a discharge pressure of 7584.2 kPa (MAOP) and the intercooler outlet temperature is 288.71

K. The intermediate compressor station is located halfway between A and B (65 km) with a

suction and discharge pressure of 5515.8 kPa and 7584.2 kPa, respectively. The simulation

results show that the natural gas can be transported to B using only two compressor stations and

that the gas pressure at the delivery point would be greater than 5515.8 kPa which can be

controlled by a back pressure regulator. The schematic view of the gas pipeline is shown in

Figure 4.3.

Cooler

Compressor station I

(A)

To B

P=5515.8 kPa

Compressor

Separator

Compressor station II

Figure 4.3. Schematic view of the existing natural gas pipeline used in this work.

109

The basic information for the equipment associated with the uncertainties propagated

from the uncertainties in all input variables including pure components properties, binary

interaction parameters, and thermodynamic model parameters are summarized in Table 4.3. The

uncertainty analysis was performed using the error propagation algorithm previously described,

assuming that the inlet and outlet temperatures and pressure drop of the intercooler, and the

adiabatic efficiency and pressure ratio of the compressor are specified with no associated errors.

Note if uncertainty information of these parameters was available, they could easily be used in

the Monte Carlo simulations.

Equipment

Compressor

Specifications

Adiabatic efficiency (%)

Pressure ratio

Inlet temperature (K)

Adiabatic work (kW)

80

1.375

288.71

10,825.1 6.2

Outlet temperature (K)

Pressure drop (kPa)

Duty (MJ/h)

323.15a

288.71

68.95

19,803.4 9.2

Intercooler

Since the hydrocarbon dew point calculation is strongly dependent on the composition of

natural gas, especially its heaviest components, the dew point of the gas will change due to the

injection of n-butane. The maximum allowable hydrocarbon dew point of 263.15 K is the

specification for the existing pipeline. By increasing the amount of n-butane in the gas stream,

the hydrocarbon dew point increases, therefore, the injection rate of liquid n-butane is limited by

110

this specification. In this study, the maximum allowable amount of n-butane was calculated

using VMGSim assuming that the liquid n-butane is injected after the first compression station,

point A, and that the pressure of the pipeline does not change during the mixing process as a

result of the small amounts of liquid n-butane injected into the natural gas. Also, the flow rate of

the final gas mixture was kept constant at the maximum gas flow rate of 25.485 MMSCMD.

Without taking into account the uncertainties, the maximum standard flow rate of nbutane is 137.52 m3/hr (116,550 ft3/day) which is added to 24.7 MMSCMD (872.26 MMSCFD)

of natural gas. The ratio of the added liquid n-butane to the transported natural gas is equivalent

to 0.0134% in standard volume (in other words, without taking into account the vaporization of

n-butane that will happen at the actual pipeline condition). As shown in Chapters 2 and 3, the

dew point calculation is also dependent on the uncertainty of the input parameters used in the

thermodynamic model. Since results from a simple dew point calculation are obtained without

taking into account the input uncertainties, the calculation is not complete from uncertainty

analysis point of view and therefore under- or over-estimation has to be applied to the calculated

amount of liquid n-butane.

4.4.2 Gasoline Blending

Blending n-butane into gasoline not only increases the RVP of the gasoline but also increases the

capacity of the gasoline supplies and reduces the gasoline price [95]. The amount of n-butane

that can be added to the blend is limited by the gasoline product specifications such as RVP.

Addition of n-butane increases the RVP and the tendency of gasoline to vaporize at high

temperatures and high altitude areas. The presence of vapour in the fuel line and the combination

of the vapour and liquid feeding the fuel pump interrupts the normal car engine operation and

111

presents a safety hazard. Similarly, gasoline with too low a RVP does not provide enough

volatility to start the engine in cold weather. In order to minimize gasoline evaporation, the

amount of n-butane in gasoline blending process must be controlled [94].

This process is illustrated by blending n-butane into 331.23 m3/hr (50,000 bbl/day) low

RVP gasoline at standard conditions, with the chemical composition given in Table 4.4, in order

to increase RVP from 70.72 kPa (10.26 psia) to 93.08 kPa (13.5 psia). Although a mixture of

pure compounds does not truly represent physical and chemical characteristics of gasoline, this

simplifying assumption is reasonably accurate, and a surrogate for gasoline is represented as a

mixture of pure compounds. The chemical composition proposed by Kreamer and Stetzenbach

[96] as a reference surrogate Low RVP gasoline for environmental research studies is used in

this study.

Table 4.4. Low RVP gasoline blend chemical composition.

Compound

i-Butane

n-Butane

i-Pentane

n-Pentane

n-Hexane

n-Heptane

2,2,4-Trimethylpentane

n-Octane

2-Methyldecane

2-Methyl-2-butene

2,3-Dimethyl-1-butene

Benzene

Toluene

m-Xylene

o-Xylene

p-Xylene

1,2,4-Trimethylbenzene

i-Butylbenzene

a

Weight Fraction a

0.030

0.030

0.050

0.050

0.050

0.050

0.050

0.140

0.050

0.050

0.050

0.020

0.150

0.034

0.033

0.033

0.080

0.050

112

0.0393

0.0379

0.0589

0.0585

0.0555

0.0535

0.0528

0.1463

0.0499

0.0553

0.0541

0.0167

0.1267

0.0289

0.0275

0.0281

0.0671

0.0430

After selecting the gasoline stock, the quantity of n-butane required to give the desired

RVP was calculated using VMGSim [7]. For the calculation, the input properties of pure

components (critical properties and acentric factors) were taken from the database previously

developed in Chapter 2. The critical properties of xylene(s) and 2-metyldecane which are not

available in the database were taken from ThermoData Engine (TDE) [2], and the acentric

factors associated with uncertainties were calculated using a similar approach to that of the

developed database [8]. The properties of these components are shown in Table 4.5.

Tc (K) a

Pc (kPa) a

m-Xylene

616.85 0.56

3540 13

0.328 0.002

o-Xylene

630.43 0.61

3745 25

0.312 0.003

p-Xylene

616.19 0.15

3528 16

0.323 0.002

2-Methyldecane

624.10 9.70

1811 23

0.545 0.006

Compound

Since the database of the binary interaction parameters [9] was developed based on the

components present in natural gas, the uncertainty information of binary interaction parameters

for some of the components considered in this case study are not available. For these binaries,

the calculation was done using the default binary interaction parameters provided by the

VMGSim for the Advanced PengRobinson (APR) [51]. The expansion of the database to

include the missing binary interaction parameters and their uncertainties is straightforward as

discussed in Chapter 3. In this example, the uncertainty analysis was conducted by taking into

account only the uncertainties of the critical properties and acentric factors of each of the

113

individual components and using the APR equation of state, and the uncertainties related to

thermodynamic models and binary interaction parameters were not considered.

Without taking into consideration the uncertainties of input parameters, the RVP of the

gasoline with the specified composition is 70.72 kPa (10.26 psia) and the flow rate of n-butane

required to provide a RVP equal to 93.08 kPa is 23.73 m3/hr (3582.44 bbl/day) at standard

conditions. The volume of the blended n-butane is equivalent to 7.17% of the initial volume of

the gasoline at standard conditions. Similarly to the dew point calculation, the RVP also depends

on the composition. Consequently, the uncertainty analysis was carried out and used to provide

an estimate of the under- or over-estimation of the blended n-butane rate.

4.5 Uncertainty Analysis Results and Discussion

In this section, the uncertainty in dew point and Reid vapour pressure calculations was quantified

using the error propagation algorithm developed in section 4.3. The uncertainty analysis results

provide an estimate for the rate of n-butane that can be safely added to the natural gas stream and

gasoline blend to meet the required specification.

For the first case study, depending on the amount of liquid hydrocarbon injected into the

pipeline, the composition of the gas will change and hence the dew point of gas will vary. The

uncertainty analysis was used to estimate the safe flow rate of injected n-butane based on the

uncertainty of dew point of gas at 5515.8 kPa.

In the previous section, a maximum standard flow rate of 137.52 m3/hr was estimated for

n-butane by setting the dew point of final gas mixture to 263.15 K without considering the

uncertainties in the input parameters. In order to find the uncertainty of dew point with the

maximum injection and compare the design parameters of the process after injection with the

114

existing pipeline specifications, the uncertainty analysis was performed using the Monte Carlo

method with the LHS sampling. Figure 4.4 shows the PT envelopes and associated uncertainties

for the natural gas before and after the n-butane injection. Points A and B in this figure indicate

the thermodynamic positions of the source and delivery locations. As shown in Figure 4.4, the

dew point curve is strongly affected by changing the gas composition, and increasing the amount

of n-butane in the gas leads to a significant increase in cricondentherm. This effect was

previously discussed in Chapter 2.

10000

After injection

Before injection

8000

A

Pressure (kPa)

Pipeline Spec

(Max. Dew-point)

6000

B

4000

2000

0

130

150

170

190

210

230

Temperature (K)

250

270

290

Figure 4.4. Pressure-temperature envelopes for a natural gas before and after the liquid nbutane injection.

The results of uncertainty analysis for the natural gas before and after the injection are

summarized in Table 4.6. As indicated in this table, there is no dew point reported for the natural

115

gas before injection at 5515.8 kPa, since that pressure is greater than the cricondenbar and there

is no possibility for condensation of the gas at that pressure by temperature reduction. The

calculated dew point of the gas after injecting 137.52 m3/hr liquid n-butane is 263.15 0.34 K at

5515.8 kPa.

Property

Before Injection

After Injection

137.52

218.18 0.77

263.35 0.34

2529.8 41.3

4978.0 12.5

199.65 2.60

239.10 0.20

5257.3 24.6

9110.5 39.4

263.15 0.34

For clarification purposes, the zoomed-in version of the PT envelope of gas after

injection and the distribution of dew points calculated using the Monte Carlo for 100 sample sets

are shown in Figure 4.5(a) and 4.5(b), respectively. Figure 4.5(a) shows a maximum dew point

located in the retrograde condensation region with the hydrocarbon dew points being greater than

263.15 K at 5515.8 kPa, and therefore gas will be condensed at the specified condition. Figure

4.5(b) also shows that half of the Monte Carlo (MC) results are located above the maximum

allowable dew point line. Two green dashed-dotted lines show the lower and upper limits of the

calculated dew points at 5515.8 kPa which represent the uncertainty of the dew point on the 95%

confidence interval (CI).

116

6000

(a)

Pressure (kPa)

5500

Pipeline Spec

(Max. Dew-point)

5000

4500

4000

261

262

263

264

Temperature (K)

263.8

MC results

95% CI

Max. allowable dew point

263.6

(b)

263.4

263.2

263.0

262.8

262.6

0

10

20

30

40

50

60

Sample Number

70

80

90

100

Figure 4.5. (a) The zoomed-in version of Figure 4.4 for pressure-temperature envelope of

gas after the injection of 137.52 m3/hr, and (b) Monte Carlo simulation results for dew

point calculation at 5515.8 kPa.

117

The uncertainty analysis shows that there is a possibility that the existing pipeline

specification cannot be met due to uncertainties in the physical properties and that the amount of

injected butane should be reduced. In order to find the maximum rate of n-butane such that the

upper limit of the calculated dew point at 5515.8 kPa is below 263.15 K, the uncertainty analysis

was performed for different standard volume amounts of the liquid n-butane injection. Figure

4.6(a) shows the results of uncertainty analysis. The intersection of the curve with the maximum

allowable dew point line (T=263.15 K) determines the maximum safe n-butane/gas standard

volume ratio which is shown more clearly in the zoomed-in version of the plot, Figure 4.6(b).

Therefore, the maximum safe standard volume ratio of the injected liquid n-butane to the

natural gas would be 0.0132% which is equivalent to 135.45 m3/hr of liquid n-butane at standard

conditions. The dew point temperature with the new injection rate was calculated using the error

propagation algorithm to ensure that the upper uncertainty of temperature is still below 263.15 K.

The reduction of n-butane injection rate from 137.52 m3/hr to 135.45 m3/hr leads to a reduction

of target dew point from 263.15 k to 262.71 K. Figure 4.7 shows the oscillation of data points

around 262.71 K with the uncertainty of 0.34 K indicated with two green dashed-dotted lines.

This type of guided determination of safety factors for design is one of the major benefits of

uncertainty analysis.

118

270

(a)

Max. allowable dew point @ 5515.8 kPa

260

250

240

230

220

0

0.005

0.01

Volume Ratio of the Injected n-Butane to Natural Gas (%)

265

0.015

(b)

263

261

259

0.012

0.013

Volume Ratio of the Injected n-Butane to Natural Gas (%)

0.014

Figure 4.6. (a) Calculated dew point and associated uncertainty at 5515.8 kPa against the

injected liquid/gas standard volume ratio, and (b) zoomed-in version of (a) in the vicinity of

maximum dew point.

119

MC results

Max. allowable dew point

95% CI

Mean dew point

263.2

263.0

262.8

262.6

262.4

262.2

0

10

20

30

40

50

60

Sample Number

70

80

90

100

Figure 4.7. Monte Carlo simulation results for the dew point calculation at 5515.8 kPa after

the injection of 135.45 m3/hr n-butane.

Since the aim of this process is to use the existing pipeline to transport the gas after

injection, it is also necessary to check that the current equipment can transport the gas with

different physical properties. In order to do so, the compressor and intercooler performance were

checked using the uncertainty analysis algorithm. Comparing the results shown in Table 4.7 with

those listed in Table 4.3 indicates that the current equipment can be used to transport the gas

without any changes since the adiabatic work of the compressor and duty of the intercooler

required to transport the gas are smaller than those of existing equipment.

Adding n-butane to the gas increases the specific gravity and ratio of specific heats which

are two main parameters in calculating of compressor work. Since the pressure ratio does not

change, increasing the values of these two parameters decreases the required compressor

horsepower. On the other hand, the specific heat of the gas increases after injection and leads to

120

an increase in the duty of the intercooler; however, it is still below the design duty of the existing

intercooler. The compressor outlet temperature was also calculated to ensure that the upper

uncertainty of temperature is below 323.15 K and did meet the pipeline specification.

Table 4.7. Physical properties of the gas and the pipeline equipment performance data

before and after the injection.

Property

Before Injection

After Injection

25.485

24.711

135.45

25.485

25.485

Specific gravity

0.583

0.626

33.98

36.35

37.67

40.21

262.71 0.34

288.71

288.71

Pressure ratio

1.375

1.375

80

80

10,825.1 6.2

10,529.1 8.6

316.22 0.01

315.10 0.01

316.22 0.01

315.10 0.01

288.71

288.71

68.95

68.95

46.29 0.02

50.08 0.03

15,858.0 6.4

16,455.5 9.0

3

Compressor

Intercooler

Inlet temperature (K)

Duty (kW)

121

The physical properties of gas including specific gravity and net and gross heating values

were also calculated, Table 4.7. The specific gravity of the gas increases from 0.583 to 0.626 due

to injection of 135.45 Sm3/hr of liquid n-butane. This significant increase in the gas specific

gravity results from the n-butane vaporization at pipeline conditions and its actual volume

fraction in the final gas is 3.04 actual volume percent corresponding to a volume flow increase of

0.774 MMSCMD. If there is a specified upper limit for the density of the gas, it should be

included in the determination of the safe injection amount. The heating value of the gas also

increases by increasing the amount of n-butane, but is still less than the maximum heating value

specified in Table 4.2.

Since the dew point temperature varies widely depending on the gas composition and

pressure of the pipeline and the model used for the calculation, it may vary by changing any one

of these parameters. Note, the effect of other compounds present in small quantities such as

methanol and ethylene glycol that may be injected as part of a hydrate formation prevention can

be quantified in the same way.

For the second case study, the uncertainty analysis was performed to estimate the safe

amount of blended n-butane into gasoline based on the uncertainty of RVP of the gasoline blend.

The uncertainty in the RVP calculation propagated from uncertainties of critical temperatures,

critical pressures, and acentric factors of each of 18 components of gasoline listed in Table 4.4

was estimated using VMGSim, the APR equation of state, and the Monte Carlo technique.

The simple calculation of RVP shows that 23.73 m3/hr of n-butane is required to increase

the RVP of the gasoline blend from 70.72 kPa to 93.08 kPa. The uncertainty analysis results

indicate that by blending of this amount of n-butane into the gasoline, there is a possibility that

122

the gasoline RVP will be greater than the maximum allowable value of 93.08 kPa for the final

blend.

The saturation pressure curves as a function of temperature and their associated

uncertainties for the gasoline blend before and after n-butane blending are shown in Figure 4.8

for the temperature range of 290330 K. The envelopes were constructed using the results of

Monte Carlo simulation for a sample size of 100 generated by the LHS method for 54 uncertain

input parameters. The uncertainty analysis shows that the RVP of the initial gasoline is 70.72

0.76 kPa (10.26 0.11 psia), and after blending of 23.73 Sm3/hr n-butane it will increase to

93.08 0.72 kPa (13.5 0.1 psia). The true mean values of RVP at initial and final conditions

are also indicated by dashed lines in this figure.

165

Before blending

Pressure (kPa)

140

After blending

115

RVP final

90

RVP initial

65

40

15

290

300

310

Temperature (K)

320

330

Figure 4.8. Pressure-temperature envelopes for the gasoline before and after n-butane

blending.

123

As shown in Figure 4.8, increasing the n-butane composition causes the bubble point

pressure and consequently the RVP to increase. Table 4.8 shows the values of calculated vapour

pressures and their estimated uncertainties at each temperature. The results would indicate that

the uncertainty of vapour pressure increases as temperature increases.

Table 4.8. Vapour pressures and uncertainties calculated using the Monte Carlo simulation

for the gasoline before and after n-butane blending at different temperatures.

Temperature (K)

Before Blending

After Blending

270

18.02 0.26

24.33 0.25

280

26.46 0.36

35.51 0.33

290

37.79 0.47

50.39 0.44

300

52.64 0.61

69.73 0.57

310

71.73 0.77

94.35 0.73

320

95.79 0.97

125.1 0.9

330

125.6 1.2

162.9 1.1

Figure 4.9 shows the result of Monte Carlo simulation as a function of the sample

number. The results are distributed around the maximum allowable RVP of 93.08 kPa (red

dashed line) with the maximum amount of 93.95 kPa at sample number 72 and the minimum

amount of 92.34 kPa at sample number 20. Two green dashed-dotted lines show the lower and

upper limits of RVP based on a 95% confidence interval (CI). For 50 points out of 100 points in

the sample set, the calculated RVPs are greater than 93.08 kPa, which represents excessive

amount of the blended n-butane.

124

MC results

95% CI

Max. allowable RVP

94.2

RVP (kPa)

93.8

93.4

93.0

92.6

92.2

0

10

20

30

40

50

60

Sample Number

70

80

90

100

Figure 4.9. Monte Carlo simulation results for the RVP calculation of the final gasoline

blend with 7.17 volume percent of blended n-butane.

In order to find the rate of n-butane based on the uncertainty analysis, the RVP of the

gasoline blend was calculated at different volume flow rates of n-butane using the Monte Carlo

technique. Figure 4.10 shows the RVP of the gasoline blend against the standard volume ratio of

the blended n-butane into 331.23 Sm3/hr of gasoline. The RVP at a volume ratio of zero

represents the RVP of the initial gasoline with an average value of 70.72 kPa. The red dashed

line indicates the maximum allowable RVP of the final blend (93.08 kPa). The numerical values

of the RVP and associated uncertainty estimated based on 95% confidence interval along with

the range of variations of Monte Carlo results of RVP are summarized in Table 4.9.

125

97

Max. allowable RVP

93

RVP (kPa)

89

85

81

77

73

69

0

2

3

4

5

6

7

Volume Ratio of the Blended n-Butane to Gasoline (%)

Figure 4.10. Calculated RVP and associated uncertainty against the blended nbutane/gasoline standard volume ratio.

Table 4.9. Results of uncertainty analysis of RVP calculation depending on the volume

ratio of the blended n-butane to gasoline at standard conditions.

Volume Ratio (%)

RVP (kPa)

0.00

70.72 0.76

69.94 71.61

1.00

74.09 0.75

73.30 74.95

2.00

77.36 0.75

76.25 78.22

3.00

80.55 0.74

79.78 81.42

4.00

83.67 0.73

82.90 84.54

5.00

86.72 0.73

85.96 87.58

6.86

92.19 0.72

91.45 93.06

7.17

93.08 0.72

92.34 93.95

8.00

95.47 0.71

94.72 96.32

126

The maximum volume ratio of the blended n-butane can be estimated using the results of

the uncertainty analysis such that the calculated RVP is always smaller than the specification

value of 93.08 kPa. The green arrow in Figure 4.10 shows that a value of 6.86 volume percent,

which is equivalent to 22.71 m3/hr of n-butane can be added to the 331.23 m3/hr gasoline at

standard conditions. The results of the uncertainty analysis at this volume ratio were listed in

Table 4.9. As shown in this table, the calculated RVP is 93.06 kPa which is smaller than the

maximum allowable RVP.

Figure 4.11 was developed for the clarity purposes to show the distribution of RVP

calculated for the gasoline blend with 6.86 volume percent using the Monte Carlo method. The

green solid line indicates the mean value of the calculated vapour pressures that would be the

true mean value of the reported RVP (92.19 kPa) and will be used as a new specification in the

gasoline blending process studied in this work, and the two green dashed-dotted lines indicate

the lower and upper limits of RVP variations with a 95% CI and represent the uncertainty of the

calculated RVP (0.72 kPa). The new specification for RVP can be determined rigorously using

the results of the uncertainty analysis such that the RVP does not exceed the defined

specification. Note, this type of analysis allows for the development of realistic safety parameters

for blending based on the uncertainty of the calculations instead of simply basing operational

guidelines on rules of thumb.

127

93.3

MC results

95% CI

Mean RVP

RVP (kPa)

92.9

92.5

92.1

91.7

91.3

0

10

20

30

40

50

60

Sample Number

70

80

90

100

Figure 4.11. Monte Carlo simulation results for RVP calculation of the final gasoline blend

with 6.86 volume percent of blended n-butane.

4.6 Conclusions

A consistent and self-contained error propagation using uncertainties in physical properties and

thermodynamic model parameters was used on two typical hydrocarbon processing problems.

This approach can provide valuable understanding about a process thanks to the calculation of

uncertainties of key operating or product specification parameters resulting from uncertainties in

the thermodynamic model and can assist engineers in providing realistic operational conditions

for safe equipment operation or reliable product production. Although not done here,

uncertainties resulting from process parameters such as temperatures, pressures, flows, and even

equipment performance can be easily implemented due to the process simulator modular

structure and the Monte Carlo algorithm.

128

One of the major advantages of the proposed uncertainty analysis is its ability to better

estimate safety factors in the design of processes or product specifications. This method was

used for the process of injection of liquid n-butane into an existing gas pipeline and also for the

process of blending of liquid n-butane to gasoline, to evaluate the error propagation in the dew

point calculation of natural gas and Reid vapour pressure calculation of gasoline.

The safe amount of liquid hydrocarbon that can be added to the existing natural gas

pipeline without resulting in hydrocarbon liquid dropout was found by taking into account the

uncertainties of the pure components properties, binary interaction parameters, and

thermodynamic model. The uncertainty in specifications for design of the existing pipeline and

equipment performance were also evaluated using the error propagation algorithm to ensure that

the injection of n-butane does not result in off-specification gas.

For the gasoline blending case, the safe rate of n-butane that can be added to gasoline,

without exceeding the RVP specification of the final blend, was calculated using the APR EOS

and default values of the VMGSim for the binary interaction parameters, by taking into

consideration only the uncertainties of pure components properties. The quality of the estimated

uncertainties for mixtures containing heavier hydrocarbons can be bettered through data

regression as discussed in Chapter 3. This self-contained and consistent computational procedure

can be used by modular process simulation systems such as VMGSim.

129

5.1 Conclusions

In this study, the reliability and accuracy of physical properties was identified as a main

parameter that has a significant impact on the quality of the process simulation and design.

However, this effect has been overlooked in commercial process simulators. This study

developed a new comprehensive mathematical procedure for error propagation calculations

based on uncertainties associated with the physical properties, binary interaction parameters, and

thermodynamic models commonly used for chemical process simulation and design.

Uncertainties related to process parameters such as process temperatures and pressures were not

considered in this study although these additional uncertainties could be easily included in the

developed mathematical procedure.

Two comprehensive databases for physical properties consisting of 176 pure components

and VLE data for 87 binary mixtures with their associated uncertainties were developed using

the uncertainty information provided by TDE. The uncertainty of relevant pure component

physical and thermo-physical properties to this research was evaluated using the standard error

propagation equation, Equation 2.21. Two generalized correlations for the estimation of critical

properties and acentric factors necessary to model oil fractions were updated. The Peng

Robinson equations of state was re-parameterized by taking into account the uncertainties in both

dependent and independent variables using a weighted least squares method and the uncertainty

information of the model parameters was presented as the variance-covariance matrix. The

regression technique used in this study is based on the maximum likelihood principle in which, at

each point, the weighting factor is inversely proportional to the square of the uncertainty in that

130

point, and it involves the recalculation of the uncertainty at each iteration of the optimization

procedure. The results obtained from the comparison of the new models to the original ones

showed that the re-parameterized models not only provide better results for pure component

properties, Tables 2.6 and 2.10, but can also be used for more advanced statistical analyses due

to the ability to calculate uncertainty information for physical properties associated with the

pseudo-components.

Since the quality of the experimental VLE data affects the quality of the binary

interaction parameters and hence process simulation and design, the accuracy of the data

reported by TDE was vetted and the data quality was tested using the high-pressure

thermodynamic consistency test. A list of typographical errors, unit-conversion errors, report

interpretation errors, and data repetition errors present in TDE were prepared by reviewing the

original literature cited by TDE, reported to NIST, and resolved during the process of the

database development.

The consistency test was performed using the ValderramaFandez method which is

based on the GibbsDuhem equation and the consistent datasets were used for determination of

the binary interaction parameters. The uncertainties of the binary interaction parameters were

evaluated using the Monte Carlo technique coupled with the nonlinear optimization method used

for estimation of the binary interaction parameters. The objective function used for the

evaluation of the parameters was a function of all process variables of the VLE data including

pressure, temperature, and both liquid and vapour phases compositions and their uncertainties.

It was shown in this study that the Monte Carlo method is a useful tool for uncertainty

analysis and can be successfully used to study and analyze the effect of input uncertainties on the

calculated values of variables of interest for flow sheets of any complexity. The Monte Carlo

131

technique coupled with Latin Hypercube Sampling (LHS) method, the developed databases for

pure component physical properties and binary interaction parameters, and the re-parameterized

PengRobinson equation of state along with the van der Waals quadratic mixing rules formed the

basis of a consistent and self-contained error propagation algorithm. The application of this

algorithm coupled with the VMGSim process simulator was illustrated through the uncertainty

evaluation for normal boiling point calculations, natural gas pressure-temperature envelopes, and

gasoline Reid vapour pressure estimations in realistic industry-based case studies.

In general, development of this error propagation algorithm with available uncertainty

information through its internal databases reduces guesswork in process simulation and design

and allows the designers to perform uncertainty analysis to critically evaluate design decisions

such as over-design for a given equipment. There is no standard practice to establish an overdesign value but rather this is currently done based on empirical rules of thumb and accumulated

experience of designer or design company. The amount of under- or over-design is a function of

what is not known by the designers and different from company to company and even from

engineer to engineer in the same company.

By having an assessment of the accuracy of a simulation or design, a company may

design a tighter piece of equipment, for example a smaller compressor, that will still work and

meet the design specifications, but may be considerably cheaper. This is, of course, a significant

advantage to the company with the knowledge of uncertainties over other companies when

bidding for a project. It should be noted that the turn-up/turn-down design factors that are

routinely applied to plants depending on the degree of flexibility required by the client, are

entirely separated from the analysis developed in this study. It should be noted that the analysis

132

of uncertainties associated with chemical processes provides a rich area for the targeting of

relevant research.

This work is one of the fundamental building blocks necessary to allow the users of

process simulators to know the expected errors in the design. It also mitigates the unknown or

little understood design risks by providing an analytical way of knowing uncertainty based on the

underlying thermodynamics. The process equipment design equations such as equations for the

calculation of heat transfer coefficients and pressure drops are the next fundamental building

blocks. In order to move uncertainty evaluation from belief to science, it is necessary to revise

the thermodynamic models and design equations that have been used for decades through

analysis of the physical property data and associated uncertainties and finally determine the

uncertainties in the model parameters.

After these two building blocks thermodynamics and design equations- are constructed

and integrated into the process simulator, the errors in the thermodynamic properties of a stream,

the area of a heat exchanger, the make-up stream required for operation, and everything in

between can be scientifically obtained using the error propagation algorithm developed in this

study. It can also be easily incorporated into plant wide flow sheeting and control by taking into

consideration the uncertainties in independent process parameters such as temperatures,

pressures, and flows.

5.2 Recommendations

One of the main features of the error propagation algorithm developed in this study is the

capability to be linked with process simulators. In order to extend the application of the error

133

propagation algorithm to quantify uncertainties related to any chemical processes, the following

recommendations are suggested for future study.

1. Extend the databases to include heavier hydrocarbons, non-hydrocarbons and water. For

instance, the uncertainty information for amines and glycols should be added to the databases

in order to use the algorithm for sweetening and dehydration plants.

2. Add other popular models used to estimate temperature-dependent physical properties such

the Antoine equation for the estimation of vapour pressures and the Rackett model for the

estimation of liquid density. The other thermodynamic models, such as the SRK and the RK

equations of state, should be re-parameterized as was done for the PengRobinson equation

of state and their variance-covariance matrix of parameters should be determined.

3. Evaluate more complex mixing rules such as the Wong-Sandler mixing rule or the HuronVidal mixing rule for the modelling of more complex phase behaviour such as liquidliquid

equilibrium (LLE) and evaluate new interaction parameters and their uncertainties.

4. Finally, the most long lasting contribution of this study would be the implementation of error

analysis and error propagation into the engineers thought process and its further usage into

other important models used for process design which are related to physical and transport

properties. For example, the availability of heat transfer coefficients with their associated

uncertainty, combined with the techniques developed in this work would allow the design of

better heat exchangers, which would effectively improve the overall quality of plant designs.

134

No

135

4

Compound

Formula

Tb (K)

(K)

SG

Tc (K)

(K)

Pc (kPa)

(kPa)

3-Methyl-1-butene

C5H10

293.20

0.02

0.6343

0.0014

452.69

0.50

3510.4

47.2

0.206

0.006

2-Methylbutane

C5H12

301.02

0.48

0.6246

0.0005

460.37

0.09

3342.9

156.8

0.224

0.022

1-Pentene

C5H10

303.10

0.03

0.6510

0.0063

464.74

0.03

3550.2

30.7

0.236

0.004

Pentane

C5H12

309.21

0.09

0.6311

0.0002

469.71

0.10

3367.0

19.0

0.251

0.003

cis-2-Pentene

C5H10

310.08

0.02

0.6594

0.0017

474.89

0.45

3691.7

27.1

0.254

0.003

2-Methyl-2-butene

C5H10

311.59

0.14

0.6643

0.0016

470.40

1.00

3415.2

137.9

0.281

0.018

3,3-Dimethyl-1-butene

C6H12

314.38

0.03

0.6581

0.0005

477.40

0.90

3025.1

154.2

0.212

0.022

Cyclopentene

C5H8

317.37

0.05

0.7771

0.0004

506.08

0.21

4783.6

107.0

0.199

0.010

Cyclopentane

C5H10

322.39

0.02

0.7502

0.0002

511.74

0.18

4515.1

83.5

0.195

0.008

10

2,2-Dimethylbutane

C6H14

322.87

0.02

0.6539

0.0003

489.09

0.47

3101.8

13.4

0.232

0.002

11

4-Methyl-1-pentene

C6H12

326.84

0.05

0.6687

0.0004

493.10

0.50

3178.4

9.4

0.256

0.001

12

2,3-Dimethyl-1-butene

C6H12

328.74

0.02

0.6830

0.0004

497.70

0.90

3044.2

120.5

0.221

0.017

13

cis-4-Methyl-2-pentene

C6H12

329.51

0.02

0.6741

0.0004

496.30

0.70

3360.6

79.9

0.284

0.010

14

2,3-Dimethylbutane

C6H14

331.12

0.06

0.6660

0.0002

500.16

0.31

3132.8

25.6

0.246

0.004

15

2-Methylpentane

C6H14

333.39

0.03

0.6576

0.0002

497.85

0.23

3032.0

13.4

0.278

0.002

16

2-Methyl-1-pentene

C6H12

335.24

0.01

0.6855

0.0011

501.90

5.08

3162.8

9.9

0.283

0.001

17

3-Methylpentane

C6H14

336.40

0.03

0.6690

0.0003

504.56

0.15

3123.1

15.3

0.272

0.002

18

1-Hexene

C6H12

336.58

0.09

0.6780

0.0004

504.07

0.89

3206.4

89.3

0.287

0.012

19

cis-3-Hexene

C6H12

339.57

0.01

0.6847

0.0004

510.20

1.40

3299.4

12.6

0.285

0.002

Reprinted from Fluid Phase Equilibria, Vol. 307, S. Hajipour, M.A. Satyro, Uncertainty Analysis Applied to Thermodynamic Models and Process Design 1.

Pure Components, 78-94, Copyright (2011), with permission from Elsevier.

No

Compound

20

(K)

SG

Tc (K)

(K)

Pc (kPa)

(kPa)

136

Formula

Tb (K)

trans-3-Hexene

C6H12

340.21

0.01

0.6820

0.0003

507.40

2.00

3333.7

87.5

0.320

0.011

21

2-Methyl-2-pentene

C6H12

340.43

0.01

0.6914

0.0004

509.30

0.50

3258.3

12.1

0.297

0.002

22

trans-2-Hexene

C6H12

341.00

0.02

0.6828

0.0004

509.00

0.70

3306.3

90.1

0.313

0.012

23

Hexane

C6H14

341.85

0.11

0.6642

0.0002

507.53

0.14

3031.2

32.4

0.301

0.005

24

cis-2-Hexene

C6H12

342.04

0.14

0.6920

0.0003

513.40

0.90

3233.9

133.8

0.280

0.018

25

Methylcyclopentane

C6H12

344.94

0.04

0.7537

0.0002

532.78

0.05

3779.5

80.5

0.229

0.009

26

4,4-Dimethyl-1-pentene

C7H14

345.63

0.03

0.6872

0.0003

516.00

4.00

3047.3

83.7

0.284

0.012

27

2,3-Dimethyl-2-butene

C6H12

346.33

0.03

0.7128

0.0006

521.00

0.90

3404.0

141.0

0.291

0.018

28

2,2-Dimethylpentane

C7H16

352.32

0.02

0.6784

0.0002

520.62

0.55

2767.8

44.9

0.285

0.007

29

Benzene

C6H6

353.23

0.03

0.8846

0.0002

562.02

0.14

4896.9

18.6

0.210

0.002

30

2,4-Dimethylpentane

C7H16

353.56

0.21

0.6773

0.0003

519.95

0.66

2732.4

57.3

0.299

0.010

31

Cyclohexane

C6H12

353.86

0.04

0.7835

0.0001

553.35

0.29

4064.0

14.0

0.210

0.002

32

2,2,3-Trimethylbutane

C7H16

354.00

0.02

0.6946

0.0001

531.27

0.49

2944.3

17.2

0.248

0.003

33

Cyclohexene

C6H10

356.06

0.06

0.8157

0.0007

560.45

0.02

4421.4

148.4

0.217

0.015

34

2,3-Dimethyl-1-pentene

C7H14

357.40

1.50

0.7098

0.0008

533.60

4.30

2856.0

795.3

0.257

0.123

35

5-Methyl-1-hexene

C7H14

358.30

1.00

0.6972

0.0010

528.70

0.40

2862.1

183.7

0.304

0.031

36

3,3-Dimethylpentane

C7H16

359.19

0.02

0.6983

0.0008

536.37

0.40

2938.8

14.2

0.266

0.002

37

2,3-Dimethylpentane

C7H16

362.95

0.24

0.6994

0.0004

537.47

0.59

2911.1

155.8

0.295

0.024

38

2-Methylhexane

C7H16

363.12

0.13

0.6833

0.0003

530.37

0.15

2734.1

24.9

0.329

0.004

39

2-Methyl-1-hexene

C7H14

364.90

1.30

0.7069

0.0012

541.80

1.10

2901.6

279.6

0.284

0.045

40

3-Methylhexane

C7H16

364.97

0.04

0.6915

0.0003

535.36

0.51

2817.0

21.1

0.322

0.003

41

3-Ethylpentane

C7H16

366.59

0.02

0.7031

0.0004

540.67

0.37

2900.3

15.5

0.311

0.002

42

1-Heptene

C7H14

366.77

0.22

0.7017

0.0006

537.34

0.28

2851.8

32.0

0.332

0.006

No

Compound

43

(K)

SG

Tc (K)

(K)

Pc (kPa)

(kPa)

137

Formula

Tb (K)

trans-3-Heptene

C7H14

369.00

1.20

0.7027

0.0015

538.60

0.70

2959.6

225.9

0.363

0.037

44

cis-2-Heptene

C7H14

370.50

1.30

0.7103

0.0018

548.50

0.60

2975.1

257.8

0.306

0.042

45

trans-2-Heptene

C7H14

371.20

1.10

0.7054

0.0013

542.80

0.40

2959.2

151.2

0.355

0.026

46

Heptane

C7H16

371.53

0.10

0.6883

0.0002

540.06

0.19

2735.8

28.4

0.350

0.005

47

2,2,4-Trimethylpentane

C8H18

372.36

0.21

0.6963

0.0002

543.91

0.44

2567.9

59.8

0.304

0.011

48

Methylcyclohexane

C7H14

374.04

0.07

0.7739

0.0002

572.31

0.05

3481.0

175.0

0.235

0.022

49

Ethylcyclopentane

C7H14

376.61

0.07

0.7710

0.0002

569.48

0.05

3396.9

40.1

0.271

0.005

50

2,2-Dimethylhexane

C8H18

379.96

0.02

0.6997

0.0003

549.88

0.40

2527.3

30.4

0.337

0.005

51

2,5-Dimethylhexane

C8H18

382.23

0.02

0.6983

0.0003

550.01

0.34

2487.7

13.5

0.356

0.002

52

2,4-Dimethylhexane

C8H18

382.55

0.02

0.7037

0.0014

553.00

3.29

2540.3

32.1

0.344

0.006

53

2,2,3-Trimethylpentane

C8H18

382.96

0.02

0.7199

0.0003

563.46

0.40

2726.0

24.5

0.297

0.004

54

Toluene

C7H8

383.73

0.11

0.8718

0.0002

591.89

0.07

4132.5

52.8

0.265

0.006

55

3,3-Dimethylhexane

C8H18

385.10

0.01

0.7140

0.0005

561.98

0.40

2655.4

8.7

0.321

0.001

56

2,3,4-Trimethylpentane

C8H18

386.60

0.02

0.7230

0.0003

566.37

0.40

2706.2

32.4

0.312

0.005

57

2,3,3-Trimethylpentane

C8H18

387.89

0.02

0.7301

0.0004

573.52

0.40

2823.7

31.3

0.291

0.005

58

2,3-Dimethylhexane

C8H18

388.73

0.02

0.7168

0.0004

563.45

0.40

2628.3

19.2

0.346

0.003

59

2-Methyl-3-ethylpentane

C8H18

388.77

0.02

0.7235

0.0003

567.05

0.40

2698.1

16.5

0.329

0.003

60

2-Methylheptane

C8H18

390.78

0.04

0.7019

0.0003

559.63

0.14

2502.1

30.5

0.381

0.005

61

4-Methylheptane

C8H18

390.83

0.02

0.7089

0.0002

561.70

0.40

2541.2

17.7

0.371

0.003

62

3,4-Dimethylhexane

C8H18

390.85

0.02

0.7232

0.0005

568.81

0.40

2691.8

17.8

0.338

0.003

63

3-Ethyl-3-methylpentane

C8H18

391.39

0.01

0.7316

0.0001

576.54

0.40

2773.4

12.4

0.299

0.002

64

3-Ethylhexane

C8H18

391.66

0.02

0.7175

0.0004

565.45

0.40

2605.1

16.1

0.360

0.003

65

Cycloheptane

C7H14

391.94

0.05

0.8159

0.0001

604.26

0.10

3858.9

86.8

0.243

0.010

No

Compound

66

(K)

SG

Tc (K)

(K)

Pc (kPa)

(kPa)

138

Formula

Tb (K)

3-Methylheptane

C8H18

392.04

0.03

0.7099

0.0004

563.68

0.40

2542.6

25.8

0.369

0.004

67

1-Heptene, 2-methyl-

C8H16

392.40

1.30

0.7248

0.0007

567.50

0.90

2629.8

231.6

0.357

0.042

68

1,trans-4-Dimethylcyclohexane

C8H16

392.47

0.02

0.7672

0.0003

587.66

1.60

3037.0

12.5

0.268

0.002

69

1-Octene

C8H16

394.42

0.07

0.7196

0.0003

566.58

0.05

2675.7

35.0

0.395

0.006

70

2-Heptene, 2-methyl-

C8H16

395.20

1.50

0.7287

0.0010

568.90

1.10

2638.2

367.3

0.379

0.063

71

2,2,4,4-Tetramethylpentane

C9H20

395.39

0.04

0.7237

0.0005

574.61

0.50

2485.1

3.4

0.312

0.001

72

trans-4-Octene

C8H16

395.54

0.08

0.7188

0.0008

566.30

1.10

2546.9

55.3

0.390

0.009

73

2,2,5-Trimethylhexane

C9H20

397.16

0.11

0.7114

0.0005

569.88

2.00

2457.3

33.0

0.364

0.006

74

1,cis-4-Dimethylcyclohexane

C8H16

397.43

0.04

0.7872

0.0003

603.19

0.33

3431.7

30.3

0.260

0.004

75

cis-1,3-Dimethylcyclohexane

C8H16

397.57

0.02

0.7711

0.0010

587.67

0.50

2879.1

12.9

0.299

0.002

76

trans-2-Octene

C8H16

398.02

0.17

0.7238

0.0011

569.80

0.40

2687.1

140.0

0.413

0.023

77

Octane

C8H18

398.81

0.04

0.7070

0.0001

568.78

0.14

2484.9

9.6

0.398

0.002

78

Ethylcyclohexane

C8H16

404.82

0.19

0.7925

0.0002

606.90

0.40

3277.8

100.9

0.292

0.014

79

Heptane, 2,2-dimethyl-

C9H20

405.76

0.53

0.7147

0.0008

576.65

0.50

2349.5

68.2

0.390

0.014

80

2,2,3,4-Tetramethylpentane

C9H20

406.14

0.12

0.7431

0.0005

592.61

0.50

2602.1

34.8

0.313

0.006

81

Ethylbenzene

C8H10

409.32

0.05

0.8724

0.0004

617.12

0.11

3615.9

12.0

0.304

0.002

82

2,2,5,5-Tetramethylhexane

C10H22

410.30

1.10

0.7228

0.0013

581.41

0.50

2186.0

3.0

0.372

0.013

83

1,4-Dimethylbenzene

C8H10

411.46

0.06

0.8657

0.0004

616.19

0.15

3527.0

16.0

0.323

0.002

84

1,3-Dimethylbenzene

C8H10

412.22

0.05

0.8687

0.0004

616.85

0.56

3539.7

13.6

0.327

0.002

85

2,2,3,3-Tetramethylpentane

C9H20

413.39

0.05

0.7607

0.0005

607.51

0.50

2742.3

15.9

0.304

0.003

86

C9H18

413.80

1.40

0.7835

0.0012

602.16

1.60

2648.9

273.2

0.331

0.047

87

2,3,3,4-Tetramethylpentane

C9H20

414.67

0.12

0.7588

0.0005

607.51

0.50

2715.8

36.3

0.313

0.006

88

Octane, 2-methyl-

C9H20

416.12

0.43

0.7173

0.0007

582.83

0.15

2302.5

21.0

0.455

0.007

No

Compound

89

(K)

SG

Tc (K)

(K)

Pc (kPa)

(kPa)

139

Formula

Tb (K)

1,2-Dimethylbenzene

C8H10

417.54

0.07

0.8844

0.0002

630.43

0.61

3745.3

24.6

0.312

0.003

90

Styrene

C8H8

418.40

0.43

0.9111

0.0005

635.20

2.00

3880.9

207.0

0.302

0.024

91

1-Nonene

C9H18

420.01

0.02

0.7335

0.0003

593.70

1.20

2378.3

12.8

0.422

0.002

92

Nonane

C9H20

423.78

0.17

0.7221

0.0002

594.12

0.67

2294.4

81.5

0.448

0.016

93

Cyclooctane

C8H16

424.29

0.03

0.8408

0.0003

647.36

0.49

3551.0

80.6

0.250

0.010

94

Isopropylbenzene

C9H12

425.51

0.13

0.8667

0.0001

631.16

1.42

3185.2

282.3

0.322

0.039

95

Isopropylcyclohexane

C9H18

427.56

0.21

0.8063

0.0004

632.20

0.40

3062.8

192.0

0.322

0.027

96

(1S)-(-)-.alpha.-pinene

C10H16

429.10

0.44

0.8623

0.0020

644.00

5.00

3353.9

205.0

0.295

0.027

97

Propylcyclohexane

C9H18

429.85

0.03

0.7977

0.0003

630.80

0.90

2868.6

40.2

0.327

0.006

98

3,3,5-Trimethylheptane

C10H22

429.90

1.90

0.7472

0.0022

609.51

0.50

2317.0

48.4

0.395

0.024

99

Propylbenzene

C9H12

432.34

0.09

0.8665

0.0003

638.29

0.14

3201.4

47.1

0.345

0.006

100

Hexane, 2,2,3,3-tetramethyl-

C10H22

432.70

1.30

0.7686

0.0017

623.01

0.50

2510.0

55.5

0.357

0.017

101

1-Ethyl-4-methylbenzene

C9H12

435.13

0.24

0.8659

0.0008

640.20

0.45

3234.1

41.9

0.365

0.006

102

1,3,5-Trimethylbenzene

C9H12

437.91

0.23

0.8695

0.0005

637.31

0.10

3127.8

53.9

0.399

0.008

103

Tert-butylbenzene

C10H14

442.26

0.03

0.8710

0.0003

648.08

1.08

2998.4

34.0

0.351

0.005

104

1,2,4-Trimethylbenzene

C9H12

442.52

0.31

0.8803

0.0003

649.12

0.11

3261.0

218.0

0.381

0.029

105

1-Decene

C10H20

443.71

0.01

0.7449

0.0004

616.00

0.30

2157.2

5.1

0.472

0.001

106

Isobutylcyclohexane

C10H20

444.45

0.13

0.7993

0.0006

642.10

0.60

2610.0

67.0

0.358

0.011

107

Tert-butylcyclohexane

C10H20

444.72

0.16

0.8168

0.0006

652.00

0.40

2824.7

94.3

0.326

0.015

108

Bicyclo[4.1.0]hept-3-ene, 3,7,7-trimethyl-

C10H16

445.00

2.50

0.8700

0.0043

660.00

21.68

2967.3

876.3

0.297

0.131

109

Isobutylbenzene

C10H14

445.87

0.31

0.8574

0.0005

650.28

3.00

3047.0

192.0

0.379

0.028

110

Sec-butylbenzene

C10H14

446.45

0.03

0.8666

0.0004

652.50

1.10

2940.5

24.5

0.355

0.004

111

Decane

C10H22

447.27

0.06

0.7341

0.0003

618.07

0.95

2102.0

51.0

0.485

0.011

No

Compound

112

(K)

SG

Tc (K)

(K)

Pc (kPa)

(kPa)

140

Formula

Tb (K)

1,2,3-Trimethylbenzene

C9H12

449.20

0.30

0.8987

0.0003

664.42

0.10

3455.1

60.6

0.367

0.009

113

p-Cymene

C10H14

450.27

0.08

0.8614

0.0005

653.80

8.06

2799.0

100.0

0.363

0.016

114

(R)-(+)-Limonene

C10H16

450.79

0.02

0.8479

0.0017

653.00

5.00

2809.0

19.1

0.376

0.003

115

Indane

C9H10

450.92

0.04

0.9672

0.0023

684.85

0.40

3965.5

49.6

0.309

0.005

116

Butylcyclohexane

C10H20

454.10

0.11

0.8033

0.0004

653.10

0.40

2556.1

54.7

0.370

0.009

117

Butylbenzene

C10H14

456.43

0.07

0.8645

0.0003

660.48

0.10

2887.1

58.5

0.393

0.009

118

1,4-Diethylbenzene

C10H14

456.89

0.17

0.8663

0.0006

657.90

0.03

2798.1

85.8

0.403

0.013

119

trans-Decalin

C10H18

460.43

0.20

0.8740

0.0002

687.02

1.00

3119.0

245.0

0.291

0.034

120

1,1'-Bicyclopentyl

C10H18

463.61

0.03

0.8686

0.0006

690.00

2.00

3268.7

31.0

0.319

0.004

121

Decahydronaphthalene

C10H18

464.90

1.00

0.8873

0.0032

645.13

10.00

2090.0

354.0

0.452

0.074

122

cis-Decalin

C10H18

468.96

0.28

0.9009

0.0004

702.22

1.00

3207.0

576.0

0.287

0.078

123

Undecane

C11H24

469.03

0.15

0.7445

0.0002

638.82

0.19

2009.0

68.0

0.545

0.015

124

1,2,4,5-Tetramethylbenzene

C10H14

470.50

1.70

0.8909

0.0200

675.68

2.00

2854.0

266.0

0.424

0.044

125

Pentylbenzene

C11H16

476.00

2.80

0.8635

0.0006

675.00

7.00

2578.2

260.0

0.443

0.053

126

1,3-Dimethyladamantane

C12H20

476.43

0.01

0.8885

0.0030

708.00

2.00

2862.7

5.5

0.276

0.001

127

Tetralin

C10H12

480.32

0.34

0.9736

0.0007

720.28

1.45

3522.7

244.4

0.313

0.030

128

p-Diisopropylbenzene

C12H18

483.42

0.04

0.8618

0.0016

675.00

1.00

2297.0

37.0

0.470

0.007

129

1-Dodecene

C12H24

486.51

0.02

0.7623

0.0003

657.60

0.60

1875.0

5.0

0.558

0.001

130

Benzene, 1,3,5-triethyl-

C12H18

488.92

0.03

0.8665

0.0009

679.00

2.00

2321.9

15.0

0.506

0.003

131

Dodecane

C12H26

489.45

0.12

0.7529

0.0004

658.28

0.59

1812.4

87.2

0.572

0.021

132

Naphthalene

C10H8

491.14

0.02

1.0303

0.0072

748.33

0.26

4050.0

44.0

0.304

0.005

133

Hexylbenzene

C12H18

498.90

1.30

0.8633

0.0009

695.00

7.00

2372.2

272.4

0.497

0.051

134

1-Tridecene

C13H26

505.91

0.11

0.7694

0.0004

673.00

7.00

1736.0

54.3

0.617

0.014

No

Compound

135

(K)

SG

Tc (K)

(K)

Pc (kPa)

(kPa)

141

Formula

Tb (K)

Tridecane

C13H28

508.60

0.12

0.7603

0.0004

675.89

0.40

1659.6

62.2

0.605

0.016

136

1,4-Di-tert-butylbenzene

C14H22

510.45

0.02

0.8679

0.0160

708.00

2.00

2233.8

11.6

0.494

0.002

137

2-Methylnaphthalene

C11H10

514.24

0.12

1.0108

0.0005

761.15

3.00

3376.9

119.6

0.354

0.015

138

Heptylbenzene

C13H20

515.40

4.40

0.8625

0.0011

708.00

7.00

2135.2

231.4

0.531

0.067

139

1-Methylnaphthalene

C11H10

517.56

0.29

1.0248

0.0011

770.71

4.64

3510.0

112.0

0.341

0.014

140

2,2,4,4,6,8,8-Heptamethylnonane

C16H34

519.44

0.03

0.7879

0.0014

691.95

4.00

1526.9

7.0

0.536

0.002

141

1-Tetradecene

C14H28

524.29

0.11

0.7757

0.0006

691.00

7.00

1584.1

74.9

0.634

0.021

142

Tetradecane

C14H30

526.70

0.25

0.7671

0.0004

692.49

1.15

1563.6

143.7

0.645

0.040

143

1,1'-Biphenyl

C12H10

528.38

0.04

1.0388

0.0066

772.16

5.22

3407.0

60.0

0.415

0.008

144

Benzene, 1,2,4,5-tetrakis(1-methylethyl)-

C18H30

533.95

0.02

0.8558

0.0851

703.00

1.00

1650.3

10.6

0.661

0.003

145

Naphthalene, 2,7-dimethyl-

C12H12

535.52

0.04

0.9960

0.0180

775.00

2.00

2948.0

31.0

0.400

0.005

146

Octylbenzene

C14H22

536.50

1.30

0.8609

0.0007

725.00

7.00

1984.2

210.0

0.589

0.047

147

Diphenylmethane

C13H12

537.45

0.07

1.0120

0.0017

775.83

9.32

3020.0

77.0

0.422

0.011

148

Hexamethylbenzene

C12H18

540.90

3.20

0.9109

0.0911

757.93

2.00

2585.7

430.7

0.508

0.078

149

1-Pentadecene

C15H30

541.55

0.07

0.7804

0.0010

705.00

7.00

1555.6

46.9

0.705

0.013

150

Pentadecane

C15H32

543.77

0.34

0.7721

0.0007

706.88

2.17

1424.0

195.0

0.678

0.060

151

1-Hexadecene

C16H32

558.00

1.40

0.7853

0.0008

718.00

7.00

1377.7

362.0

0.728

0.115

152

Hexadecane

C16H34

560.10

1.10

0.7774

0.0005

722.25

0.83

1411.9

319.9

0.726

0.099

153

Decylbenzene

C16H26

570.96

0.35

0.8595

0.0006

752.00

8.00

1724.5

95.6

0.681

0.024

154

1-Heptadecene

C17H34

573.90

1.30

0.7898

0.0011

734.00

7.00

1344.2

81.8

0.758

0.028

155

Heptadecane

C17H36

575.80

1.20

0.7818

0.0005

735.71

0.95

1318.9

102.7

0.756

0.035

156

Benzene, undecyl-

C17H28

584.80

1.40

0.8607

0.0019

763.00

8.00

1627.5

129.5

0.732

0.036

157

1-Octadecene

C18H36

588.70

1.00

0.7933

0.0018

748.00

8.00

1286.5

140.2

0.792

0.048

(K)

SG

Tc (K)

(K)

Pc (kPa)

(kPa)

142

No

Compound

Formula

Tb (K)

158

Octadecane

C18H38

589.50

1.90

0.7868

0.0100

747.63

1.00

1204.6

224.9

0.778

0.082

159

1,1'-Methylenebis[(1-methylethyl)benzene]

C19H24

592.00

35.00

0.9913

0.0292

795.00

8.00

1550.0

111.7

0.500

0.435

160

Nonadecane

C19H40

602.81

0.73

0.7912

0.0077

755.68

5.20

1156.0

74.0

0.835

0.028

161

1-Nonadecene

C19H38

604.00

16.00

0.7949

0.0042

755.00

8.00

1190.0

131.1

0.877

0.217

162

1,1':2',1''-Terphenyl

C18H14

610.70

1.40

1.0851

0.0120

857.12

6.00

2884.0

97.0

0.548

0.019

163

Tridecylbenzene

C19H32

613.20

2.00

0.8558

0.0280

790.00

8.00

1530.5

116.2

0.798

0.037

164

Eicosane

C20H42

617.25

0.24

0.7930

0.0012

768.22

5.77

1078.0

49.0

0.869

0.020

165

1-Eicosene

C20H40

620.00

15.00

0.8275

0.0250

772.00

15.00

1140.0

266.9

0.881

0.222

166

Heneicosane

C21H44

632.10

5.90

0.7944

0.0086

777.60

7.80

1030.0

109.0

0.923

0.073

167

Docosane

C22H46

641.90

3.50

0.7994

0.0031

785.52

5.75

991.9

129.7

0.966

0.061

168

m-Terphenyl

C18H14

647.80

2.20

1.0901

0.0360

882.51

6.80

2115.0

191.0

0.581

0.043

169

Tricosane

C23H48

653.80

9.10

0.8033

0.0045

789.70

7.90

914.3

133.2

1.047

0.110

170

p-Terphenyl

C18H14

657.01

1.39

1.1461

0.1141

912.94

21.58

2406.5

533.3

0.526

0.097

171

Tetracosane

C24H50

664.20

2.50

0.8007

0.0059

799.56

5.24

868.7

114.3

1.058

0.058

172

Hexacosane

C26H54

688.00

11.00

0.8071

0.0037

816.00

8.00

787.2

189.2

1.125

0.142

173

2,6,10,15,19,23-Hexamethyltetracosane

C30H62

693.50

2.60

0.8138

0.0011

795.90

2.00

595.5

37.6

1.264

0.038

174

Octacosane

C28H58

707.00

3.20

0.8092

0.0032

824.00

8.00

751.5

117.9

1.264

0.068

175

Triacontane

C30H62

725.70

8.40

0.8088

0.0130

843.00

8.00

645.1

140.7

1.181

0.117

176

Hexatriacontane

C36H74

777.30

6.70

0.8217

0.0070

872.00

9.00

471.4

71.9

1.500

0.094

APPENDIX B: CALCULATED UNCERTAINTY OF VAPOUR PRESSURE USING NEW 3-PARAMETER PENGROBINSON EQUATION OF STATE BY COVARIANCE APPROACH5

Methane (= 0.0116)

T

(K)

Pexp

(kPa)

143

(kPa)

Pcal

(kPa)

111.69

101.32

0.29

112.50

108.29

117.00

n-Hexane (= 0.3009)

(kPa)

T

(K)

P exp

(kPa)

(kPa)

P cal

(kPa)

98.25

1.16

341.85

101.31

0.33

0.31

105.07

1.21

349.60

128.42

153.77

0.46

149.67

1.54

358.80

121.50

212.51

0.69

207.45

1.91

126.00

286.70

1.00

280.68

130.50

378.80

1.40

135.00

491.00

139.50

n-Dodecane (= 0.5715)

(kPa)

T

(K)

P exp

(kPa)

(kPa)

P cal

(kPa)

(kPa)

101.23

1.74

489.45

101.33

0.28

99.91

6.26

0.46

128.21

2.10

496.61

119.78

0.39

118.22

7.22

167.58

0.66

167.21

2.60

505.98

147.80

0.61

146.11

8.65

368.00

215.37

0.90

214.87

3.18

515.35

180.70

0.95

178.94

10.30

2.31

377.20

273.00

1.20

272.41

3.85

524.72

219.00

1.40

217.31

12.19

371.73

2.73

386.40

341.60

1.60

341.11

4.62

534.09

263.40

2.10

261.84

14.36

1.90

483.08

3.17

395.60

422.50

2.00

422.34

5.51

543.46

314.40

3.10

313.19

16.82

625.80

2.60

617.28

3.60

404.80

517.10

2.50

517.53

6.53

552.83

372.70

4.40

372.06

19.63

144.00

785.60

3.20

776.92

4.04

414.00

626.80

3.00

628.16

7.70

562.20

439.00

6.10

439.18

22.81

148.50

973.00

4.00

964.70

4.45

423.20

753.00

3.70

755.80

9.04

571.57

514.10

8.30

515.33

26.41

153.00 1190.60

4.80

1183.30

4.85

432.40

897.30

4.40

902.09

10.55

580.94

599.00

11.00

601.32

30.46

157.50 1440.90

5.60

1435.60

5.22

441.60 1061.50

5.40

1068.72

12.27

590.31

694.00

15.00

698.01

35.01

162.00 1726.80

6.30

1724.40

5.56

450.80 1247.20

6.60

1257.49

14.22

599.68

800.00

19.00

806.32

40.11

Reprinted from Fluid Phase Equilibria, Vol. 307, S. Hajipour, M.A. Satyro, Uncertainty Analysis Applied to Thermodynamic Models and Process Design 1.

Pure Components, 78-94, Copyright (2011), with permission from Elsevier.

Methane (= 0.0116)

(kPa)

Pcal

(kPa)

(kPa)

P cal

(kPa)

(kPa)

166.50 2051.20

6.80

2052.60

5.90

460.00 1456.70

8.20

171.00 2417.30

7.20

2423.30

6.25

469.20 1692.00

175.50 2828.70

7.40

2839.50

6.65

180.00 3289.70

7.30

3304.50

184.50 3806.00

7.20

189.00 4386.40

190.56 4606.80

T

(K)

Pexp

(kPa)

n-Hexane (= 0.3009)

144

(kPa)

T

(K)

P exp

(kPa)

(kPa)

P cal

(kPa)

(kPa)

1470.26

16.42

609.05

919.00

25.00

927.21

45.82

10.00

1709.01

18.91

618.42 1052.00

32.00

1061.69

52.20

478.40 1956.00

13.00

1975.80

21.70

627.79 1199.00

41.00

1210.85

59.29

7.15

487.60 2253.00

18.00

2272.83

24.83

637.16 1364.00

52.00

1375.84

67.18

3821.60

7.84

496.80 2585.00

23.00

2602.43

28.34

646.53 1548.00

65.00

1557.91

75.93

8.20

4394.30

8.80

506.00 2963.00

31.00

2967.03

32.26

655.90 1755.00

82.00

1758.35

85.62

9.10

4606.80

9.20

507.53 3031.18

32.39

3031.18

32.96

658.28 1812.40

87.19

1812.40

88.24

T

(K)

P exp

(kPa)

n-Dodecane (= 0.5715)

The detailed information about the constructed VLE database for 87 binary mixtures of interest

in this study is summarized in Table C.1. The number of data points (NP), number of isothermal

datasets with more than three data points (NT=cte.), and the ranges of variation in temperature and

pressure values are shown in this table. This table shows information for all experimental VLE

data used in this study before performing consistency test.

Table C.1. Detailed information about the developed binary VLE database.

No.

Binary

NP

NT=cte.

Range T (K)

Range P (kPa)

Methane/Ethane

511

49

110.90 283.15

15.789 6894.8

Methane/Propane

604

54

114.10 363.15

42.058 10163

Methane/i-Butane

93

191.50 377.55

490.33 11768

Methane/n-Butane

422

40

144.26 410.95

137.90 13135

Methane/i-Pentane

21

344.26 410.93

3440.5 15106

Methane/n-Pentane

1140

64

176.21 460.93

60.795 16719

Methane/n-Hexane

170

16

190.50 444.25

137.21 19783

Methane/n-Heptane

165

14

199.82 510.93

689.48 24883

Methane/n-Octane

71

273.15 423.15

1013.3 28878

10

Methane/n-Nonane

127

223.15 423.15

1013.2 31917

11

Methane/n-Decane

234

19

277.59 583.05

137.90 36198

12

Methane/Nitrogen

678

54

91.600 199.82

21.198 5061.5

13

Methane/Argon

181

17

91.600 178.00

16.132 5098.7

14

Methane/Helium

484

44

91.100 290.00

481.29 1013250

15

Methane/H2S

145

188.71 366.48

860.00 13100

16

Methane/CO2

339

35

153.15 301.00

1078.0 8519.4

17

Ethane/Propane

581

35

127.59 369.18

0.0180 5184.9

18

Ethane/i-Butane

36

311.26 394.04

1068.7 5371.0

Reprinted from Fluid Phase Equilibria, Vol. 364, S. Hajipour, M.A. Satyro, M.W. Foley, Uncertainty Analysis

Applied to Thermodynamic Models and Process Design 2. Binary Mixtures, 15-30, Copyright (2013), with

permission from Elsevier.

145

No.

Binary

NP

NT=cte.

Range T (K)

Range P (kPa)

19

Ethane/n-Butane

112

13

260.00 366.45

161.30 5571.0

20

Ethane/n-Pentane

91

10

277.59 449.82

344.74 6550.0

21

Ethane/n-Hexane

60

298.15 449.82

172.37 7901.4

22

Ethane/n-Heptane

89

10

338.71 449.82

2757.9 8618.4

23

Ethane/n-Octane

64

313.15 373.15

405.30 6800.0

24

Ethane/Nitrogen

332

28

110.93 290.00

196.50 13466

25

Ethane/Argon

84.760 113.52

64.636 690.83

26

Ethane/Helium

73

10

133.15 273.15

490.30 11768

27

Ethane/H2S

45

199.93 283.15

65.155 3052.3

28

Ethane/CO2

382

30

207.00 298.15

329.20 6629.7

29

Propane/i-Butane

230

32

237.15 395.01

40.797 4171.3

30

Propane/n-Butane

241

18

236.53 414.35

26.265 4357.5

31

Propane/n-Pentane

149

14

336.56 460.93

334.37 4481.6

32

Propane/n-Octane

13

473.10 523.10

2540.0 5140.0

33

Propane/n-Nonane

376.75 377.15

938.00 3468.0

34

Propane/n-Decane

376.85 377.15

945.00 3516.0

35

Propane/Nitrogen

178

23

114.10 353.15

150.31 21919

36

Propane/H2S

54

217.59 367.04

137.90 4143.7

37

Propane/CO2

422

43

230.00 361.15

194.00 6894.8

38

n-Butane/i-Butane

24

273.15

108.72 153.45

39

i-Butane/Nitrogen

90

120.00 310.87

232.35 20774

40

i-Butane/H2S

84

10

277.65 398.15

206.84 8887.0

41

i-Butane/CO2

129

11

273.15 398.15

273.58 7400.0

42

n-Butane/n-Pentane

89

270.00 409.96

34.000 2484.0

43

n-Butane/n-Heptane

36

339.26 525.93

689.48 2757.9

44

n-Butane/n-Decane

61

310.93 510.93

172.37 4826.3

45

n-Butane/Nitrogen

152

16

250.00 422.04

452.00 28751

46

n-Butane/Argon

43

339.67 380.25

1393.0 18485

47

n-Butane/H2S

51

366.45 418.15

1482.0 7894.0

48

n-Butane/CO2

510

35

227.98 418.48

33.095 8087.6

49

i-Pentane/n-Pentane

13

328.15 384.82

234.38 785.93

146

No.

Binary

NP

NT=cte.

Range T (K)

Range P (kPa)

50

i-Pentane/n-Hexane

32

306.89 335.25

101.33

51

i-Pentane/H2S

35

323.15 413.15

310.00 8377.0

52

i-Pentane/CO2

171

19

253.15 453.15

151.68 9230.0

53

n-Pentane/n-Hexane

32

298.70 308.70

25.80 94.66

54

n-Pentane/n-Heptane

36

293.15 521.95

101.33 3060.0

55

n-Pentane/n-Octane

34

303.70 313.70

5.700 97.00

56

n-Pentane/n-Decane

17

317.70 333.70

48.180 146.41

57

n-Pentane/Nitrogen

113

277.43 447.90

250.28 35470

58

n-Pentane/H2S

53

277.59 444.26

137.90 8963.2

59

n-Pentane/CO2

231

21

252.67 463.15

159.00 9671.0

60

n-Hexane/n-Heptane

31

339.70 369.45

94.00 101.00

61

n-Hexane/n-Octane

11

328.15

10.839 61.275

62

n-Hexane/Nitrogen

124

10

310.93 488.40

960.00 51470

63

n-Hexane/H2S

25

322.95 422.65

430.00 7545.0

64

n-Hexane/CO2

134

15

298.15 393.15

443.70 12630

65

n-Heptane/n-Octane

20

369.55 394.45

94.00

66

n-Heptane/Nitrogen

332

25

305.37 523.70

1200.0 99850

67

n-Heptane/H2S

49

293.25 477.59

397.90 8363.3

68

CO2/n-Heptane

93

310.65 502.00

186.16 13314

69

n-Octane/n-Decane

27

349.15 392.25

20.00

70

n-Octane/Nitrogen

73

344.50 543.50

2050.0 50140

71

n-Octane/CO2

167

18

298.20 393.20

600.00 14440

72

n-Nonane/Nitrogen

70

344.30 543.40

1970.0 49750

73

n-Nonane/CO2

77

298.20 418.82

520.00 16773

74

n-Decane/Nitrogen

232

11

310.93 563.10

1040.0 50320

75

n-Decane/H2S

44

277.59 444.26

137.90 12411

76

n-Decane/CO2

212

22

277.59 594.20

344.74 17990

77

Nitrogen/Oxygen

318

76.79 136.17

60.440 2966.6

78

Nitrogen/H2S

126

12

200.15 344.26

140.65 20705

79

Argon/Nitrogen

271

11

95.02 133.72

253.90 2839.1

80

Helium/Nitrogen

519

32

76.50 136.05

1379.0 413710

147

No.

Binary

NP

NT=cte.

Range T (K)

Range P (kPa)

81

CO2/Nitrogen

234

22

218.15 303.30

1276.7 16706

82

Argon/Oxygen

343

84.81 138.67

63.995 2634.5

83

CO2/Oxygen

112

12

218.15 298.15

1013.2 14297

84

Argon/Helium

217

21

91.34 159.90

1418.6 413710

85

CO2/Argon

77

233.15 299.21

1520.0 14034

86

CO2/Helium

59

219.90 293.13

2979.0 20123

87

CO2/H2S

152

224.82 363.71

689.48 8273.7

148

UNCERTAINTIES 7

The evaluated binary interaction parameters associated with their uncertainties for 87 binary

mixtures are listed in Table D.1. The number of VLE data points used to estimate the binary

interaction parameters, the ranges of variation in temperature and pressure for these data and the

Monte Carlo standard error (MCSE) for sample size of 100 are also indicated in this table.

Table D.1. Binary interaction parameters associated uncertainties.

No.

Binary

NP

Range T (K)

Range P (kPa)

k 12 k12

MCSE (%)

Methane/Ethane

277

130.37 280.00

123.30 6894.8

0.0106 0.0025

0.013

Methane/Propane

148

187.54 343.15

282.69 9625.9

0.0316 0.0048

0.024

Methane/i-Butane

72

233.15 377.55

490.33 11768

0.0479 0.0111

0.055

Methane/n-Butane

250

166.48 394.26

137.90 13100

0.0146 0.0023

0.011

Methane/i-Pentane

15

344.26 377.59

3440.5 15106

0.0307 0.0172

0.086

Methane/n-Pentane

883

299.82 460.00

101.33 16719

0.0091 0.0072

0.036

Methane/n-Hexane

70

190.50 310.95

137.90 18271

0.0025 0.0171

0.085

Methane/n-Heptane

75

310.93 510.93

1379.0 24132

0.0066 0.0052

0.026

Methane/n-Octane

13

373.15 423.15

1013.3 7092.8

0.0721 0.0061

0.031

10 Methane/n-Nonane

20

373.15 423.15

1013.2 10133

0.0495 0.0160

0.080

11 Methane/n-Decane

98

348.15 583.05

137.90 27579

0.0168 0.0143

0.071

12 Methane/Nitrogen

366

95.00 180.00

172.37 4964.2

0.0387 0.0011

0.005

13 Methane/Argon

109

112.55 178.00

141.30 4976.1

0.0328 0.0019

0.009

14 Methane/Helium

46

113.15 188.15

1134.8 20528

0.6780 0.0122

0.061

15 Methane/H2S

61

252.00 310.93

1379.0 13100

0.0503 0.0045

0.022

16 Methane/CO2

104

219.26 301.00

1398.0 8519.4

0.0965 0.0016

0.008

17 Ethane/Propane

129

172.04 355.37

4.00 4998.7

0.0739 0.0067

0.033

Reprinted from Fluid Phase Equilibria, Vol. 364, S. Hajipour, M.A. Satyro, M.W. Foley, Uncertainty Analysis

Applied to Thermodynamic Models and Process Design 2. Binary Mixtures, 15-30, Copyright (2013), with

permission from Elsevier.

149

NP

Range T (K)

Range P (kPa)

k 12 k12

MCSE (%)

18 Ethane/i-Butane

22

311.26 344.48

1068.7 5371.0

0.0302 0.0072

0.036

19 Ethane/n-Butane

61

260.00 363.40

161.30 5326.5

0.0110 0.0039

0.019

20 Ethane/n-Pentane

78

310.93 444.26

344.74 6550.0

0.0083 0.0026

0.013

21 Ethane/n-Hexane

12

338.71

172.37 5515.8

0.0696 0.0298

0.149

22 Ethane/n-Heptane

87

338.71 449.82

2757.9 8518.0

0.0371 0.0076

0.038

23 Ethane/n-Octane

12

318.15 338.15

1500.0 6800.0

0.0177 0.0017

0.009

24 Ethane/Nitrogen

106

125.00 290.00

644.0 13195

0.0335 0.0073

0.037

25 Ethane/Argon

84.760 113.52

64.636 690.83

0.0578 0.0022

0.011

26 Ethane/Helium

62

173.15 273.15

490.30 11768

1.1624 0.0433

0.216

27 Ethane/H2S

20

255.32 283.15

642.59 3052.3

0.0869 0.0029

0.014

28 Ethane/CO2

180

207.00 283.15

329.20 4994.3

0.1330 0.0022

0.011

29 Propane/i-Butane

131

260.00 395.01

132.38 3659.1

0.0593 0.0057

0.028

30 Propane/n-Butane

109

260.00 363.38

75.900 3413.6

0.0498 0.0046

0.023

31 Propane/n-Pentane

114

336.56 444.26

334.37 4481.6

0.0369 0.0042

0.021

32 Propane/n-Octane

13

473.10 523.10

2540.0 5140.0

0.0079 0.0036

0.018

33 Propane/n-Nonane

376.75 377.15

938.00 3468.0

0.0505 0.0046

0.023

34 Propane/n-Decane

376.85 377.15

945.00 3516.0

0.0419 0.0036

0.018

35 Propane/Nitrogen

58

173.15 330.00

1379.0 15903

0.0744 0.0077

0.038

36 Propane/H2S

52

217.59 355.37

137.90 4136.9

0.0228 0.0047

0.023

37 Propane/CO2

194

263.15 327.75

423.10 6677.7

0.0685 0.0053

0.026

38 n-Butane/i-Butane

24

273.15

108.72 153.45

0.0015 0.0037

0.018

39 i-Butane/Nitrogen

30

255.37 310.87

418.51 20774

0.0377 0.0119

0.060

40 i-Butane/H2S

64

310.93 398.15

740.50 7412.0

0.0352 0.0045

0.023

41 i-Butane/CO2

114

273.15 394.26

273.58 7196.0

0.1097 0.0043

0.021

42 n-Butane/n-Pentane

89

270.00 409.96

34.000 2484.0

0.0154 0.0061

0.030

43 n-Butane/n-Heptane

36

339.26 525.93

689.48 2757.9

0.0009 0.0043

0.021

44 n-Butane/n-Decane

55

377.59 510.93

172.37 4826.3

0.0067 0.0053

0.027

45 n-Butane/Nitrogen

60

250.00 411.10

452.00 15785

0.0509 0.0147

0.073

46 n-Butane/Argon

23

339.67 380.25

1393.0 18485

0.0079 0.0194

0.097

47 n-Butane/H2S

41

366.45 418.15

1482.0 7894.0

0.0468 0.0027

0.013

48 n-Butane/CO2

437

250.00 418.48

104.80 7929.0

0.1175 0.0039

0.020

No.

Binary

150

NP

Range T (K)

Range P (kPa)

k 12 k12

MCSE (%)

49 i-Pentane/n-Pentane

13

328.15 384.82

234.38 785.93

0.0469 0.0108

0.054

50 i-Pentane/n-Hexane

32

306.89 335.25

101.33

0.0003 0.0072

0.036

51 i-Pentane/H2S

23

323.15 413.15

310.00 7632.0

0.0524 0.0044

0.022

52 i-Pentane/CO2

127

272.43 443.55

151.68 8984.0

0.0953 0.0216

0.108

53 n-Pentane/n-Hexane

32

298.70 308.70

25.80 94.66

0.0075 0.0035

0.018

54 n-Pentane/n-Heptane 36

293.15 521.95

101.33 3060.0

0.0077 0.0026

0.013

55 n-Pentane/n-Octane

34

303.70 313.70

5.700 97.00

0.0098 0.0083

0.042

56 n-Pentane/n-Decane

17

317.70 333.70

48.180 146.41

0.0139 0.0141

0.071

57 n-Pentane/Nitrogen

70

310.71 447.90

250.28 21230

0.0665 0.0082

0.041

58 n-Pentane/H2S

35

277.59 410.93

137.90 8273.7

0.0432 0.0055

0.028

59 n-Pentane/CO2

156

273.41 438.15

172.00 9651.0

0.1077 0.0204

0.102

60 n-Hexane/n-Heptane 31

339.70 369.45

94.00 101.00

0.0008 0.0010

0.005

No.

Binary

61 n-Hexane/n-Octane

11

328.15

10.839 61.275

0.0084 0.0048

0.024

62 n-Hexane/Nitrogen

42

377.90 488.40

960.00 20930

0.0823 0.0091

0.045

63 n-Hexane/H2S

25

322.95 422.65

430.00 7545.0

0.0570 0.0033

0.016

64 n-Hexane/CO2

36

313.15 393.15

779.11 11597

0.1086 0.0069

0.034

65 n-Heptane/n-Octane

20

369.55 394.45

94.00

0.0029 0.0019

0.010

66 n-Heptane/Nitrogen

149

305.45 523.70

1520.0 99850

0.0816 0.0052

0.026

67 n-Heptane/H2S

31

333.28 477.59

449.50 8363.3

0.0653 0.0092

0.046

68 CO2/n-Heptane

73

310.65 502.00

186.16 11611

0.1082 0.0245

0.123

69 n-Octane/n-Decane

27

349.15 392.25

20.00

0.0011 0.0018

0.009

70 n-Octane/Nitrogen

54

344.50 543.50

2050.0 50140

0.1341 0.0074

0.037

71 n-Octane/CO2

29

322.39 372.53

2000.0 13772

0.1117 0.0131

0.065

72 n-Nonane/Nitrogen

70

344.30 543.40

1970.0 49750

0.1136 0.0194

0.097

73 n-Nonane/CO2

77

298.20 418.82

520.00 16773

0.1273 0.0067

0.033

74 n-Decane/Nitrogen

232

310.93 563.10

1040.0 50320

0.1227 0.0145

0.073

75 n-Decane/H2S

41

277.59 444.26

137.90 9652.7

0.0228 0.0046

0.023

76 n-Decane/CO2

51

344.30 542.95

1379.0 16060

0.1161 0.0072

0.036

77 Nitrogen/Oxygen

84

90.34 125.06

119.26 2966.6

0.0087 0.0046

0.023

78 Nitrogen/H2S

93

227.98 344.26

334.40 20684

0.1555 0.0063

0.031

79 Argon/Nitrogen

62

100.00 122.89

394.15 2839.1

0.0075 0.0023

0.012

151

Binary

NP

Range T (K)

Range P (kPa)

k 12 k12

MCSE (%)

80 Helium/Nitrogen

156

85.00 120.00

1379.0 13824

0.4581 0.0122

0.061

81 CO2/Nitrogen

121

220.00 293.15

1373.0 16706

0.0315 0.0035

0.017

82 Argon/Oxygen

343

84.81 138.67

63.995 2634.5

0.0134 0.0002

0.002

83 CO2/Oxygen

61

218.15 273.15

1013.2 14297

0.0496 0.0069

0.035

84 Argon/Helium

24

91.34 148.03

1418.6 27358

0.4507 0.0112

0.056

85 CO2/Argon

66

233.32 299.21

1520.0 14034

0.0922 0.0041

0.020

86 CO2/Helium

59

219.90 293.13

2979.0 20123

0.8765 0.0090

0.045

87 CO2/H2S

151

224.82 363.71

689.48 8273.7

0.0962 0.0025

0.012

No.

152

References

1.

M. Frenkel, R.D. Chirico, V. Diky, X.J. Yan, Q. Dong, C. Muzny, ThermoData Engine

(TDE): Software Implementation of the Dynamic Data Evaluation Concept, Journal of

Chemical Information and Modeling 45 (2005) 816-838.

2.

M. Frenkel, R.D. Chirico, V. Diky, C.D. Muzny, A.F. Kazakov, NIST ThermoData Engine

(TDE), NIST Standard Reference Database 103b-Pure Compounds, Equations of State,

Binary Mixtures, and Chemical Reactions, version 5.0, National Institute of Standards and

Technology: Gaithersburg, MD, 2010, http://www.nist.gov.

3.

M. Frenkel, Q. Dong, R.C. Wilhoit, K.R. Hall, TRC SOURCE Database: A Unique Tool for

Automatic Production of Data Compilations, International Journal of Thermophysics 22

(2001) 215-226.

4.

Structure and Internet Distribution, International Journal of Thermophysics 22 (2001) 227241.

5.

Quantitative Risk and Policy Analysis, Cambridge University Press: Cambridge, UK, 1990.

6.

R.L. Iman,M.J. Shortencarier, Fortran 77 Program and User's Guide for the Generation of

Latin Hypercube and Random Samples for Use with Computer Models, Report NUREG/CR3624, SAND-83-2365, National Technical Service: Springfield, VA, 1984, p. 67.

7.

VMGSim Process Simulator, version 6.5, Virtual Materials Group Inc.: Calgary, AB,

Canada, 2011, http://www.virtualmaterials.com.

8.

Process Design 1. Pure Components, Fluid Phase Equilibria 307 (2011) 78-94.

9.

Models and Process Design 2. Binary Mixtures, Fluid Phase Equilibria 364 (2013) 15-30.

10. S. Hajipour, M.A. Satyro, M.W. Foley, Uncertainty Analysis Applied to Thermodynamic

Models and Fuel Properties Natural Gas Dew Points and Gasoline Reid Vapour

Pressures, Energy & Fuels (2013), published online, DOI: 10.1021/ef4019838.

11. G. Soave, Equilibrium Constants from a Modified Redlich-Kwong Equation of State,

Chemical Engineering Science 27 (1972) 1197-1203.

12. D.-Y. Peng,D.B. Robinson, A New Two-Constant Equation of State, Industrial &

Engineering Chemistry Fundamentals 15 (1976) 59-64.

153

13. W.B. Whiting, Effects of Uncertainties in Thermodynamic Data and Models on Process

Calculations, Journal of Chemical & Engineering Data 41 (1996) 935-941.

14. M.E. Reed,W.B. Whiting, Sensitivity and Uncertainty of Process Designs to

Thermodynamic Model Parameters: A Monte Carlo Approach, Chemical Engineering

Communications 124 (1993) 39-48.

15. W.B. Whiting, T.M. Tong, M.E. Reed, Effect of Uncertainties in Thermodynamic Data and

Model Parameters on Calculated Process Performance, Industrial & Engineering Chemistry

Research 32 (1993) 1367-1371.

16. W.B. Whiting, V.R. Vasquez, M.M. Meerschaert, Techniques for Assessing the Effects of

Uncertainties in Thermodynamic Models and Data, Fluid Phase Equilibria 158-160 (1999)

627-641.

17. V.R. Vasquez,W.B. Whiting, Effect of Systematic and Random Errors in Thermodynamic

Models on Chemical Process Design and Simulation: A Monte Carlo Approach, Industrial

& Engineering Chemistry Research 38 (1999) 3036-3045.

18. Y. Xin,W.B. Whiting, Case Studies of Computer-Aided Design Sensitivity to

Thermodynamic Data and Models, Industrial & Engineering Chemistry Research 39 (2000)

2998-3006.

19. D. Zudkevitch, Imprecise Data Impacts Plant Design and Operation, Hydrocarbon

Processing 54 (1975) 97-103.

20. D. Zudkevitch,R.D. Gray, Jr., Impact of Fluid Properties on the Design of Equipment for

Handling LNG, Advances in Cryogenic Engineering 20 (1975) 103-123.

21. A.H. Larsen, Data Quality for Process Design, Fluid Phase Equilibria 29 (1986) 47-58.

22. S. Zeck, Thermodynamics in Process-Development in the Chemical Industry-Importance,

Benefits, Current State and Future-Development, Fluid Phase Equilibria 70 (1991) 125-140.

23. K.P. Halemane,I.E. Grossmann, Optimal Process Design under Uncertainty, AIChE Journal

29 (1983) 425-433.

24. U.M. Diwekar,E.S. Rubin, Stochastic Modeling of Chemical Processes, Computers &

Chemical Engineering 15 (1991) 105-114.

25. E.N. Pistikopoulos,M.G. Ierapetritou, Novel-Approach for Optimal Process Design under

Uncertainty, Computers & Chemical Engineering 19 (1995) 1089-1110.

26. P.D. Chaudhuri,U.M. Diwekar, Synthesis under Uncertainty with Simulators, Computers &

Chemical Engineering 21 (1997) 733-738.

154

27. R.L. Rowley, W.V. Wilding, J.L. Oscarson, N.A. Zundel, T.L. Marshal, T.E. Daubert, R.P.

Danner, DIPPR Data Compilation of Pure Compound Properties, Design Institute for

Physical Properties, AIChE: New York, NY, 2008.

28. A. Vetere, Methods to Predict the Vaporization Enthalpies at the Normal Boiling

Temperature of Pure Compounds Revisited, Fluid Phase Equilibria 106 (1995) 1-10.

29. W.J. Sim,T.E. Daubert, Prediction of Vapor-Liquid Equilibria of Undefined Mixtures,

Industrial & Engineering Chemistry Process Design and Development 19 (1980) 386-393.

30. R.H. Cavett. Physical Data for Distillation Calculations, Vapor-Liquid Equilibria, in:

Processing of 27th API Meeting, API Division of Refining 42 (1962) 351-366.

31. H.-M. Lin,K.-C. Chao, Correlation of Critical Properties and Acentric Factor of

Hydrocarbons and Derivatives, AIChE Journal 30 (1984) 981-983.

32. M.R. Riazi, T.A. Al-Sahhaf, M.A. Al-Shammari, A Generalized Method for Estimation of

Critical Constants, Fluid Phase Equilibria 147 (1998) 1-6.

33. K.M. Watson,E.F. Nelson, Improved Methods for Approximating Critical and Thermal

Properties of Petroleum Fractions, Industrial & Engineering Chemistry 25 (1933) 880-887.

34. A.S. Teja, R.J. Lee, D. Rosenthal, M. Anselme, Correlation of the Critical Properties of

Alkanes and Alkanols, Fluid Phase Equilibria 56 (1990) 153-169.

35. M.G. Kesler,B.I. Lee, Improve Prediction of Enthalpy of Fractions, Hydrocarbon Processing

55 (1976) 153-158.

36. B.I. Lee,M.G. Kesler, Improve Vapor Pressure Prediction, Hydrocarbon Processing 59

(1980) 163-167.

37. M.R. Riazi,T.E. Daubert, Simplify Property Prediction, Hydrocarbon Processing 59 (1980)

115-116.

38. G.M. Wilson, R.H. Johnston, S.-C. Hwang, C. Tsonopoulos, Volatility of Coal Liquids at

High Temperatures and Pressures, Industrial & Engineering Chemistry Process Design and

Development 20 (1981) 94-104.

39. M.R. Brule, C.T. Lin, L.L. Lee, K.E. Starling, Multiparameter Corresponding-States

Correlation of Coal-Fluid Thermodynamic Properties, AIChE Journal 28 (1982) 616-625.

40. C.H. Twu, An Internally Consistent Correlation for Predicting the Critical Properties and

Molecular Weights of Petroleum and Coal-Tar Liquids, Fluid Phase Equilibria 16 (1984)

137-150.

41. P.R. Bevington,D.K. Robinson, Data Reduction and Error Analysis for the Physical

Sciences, 2nd ed., McGraw-Hill: New York, NY, 1992.

155

42. K.S. Pitzer, D.Z. Lippmann, R.F. Curl, C.M. Huggins, D.E. Petersen, The Volumetric and

Thermodynamic Properties of Fluids. II. Compressibility Factor, Vapor Pressure and

Entropy of Vaporization, Journal of the American Chemical Society 77 (1955) 3433-3440.

43. W. Wagner, New Vapour Pressure Measurements for Argon and Nitrogen and a New

Method for Establishing Rational Vapour Pressure Equations, Cryogenics 13 (1973) 470482.

44. M. Voulgaris, S. Stamatakis, K. Magoulas, D. Tassios, Prediction of Physical Properties for

Non-Polar Compounds, Petroleum and Coal Liquid Fractions, Fluid Phase Equilibria 64

(1991) 73-106.

45. D.W. Marquardt, An Algorithm for Least-Squares Estimation of Nonlinear Parameters,

Journal of the Society for Industrial & Applied Mathematics 11 (1963) 431-441.

46. P. Englezos,N. Kalogerakis, Applied Parameter Estimation for Chemical Engineers, Marcel

Dekker Inc.: New York, NY, 2001.

47. P. Fornasini, The Uncertainty in Physical Measurements: An Introduction to Data Analysis

in the Physics Laboratory, Springer: New York, NY, 2008.

48. W.H. Press, S.A. Teukolsky, W.T. Vetterling, B.P. Flannery, Numerical Recipes in C: The

Art of Scientific Computing, Cambridge University Press: Cambridge, UK, 1992.

49. J.R. Kalagnanam,U.M. Diwekar, An Efficient Sampling Technique for Off-Line Quality

Control, Technometrics 39 (1997) 308-319.

50. G. Soave, Direct Calculation of Pure-Compound Vapour Pressures through Cubic

Equations of State, Fluid Phase Equilibria 31 (1986) 203-207.

51. D.B. Robinson,D.-Y. Peng, The Characterization of the Heptanes and Heavier Fractions for

the GPA Peng-Robinson Programs, Gas Processors Association (GPA): Tulsa, OK, 1978.

52. G. Sin, K.V. Gernaey, A.E. Lantz, Good Modeling Practice for PAT Applications:

Propagation of Input Uncertainty and Sensitivity Analysis, Biotechnology Progress 25

(2009) 1043-1053.

53. G. Sin, A.S. Meyer, K.V. Gernaey, Assessing Reliability of Cellulose Hydrolysis Models to

Support Biofuel Process Design-Identifiability and Uncertainty Analysis, Computers &

Chemical Engineering 34 (2010) 1385-1392.

54. P. Cinnella, P.M. Congedo, V. Pediroda, L. Parussini, Sensitivity Analysis of Dense Gas

Flow Simulations to Thermodynamic Uncertainties, Physics of Fluids 23 (2011) 116101.

55. V. Diky, R.D. Chirico, A.F. Kazakov, C.D. Muzny, M. Frenkel, ThermoData Engine (TDE):

Software Implementation of the Dynamic Data Evaluation Concept. 3. Binary Mixtures,

Journal of Chemical Information and Modeling 49 (2009) 503-517.

156

56. D.E. Matschke,G. Thodos, Vapor-Liquid Equilibria for the Ethane-Propane System, Journal

of Chemical and Engineering Data 7 (1962) 232-234.

57. M. Fenske, Fractionation of Straight-Run Pennsylvania Gasoline, Industrial & Engineering

Chemistry 24 (1932) 482-485.

58. R. Dohrn,O. Pfohl, Thermophysical Properties-Industrial Directions, Fluid Phase Equilibria

194-197 (2002) 15-29.

59. J.D. Raal,A.L. Mhlbauer, Phase Equilibria: Measurement & Computation, Taylor &

Francis: Bristol, PA, 1998.

60. P.L. Chueh, N.K. Muirbrook, J.M. Prausnitz, Multicomponent Vapor-Liquid Equilibria at

High Pressures: Part II. Thermodynamic Analysis, AIChE Journal 11 (1965) 1097-1102.

61. K.W. Won,J.M. Prausnitz, High-Pressure Vapor-Liquid Equilibria. Calculation of Partial

Pressures from Total Pressure Data. Thermodynamic Consistency, Industrial & Engineering

Chemistry Fundamentals 12 (1973) 459-463.

62. L.J. Christiansen,A. Fredenslund, Thermodynamic Consistency Using Orthogonal

Collocation or Computation of Equilibrium Vapor Compositions at High Pressures, AIChE

Journal 21 (1975) 49-57.

63. A.L. Muhlbauer,J.D. Raal, Measurement and Thermodynamic Interpretation of HighPressure Vapour-Liquid Equilibria in the Toluene-CO2 System, Fluid Phase Equilibria 64

(1991) 213-236.

64. P.L. Jackson,R.A. Wilsak, Thermodynamic Consistency Tests Based on the Gibbs-Duhem

Equation Applied to Isothermal, Binary Vapor-Liquid Equilibrium Data: Data Evaluation

and Model Testing, Fluid Phase Equilibria 103 (1995) 155-197.

65. A. Bertucco, M. Barolo, N. Elvassore, Thermodynamic Consistency of Vapor-Liquid

Equilibrium Data at High Pressure, AIChE Journal 43 (1997) 547-554.

66. J.O. Valderrama,C.A. Faundez, Thermodynamic Consistency Test of High Pressure GasLiquid Equilibrium Data Including Both Phases, Thermochimica Acta 499 (2010) 85-90.

67. D.S.H. Wong,S.I. Sandler, A Theoretically Correct Mixing Rule for Cubic Equations of

State, AIChE Journal 38 (1992) 671-680.

68. T.L. Sutton,J.F. Macgregor, The Analysis and Design of Binary Vapour-Liquid Equilibrium

Experiments. Part I: Parameter Estimation and Consistency Tests, The Canadian Journal of

Chemical Engineering 55 (1977) 602-608.

69. R. Paunovic, S. Jovanovic, A. Mihajlov, Rapid Computation of Binary Interaction

Coefficients of an Equation of State for Vapor-Liquid Equilibrium Calculations. Application

to the Redlich-Kwong-Soave Equation of State, Fluid Phase Equilibria 6 (1981) 141-148.

157

Parameters of a Model for the Simultaneous Representation of Experimental Binary and

Ternary Vapor-Liquid and Liquid-Liquid Equilibrium Data, Fluid phase equilibria 27 (1986)

383-403.

71. V.G. Niesen,V.F. Yesavage, Application of a Maximum Likelihood Method Using Implicit

Constraints to Determine Equation of State Parameters from Binary Phase Behavior Data,

Fluid phase equilibria 50 (1989) 249-266.

72. P. Englezos, N. Kalogerakis, P.R. Bishnoi, Estimation of Binary Interaction Parameters for

Equations of State Subject to Liquid Phase Stability Requirements, Fluid Phase Equilibria 53

(1989) 81-88.

73. P. Englezos, N. Kalogerakis, M.A. Trebble, P.R. Bishnoi, Estimation of Multiple Binary

Interaction Parameters in Equations of State Using VLE Data. Application to the TrebbleBishnoi Equation of State, Fluid Phase Equilibria 58 (1990) 117-132.

74. I. Ashour,G. Aly, Effect of Computation Techniques for Equation of State Binary Interaction

Parameters on the Prediction of Binary VLE Data, Computers & Chemical Engineering 20

(1996) 79-91.

75. T.F. Anderson,J.M. Prausnitz, Computational Methods for High-Pressure Phase Equilibria

and Other Fluid-Phase Properties Using a Partition Function. 2. Mixtures, Industrial &

Engineering Chemistry Process Design and Development 19 (1980) 9-14.

76. J. Wakefield, Bayesian and Frequentist Regression Methods, Springer: New York, NY,

2013.

77. T. Ando, Bayesian Model Selection and Statistical Modeling, Chapman and Hall/CRC Press,

Taylor & Francis Group: Boca Rapton, FL, 2010.

78. B. Efron, Bootstrap Methods: Another Look at the Jackknife, The Annals of Statistics 7

(1979) 1-26.

79. B. Efron, Why Isn't Everyone a Bayesian?, The American Statistician 40 (1986) 1-5.

80. J.O. Valderrama,V.H. Alvarez, A Versatile Thermodynamic Consistency Test for Incomplete

Phase Equilibrium Data of High-Pressure Gas-Liquid Mixtures, Fluid Phase Equilibria 226

(2004) 149-159.

81. F. Brandani, S. Brandani, V. Brandani, The Wong-Sandler Mixing Rules and EOS Which

Are Thermodynamically Consistent at Infinite Pressure, Chemical Engineering Science 53

(1998) 853-856.

82. A.R. Price,R. Kobayashi, Low Temperature Vapor-Liquid Equilibrium in Light

Hydrocarbon Mixtures: Methane-Ethane-Propane System, Journal of Chemical and

Engineering Data 4 (1959) 40-52.

158

83. L.C. Kahre, Liquid Density of Light Hydrocarbon Mixtures, Journal of Chemical and

Engineering Data 18 (1973) 267-270.

84. G.V. Burova, V.B. Kogan, M.S. Nemtsov, Liquid-Vapor Equilibria in Ternary and

Quaternary Systems Consisting of C5 Hydrocarbons and Separating Agents, Zhurnal

Prikladnoi Khimii (Leningrad) 38 (1965) 121-128.

85. C.K. Heck,M.J. Hiza, Liquid-Vapor Equilibrium in the System Helium-Methane, AIChE

Journal 13 (1967) 593-599.

86. C.J. Blanc,J.C.B. Setier, Vapor-Liquid Equilibria for the Ethane-Propane System at Low

Temperature, Journal of Chemical & Engineering Data 33 (1988) 111-115.

87. N.L. Yarym-Agaev, L.D. Afanasenko, V.G. Matvienko, Y.Y. Ryabkin, G.B. Tolmacheva,

The Gas-Liquid Equilibrium in the Methane-Hydrogen Sulfide System at a Temperature

Below 273 K, Ukrainskii Khimicheskii Zhurnal 57 (1991) 701-704.

88. H.H. Reamer, B.H. Sage, W.N. Lacey, Phase Equilibria in Hydrocarbon SystemsVolumetric and Phase Behavior of the Methane-Hydrogen Sulfide System, Industrial &

Engineering Chemistry 43 (1951) 976-981.

89. V. Stark, A.E. Wastie, J. Sliosberg, Fuel Gas Pipeline System, U.S. Patent 3,689,237,

September 5,1972.

90. E.M. Arenson, Method of Vaporizing and Combining a Liquefied Cryogenic Fluid Stream

with a Gas Stream, U.S. Patent 3,771,260, November 13,1973.

91. T.G. Chin, R.F. Klaver, A. Alston, Gas Saturation Monitoring System and Method for

Controlling Condensable Fuel Added to a Gas, U.S. Patent 4,675,028, June 23,1987.

92. American Society for Testing and Materials, Annual Book of the ASTM Standards, Vol.

05.01, ASTM: Philadelphia, PA, 2013, http://www.astm.org.

93. W.L. Leffler, Petroleum Refining in Nontechnical Language, 4th ed., Penn Well: Tulsa, OK,

2008.

94. J.H. Gary,G.E. Handwerk, Petroleum Refining : Technology and Economics, 4th ed., Marcel

Dekker, Inc.: New York, NY, 2001.

95. R. Rapier. Refining 101: Winter Gasoline. 2006

http://www.theoildrum.com/story/2006/9/13/234043/431.

Gasoline Mixture for Use as a Reference in Field and Laboratory Experiments, Ground

Water Monitoring and Remediation 10 (1990) 135-145.

159

- distillation projectUploaded bySayantan Roy Choudhury
- Compositional Hydrocarbon Reservoirs. Continuous ThermodynamicsUploaded byleo_ruge
- Section 3 Well PerformanceUploaded bySudharsanViki
- TDA 301T-8c - Thermodynamic Properties Real SubstancesUploaded byPortia Shilenge
- Equation of StateUploaded byDipro Mondal
- Tutorial Sheet 04 Answers 2014Uploaded bycheckmeout803
- Physical Principles of Food PreservationUploaded byrodorojas9839
- Basic(2)Uploaded byValya Ruseva
- lleUploaded byBasilGhani
- rpi_physics1_lec01Uploaded byKevin Lyman
- Topic 4. Binary Distillation V2Uploaded byLaura Natalia Nuñez
- soal matekkim.pdfUploaded bydila
- Calypso_07_OVCMM.pdfUploaded byDragu Stelian
- Distillation PostLab FinalUploaded byAnthea Bettina Fresnoza
- DistillationUploaded byAmeelaD
- Equotip Uncertainty Clarification Short E 2014.01.10Uploaded bysharontanas
- 03 Reliability of Generation Systems[1]Uploaded byrvillasa
- 43072296 HTFS Presentation 2Uploaded byDivyesh Patel
- SPE Phase Behavior Monograph Ch 5Uploaded byJuan Marcelo Aguirre
- 1_5024240515088908344Uploaded byNavvab Salehi
- 01. Financial Modeling-monte Carlo Simulation (1)Uploaded byRavi Sankar
- 05 Cylinder Performance(Compressed)Uploaded bySomen Mukherjee
- Problem Set 6 SolutionsUploaded byBeriosca Cueto Amudio
- unit 1 - uncertaintyUploaded byapi-323795755
- Unit8-1-TNSUploaded byJyoti Sharma
- Estudio de la corrosión con HYSYSUploaded byCuando la dictadura es un hecho, la Revolución es un derecho
- Lesson 3Uploaded byWaseem Ahmed
- Error Analysis ImpUploaded byPrasad Rathod
- 32,,ensUploaded byColleen Murphy
- 1-s2.0-000862239500131X-mainUploaded byWilbert James Futalan

- 241ce II Ehs English Reve PDFUploaded byelizabethchemestry
- API MPMS 7- ADD 1Uploaded byelizabethchemestry
- Jp 8050593Uploaded byelizabethchemestry
- CienciaBtex2004Uploaded byAnNy Arroyo
- PRH 1Uploaded byelizabethchemestry
- FQE-Chemicals-NORM-Decontamination-Brochure.pdfUploaded byelizabethchemestry
- Referencia 1.pdfUploaded byelizabethchemestry
- te_1225_prn.pdfUploaded byelizabethchemestry
- Norm PaperUploaded byelizabethchemestry
- 910-Article Text-1132-1-10-20151030Uploaded byelizabethchemestry
- QUAM2012_P1.pdfUploaded byahmad Yaghi
- Referencia 2.pdfUploaded byelizabethchemestry
- MOUHOUBI Seloua Abstract GLS 13Uploaded byelizabethchemestry
- Evaluation of Engine Parts Wear Using Nano Lubrication OilUploaded byJoel E Valencia
- 0263617011494141Uploaded byelizabethchemestry
- s11837-005-0180-4Uploaded byelizabethchemestry
- 10.1088@2053-1591@aa707bUploaded byelizabethchemestry
- Artículos IRUploaded byelizabethchemestry
- SM Chapter3Uploaded byantoniotoledo20
- Flare Gas MeasurementUploaded byelizabethchemestry
- API 12BUploaded byLENIN GAMARRA
- Almada 2017Uploaded byelizabethchemestry
- Factor de Co2Uploaded byelizabethchemestry
- Factor CO2 (2)Uploaded byelizabethchemestry
- Sources of Uncertainty in GC and HPLC. ReviewUploaded bysorinscribd
- The state of the cubic equations of state, valderramaUploaded byxx_aleksa_hrvatska_xx
- Cromatografia MSUploaded byiMarkonikov

- HPLCSol87naUploaded bypasargadae_m
- A standard exam time table in a semesterUploaded byAalok Gangopadhyay
- DNV-OS-F101 2000 submarine pipeline system.pdfUploaded byMichael Moore
- Degradation of Gas Turbine Performance in Natural Gas ServiceUploaded byeankibo
- Artemia Culture for Intensive Finfish.pdfUploaded bygollakoti
- Poultry Science 2003 Ricke 632 9Uploaded byJose Mario Ferriere Sepulveda
- Plastics Used by Bright AgrotechUploaded bypwilkers36
- P. M. Sheridan et al- High-Resolution Spectroscopic Investigation of the B^2-A1-X^2-A1 Transitions of CaCH3 and SrCH3Uploaded byRemazzz
- Aerobic ExcersiceUploaded byizzat zafireen
- Haarman 2016 SRI-IndiaUploaded byAnonymous t7MdBjnO
- Prof. Zahid Ahmad Siddiqi Lec-3-Flexural Analysis and Design of BeamnsUploaded byrana
- apes chapter 3Uploaded byapi-234999021
- FR530Uploaded byrocao
- High Rate Nitrogen Removal by ANAMMOX Internal Circulation Reactor (IC) for Old Landfill Leachate TreatmentUploaded byTerence Chan
- Literature SurveyUploaded byify
- PhD Proposal_HamidahUploaded byHamidah Abd Hamid
- Chapter 15Uploaded byimneo
- Penguapan-pengembunan-3Uploaded byDahniarIka
- 314 Monofinish GbUploaded bydimitrios25
- nitrogen in plant mineral nutritionUploaded bysadekali
- Waste to Wealth by Dr Sivapalan KathiravaleUploaded bykaitzer
- Evak Multistage PumpsUploaded byRahid Bhatti
- Silica Gel Chromatography MSDSUploaded byRajesh Galgalikar
- Flash Point and Chemical Composition of Aviation Kerosene (Jet A)Uploaded byMartin Wac Hand
- FitoUploaded byLucas Sanchez
- Nuclear Energy_ the Good, The Bad, And the Debatable - Curriculum Booklet - DesconocidoUploaded byJosé Luis
- Ramsbootom carbon residue.pdfUploaded bynishanthpobbathi
- msdsUploaded byM Nur Hidayat
- Growing E. coli to high cell density—A historical perspective on method developmentUploaded byHui Zhang
- ieltsfever-academic-reading-practice-test-7-pdf.pdfUploaded byDüb daRy