Hlabano-Moyo BM

Separation of SO2/O2 using membrane technology

Bongibethu. M. Hlabano-Moyo (B.Eng) Chemical (Hons)

Dissertation submitted in partial fulfillment of the requirements of the degree Master of

Engineering in Chemical Engineering of the North West University in Potchefstroom

Supervisor: Dr Percy. van der Gryp (School of Chemical and Minerals Engineering)

Co-supervisors: Dr Dmtri Bessarabov (Hydrogen South Africa Infrastructure),

: Prof. Henning Krieg (Chemical Resource Beneficiation)

ABSTRACT

i

ABSTRACT

The Hybrid Sulphur process is one technology out of a multitude of known technologies

responsible for hydrogen production. Within the latter hydrogen production cycle, it is pivotal

to recover O2 as a by-product from a sulphuric acid decomposition reaction that produces

SO2, H2O and O2. It is assumed that a simple phase separation stage carried out on the

reaction products would liberate SO2 and O2 as a gaseous mixture leaving behind H2O in the

liquid state.

Several separation technologies are available to effect SO2/O2 separation, but membrane

technology has proved to be dearer due to simplicity of the technology, low capital and

energy costs. It is a pity though that insignificant work has been done that considers the

SO2/O2 binary system in the membrane technology context. Of the insignificant work done,

non commercial membranes were employed. It is on the latter background that the present

study was proposed.

Six commercial membranes were selected from literature, two (Udel Polysulfone and Teflon

AF 2400) of which are currently used in gas separation applications and the remainder

(Hyflon M, Hyflon F, Halar and Nafion 117) not necessarily used as gas separation

membranes but present a potential of separating SO2/O2. The inclusion of the latter four

membranes sought to unearth unknown gas separation potentials of the membranes based

on hypothetical 1 m thick membranes.

A screening technique was employed to eliminate poor performing membranes through pure

component permeation of SO2, O2, N2 and CO2. The use of the additional gases (N2 and

CO2) was meant to allow the generation of a pool of data that would be used as a yardstick

to compare to literature and thus validate the authenticity of the designed set up. The single

permeation experiments were carried out at 25C and at absolute gas feed pressures of 1

bar, 2 bar and 3 bar, with the exception of Hyflon F experiments that were carried out at 3.85

bar, 2.85 bar and 1.85 bar also at 25C. The effect of pressure on gas permeability and ideal

selectivity of all gases against O2 was investigated. Udel Polysulfone and Nafion 117

presented clearly evident pressure dependant SO2 permeabilities whilst CO2, N2 and O2

permeabilities were sluggishly dependant on pressure in all membranes. Gas flux in general

increased with increasing pressure as pressure is essentially the driving force for

permeability. Membrane screening for further investigation was then performed based on a

compromise between SO2/O2 ideal selectivity and SO2 flux in hypothetical 1 m thick

membranes. Membranes that presented the best SO2/O2 selectivity include, Udel Polysulfone

with SO2/O2 selectivities of 46, 58 and 314 at 1 bar, 2 bar and 3 bar respectively, Nafion 117

with SO2/O2 selectivities of 30, 35 and 40 at 1 bar, 2 bar and 3 bar respectively and Halar

ABSTRACT

ii

with a SO2/O2 selectivity of 17 at 3 bar. The best SO2 flux through hypothetical 1 m thick

membranes was manifested in Teflon AF 2400 with SO2 fluxes of 3.6 m3.m-2.hr-1, 5.9 m3.m-

2.hr-1 and 9.9 m3.m-2.hr-1 at trans-membrane pressures of 1 bar, 2 Bar and 3 Bar respectively,

Udel Polysulfone with SO2 fluxes of 0.13 m3.m-2.hr-1, 0.32 m3.m-2.hr-1 and 2.56 m3.m-2.hr-1 at

trans-membrane pressures of 1 bar, 2 bar and 3 bar respectively and Nafion 117 with SO2

fluxes of 0.48 m3.m-2.hr-1, 1.03 m3.m-2.hr-1 and 1.79 m3.m-2.hr-1 at 1 bar, 2 bar and 3 bar trans-

membrane pressures respectively. Despite Teflon AF 2400 presenting the highest SO2 flux,

the poor SO2/O2 ideal selectivity 1 rendered the membrane unfit for further investigation.

The low SO2 flux (0.02 m3.m-2.hr-1) presented by Halar also rendered the membrane unfit for

further investigation despite the relatively fair SO2/O2 ideal selectivity of 17.

Binary permeation experiments were then performed on Udel Polysulfone and Nafion 117

after passing the single permeation screening test. Gas mixture compositions of (25 wt %:75

wt %, SO2:O2), (50 wt %:50 wt %, SO2:O2) and (75 wt %:25 wt %, SO2:O2) were employed.

The binary permeation experiments were carried out at a temperature range of 15C to 55C

and a SO2 feed partial pressure range of 1.1 0.1 bar to 2.3 0.1 bar.

The SO2 permeate composition increased with pressure and decreased with temperature in

both Udel Polysulfone and Nafion 117. Udel Polysulfone presented a superior SO2/O2

separation potential, concentrating a (25 wt %:75 wt %, SO2:O2) gas mixture to (94 wt %:6 wt

%, SO2:O2) in a single step at 15C and 2.2 0.1 bar SO2 feed partial pressure. Nafion 117

concentrated the same gas mixture to (87 wt %:13 wt %, SO2:O2) also in a single step at 15

C and 2.4 0.1 bar SO2 feed partial pressure. Based on hypothetical 1 m thick

membranes, Nafion 117 presented generally high SO2 molar fluxes in mixture with O2 of

about a magnitude higher than the SO2 molar fluxes presented in Udel Polysulfone. Also,

Nafion 117 proved to be less prone to plasticisation within the pressure range considered.

Despite Udel Polysulfone presenting generally lower SO2 molar fluxes, Udel Polysulfone was

deemed to be the ideal membrane for the current SO2/O2 separation application as

thicknesses of 1 m of Nafion the perfluorosulfonic acid based membrane are currently

unknown and also Udel Polysulfone presented the best SO2/O2 separation capability. The

latter findings are envisaged to prompt further research on the production of ultra-thin

perfluoro-sulfonic acid based membranes for the current application.

Key words: Sulphur dioxide, membrane, Hybrid-sulphur, Udel Polysulfone, Nafion 117

DECLARATION

iii

DECLARATION

I hereby declare that all the content compiled in this dissertation is my original work with the

exception of referenced work. The current study has not been presented in any form to any

institution.

Signed at on the day of

Bongibethu. M. Hlabano-Moyo

ACKNOWLEDGEMENTS

iv

ACKNOWLEDGEMENTS

I would like to acknowledge the efforts of the following individuals that contributed to the

fruition of this study. Many thanks to my supervisor Dr Percy van der Gryp for the

unfathomable guidance he afforded me. Thanks to my Co-supervisors Dr Dmtri Bessarabov

and Prof Henning Krieg. I am grateful for the technical advice from Professor Hein

Neomagus and Dr Kaitano Rufaro at the commencement of the project. Vital analytical work

done by Dr L. Tiedt and Dr Annine Jordan is acknowledged. The administrative assistance

from Mr. Frikkie van der Merwe, Mrs Hestelle Stoppel, Mrs. Eleanor De Koker and Miss

Annieta Bok is not negated. The technical support from Mr. Adrian Brock, Mr Jan Croez, Mr

Johan Broodryk, Mr. Dawie Branken and Mr. Andries Kruger was invaluable. A big thank you

to Hydrogen South Africa Infrastructure for the financial support, particularly Dr Dmtri

Bessarabov for his benevolence. Many thanks to my colleagues:

Bothwell Nyoni

Liberty Mapamba

Steven Chiuta

Sandile Madonsela

Dursman Mchabe

Hope Baloyi

Gregory Okolo

Leonard Ndlovu

Wisdom Dube

Special thanks go to my beloved parents and family, above all I place all my gratitude to the

Almighty God.

TABLE OF CONTENTS

v

TABLE OF CONTENTS

ABSTRACT ................................................................................................................................... I

DECLARATION ............................................................................................................................III

ACKNOWLEDGEMENTS ............................................................................................................ IV

TABLE OF CONTENTS ............................................................................................................... V

LIST OF SYMBOLS AND ABBREVIATIONS ................................................................................ X

LIST OF TABLES ...................................................................................................................... XIII

LIST OF FIGURES ................................................................................................................ XXVII

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

OVERVIEW .................................................................................................................................. 1

1.1 BACKGROUND AND MOTIVATION ...................................................................................... 2

1.2 OBJECTIVES ......................................................................................................................... 6

1.3 SCOPE OF THE STUDY ........................................................................................................ 6

CHAPTER 2 : LITERATURE OVERVIEW ...................................................................................10

OVERVIEW .................................................................................................................................10

2.1 APPLICATION OF MEMBRANE GAS SEPARATION ...........................................................11

2.1.1 HISTORY OF MEMBRANE SEPARATION PROCESSES .................................................................11

2.1.2 COMMERCIAL APPLICATIONS OF MEMBRANE GAS SEPARATION .................................................15

2.2 PRINCIPLES OF GAS SEPARATION THROUGH MEMBRANES ........................................16

2.2.1 POLYMERIC MEMBRANES IN GAS SYSTEMS .............................................................................16

2.2.2 FUNDAMENTALS OF GAS TRANSPORT IN NON-POROUS DENSE POLYMERIC FILMS ......................16

2.2.2.1 Diffusion modes in dense polymeric films ........................................................................17

2.2.2.2 Solubility modes in dense polymeric films ........................................................................19

2.2.2.3 Permeability and Selectivity .............................................................................................21

2.3 CRITICAL PARAMETERS AFFECTING GAS TRANSPORT IN POLYMERIC FILMS ...........22

2.3.1 TEMPERATURE .....................................................................................................................22

2.3.2 PRESSURE ...........................................................................................................................23

2.4 STATE OF THE ART REVIEW OF SO2 GAS SEPARATION THROUGH MEMBRANES ......25

TABLE OF CONTENTS

vi

2.4.1 SIGNIFICANCE OF SO2 MEMBRANE SEPARATION RESEARCH .....................................................29

2.4.2 SO2 MEMBRANE SEPARATION RESEARCH OBJECTIVES ............................................................30

2.4.3 SO2 MEMBRANE SEPARATION RESEARCH APPROACH ..............................................................30

2.4.4 SO2 MEMBRANE SEPARATION RESEARCH FINDINGS ................................................................31

2.5 GENERAL REVIEW OF SO2 SEPARATION THROUGH MEMBRANES ...............................35

2.6 REFERENCES .....................................................................................................................37

CHAPTER 3 :EXPERIMENTAL ...................................................................................................40

OVERVIEW .................................................................................................................................40

3.1 MEMBRANES USED ............................................................................................................41

3.1.1 HYFLON PFA/MFA ...............................................................................................................44

3.1.2 HALAR ECTFE (ETHYLENE-CHLOROTRIFLUOROETHYLENE) ....................................................44

3.1.3 UDEL POLYSULFONE ............................................................................................................45

3.1.4 TEFLON AF 2400 .................................................................................................................45

3.1.5 NAFION 117 .........................................................................................................................46

3.2 CHEMICALS AND GASES USED .........................................................................................47

3.3 EXPERIMENTAL METHODOLOGY ......................................................................................48

3.3.1 INTRODUCTION .....................................................................................................................48

3.3.2 EXPERIMENTAL SETUP AND PROCEDURE ................................................................................48

3.3.2.1 Determination of permeate side volume ..........................................................................52

3.3.2.2 Determination of leak rate ................................................................................................52

3.3.2.3 Single permeation ............................................................................................................53

3.3.2.4 Binary permeation ...........................................................................................................56

3.3.3 VALIDATION OF EXPERIMENTAL METHOD ...............................................................................57

3.4 EXPERIMENTAL DESIGN AND PLANNING .........................................................................61

3.4.1 PROCESS CONDITIONS IN THE HYBRID SULPHUR PROCESS .....................................................61

3.4.2 EXPERIMENTAL RANGE .........................................................................................................65

3.5 ANALYTICAL EQUIPMENT AND CALIBRATION CURVES ..................................................66

3.5.1 GAS CHROMATOGRAPH SPECIFICATIONS ................................................................................66

3.5.2 GAS CHROMATOGRAPH CALIBRATION .....................................................................................67

3.6 REFERENCES ......................................................................................................................69

CHAPTER 4 :RESULTS AND DISCUSSION ..............................................................................71

TABLE OF CONTENTS

vii

OVERVIEW .................................................................................................................................71

4.1 MEMBRANE SELECTION .....................................................................................................72

4.1.1 CHOICE OF MEMBRANE BASED ON MATERIAL TYPE ..................................................................72

4.1.2 CHOICE OF MEMBRANES BASED ON INTRINSIC PROPERTIES .....................................................75

4.1.3 CHOICE OF MEMBRANE BASED ON SCREENING EXPERIMENTS ..................................................78

4.2 SINGLE COMPONENT PERMEATION OF SO2 AND O2 IN NAFION AND UPS ...................82

4.2.1SINGLE PERMEATION IN UDEL POLYSULFONE ..........................................................................82

4.2.2 SINGLE PERMEATION IN NAFION 117 .....................................................................................86

4.2.3 COMPARISON OF THE SO2 AND O2 PERMEATION IN THE NAFION 117 AND UPS .........................90

4.3 BINARY PERMEATION OF SO2/O2 GAS MIXTURES IN NAFION AND UPS .......................92

4.3.1 BINARY PERMEATION IN NAFION 117 ......................................................................................92

4.3.2 BINARY PERMEATION IN UDEL POLYSULFONE ....................................................................... 103

4.3.3 COMPARISON OF THE SO2/O2 SEPARATION POTENTIAL AND THE GAS FLUX THROUGH NAFION

117 AND UDEL POLYSULFONE ............................................................................................ 112

4.4 CONCLUSION .................................................................................................................... 121

4.6 REFERENCES ................................................................................................................... 123

CHAPTER 5 : CONCLUSION AND RECOMMENDATIONS...................................................... 127

OVERVIEW ............................................................................................................................... 127

5.1 CONCLUSION .................................................................................................................... 128

5.1.1 SINGLE PERMEATION .......................................................................................................... 128

5.1.2 BINARY PERMEATION .......................................................................................................... 129

5.2 RECOMMENDATIONS ....................................................................................................... 129

APPENDIX A :MEMBRANE CELL & FILM DIMENSIONS ......................................................... 130

OVERVIEW ............................................................................................................................... 130

APPENDIX B :MEASUREMENT OF PERMEATE CHAMBER VOLUME .................................. 138

OVERVIEW ............................................................................................................................... 138

MEASUREMENT OF PERMEATE CHAMBER CONSTANT VOLUME ........................................................ 139

APPENDIX C :CONSISTENCY OF UNITS AND SAMPLE CALCULATIONS ............................ 143

OVERVIEW ............................................................................................................................... 143

TABLE OF CONTENTS

viii

SAMPLE CALCULATIONS ....................................................................................................... 144

DERIVATION OF PERMEABILITY EQUATION AND CONSISTENCY OF UNITS .......................................... 144

SINGLE PERMEATION SAMPLE CALCULATIONS ............................................................................... 148

Permeability .............................................................................................................................. 148

Flux ........................................................................................................................................... 150

Ideal selectivity .......................................................................................................................... 151

BINARY PERMEATION SAMPLE CALCULATIONS ............................................................................... 151

Flux ........................................................................................................................................... 151

Pseudo permeability .................................................................................................................. 153

Real selectivity .......................................................................................................................... 154

ESTIMATION OF SOME PERMEATE COMPOSITIONS .......................................................................... 154

Estimation of Nafion 117 permeate composition with (25:75, SO2:O2) wt % feed at pSO2 = 1.2

bar .......................................................................................................................................... 155

Estimation of Udel Polysulfone SO2 permeate composition with (25:75, SO2:O2) wt % feed at

pSO2 = 1.2 bar ........................................................................................................................ 157

CALCULATION OF POLYMER FREE VOLUME .................................................................................... 161

Halar free volume ...................................................................................................................... 161

Hyflon M free volume ................................................................................................................ 163

REFERENCES .......................................................................................................................... 166

APPENDIX D :SINGLE AND BINARY PERMEATION RESULTS ............................................. 167

OVERVIEW ............................................................................................................................... 167

APPENDIX E : EFFECT OF HUMIDITY ON GAS TRANSPORT IN A NAFION BASED

MEMBRANE .................................................................................................................... 325

OVERVIEW ............................................................................................................................... 325

REFERENCES .......................................................................................................................... 327

APPENDIX F : ERROR AND REPEATABILITY OF RESULTS ................................................. 328

OVERVIEW ............................................................................................................................... 328

EXPERIMENTAL ERROR AND REPEATABILITY FOR PERMEATION EXPERIMENTS .................................. 329

EXPERIMENTAL ERROR AND REPEATABILITY FOR COMPOSITION EXPERIMENTS ................................ 331

APPENDIX G :CALIBRATION CURVE ..................................................................................... 333

OVERVIEW ............................................................................................................................... 333

TABLE OF CONTENTS

ix

GAS CHROMATOGRAPH CALIBRATION CURVE ................................................................................ 337

APPENDIX H :VAPOR LIQUID EQUILIBRIUM DATA ............................................................... 339

OVERVIEW ............................................................................................................................... 339

VAPOR LIQUID PROPERTIES OF PROCESS STREAMS ....................................................................... 340

DETERMINATION OF THE OPTIMUM FLASH TEMPERATURE RANGE .................................................... 341

REFERENCES .......................................................................................................................... 347

LIST OF SYMBOLS AND ABBREVIATIONS

x


Symbol Description Unit

A Membrane area m2

b Langmuir affinity constant Kpa-1

C Concentration of gas mole.cm-3 of polymer

C* Saturation concentration of gas mole.cm-3 of polymer

CD Dissolved gas concentration in polymer mole.cm-3 of polymer

CH Adsorbed gas concentration in polymer mole.cm-3 of polymer

CH Langmuir capacity constant mole.cm-3 of polymer

CO Carbon Monoxide -

CO2 Carbon Dioxide -

D Diffusivity cm2.s-1

D0 Pre-exponential constant for diffusivity cm2.s-1

(dp/dt)leak p/t)leak Pressure build up in permeate due to leakage mbar.s-1

(dp/dt)ss p/t)ss Steady state pressure build up in permeate mbar.s-1

(dv/dt) Volumetric displacement cm3.s-1

ED Diffusion activation energy KJ.mol-1

EP Permeation activation energy KJ.mol-1

H2 Hydrogen -

H2O Water -

H2S Hydrogen Sulfide -

H2SO4 Sulphuric acid -

Hcondensation Enthalpy of condensation of gas in Polymer KJ.mol-1

Hmixing Enthalpy of creating polymer gas molecular gaps KJ.mol-1

Hs Enthalpy of solution KJ.mol-1

J Flux mole.m-2.s-1

KD Henrys law constant mole.cm-3.pa-1

l Membrane thickness m

NaOH Sodium Hydroxide -

N2 Nitrogen -

P, PA Permeability coefficient Barrer

patm Atmospheric pressure Pa, Bar, atmosphere

p1 Downstream pressure Pa, Bar, atmosphere


xi

Greek symbol Description Unit

Selectivity -

SO2 Sulphur dioxide pseudo permeability coefficient mol.m.s-1.m-2.pa-1

O2 Oxygen pseudo permeability coefficient mol.m.s-1.m-2.pa-1

Abbreviation Description

ASTM American Standard Testing Method

AF Amorphous polymer

BPR Back Pressure Regulator

CSIR Council for Scientific and Industrial Research

ECTFE Ethylene-Chlorotrifluoro ethylene

GC Gas Chromatograph

HP Hewlett Packard

HySA Hydrogen South Africa

MD Machine Direction

MFC Mass Flow Controller

PFA Perfluoroalkoxy fluorocarbon

Symbol Description Unit

p2 Upstream pressure Pa, Bar, atmosphere

pso2 Sulphur dioxide partial pressure Pa, Bar, atmosphere

po2 Oxygen partial pressure Pa, Bar, atmosphere

p Trans-membrane pressure Pa, Bar, atmosphere

R Molar gas constant J.K-1.mol-1

S Solubility mole.cm-3 of polymer.pa-1

S0 Pre-exponential factor for solubility mole.cm-3 of polymer.pa-1

SF Sweep gas flow rate cm3.s-1

T Temperature C, F, K

TC Critical temperature C, F, K

Tg Glass transition temperature C, F, K

V Volumetric flowrate m3.hr-1

Vd Downstream volume cm3

xi Gas mole fraction -


xii

Abbreviation Description

ppm Parts per million

PR Pressure regulator

PT Pressure transducer

SEM Scanning electron microscope

SILM Supported Ionic Iiquid Membrane

TD Transverse Direction

UPS Udel Polysulfone

VLE Vapour Liquid Equilibrium

LIST OF TABLES

xiii

LIST OF TABLES

Table 2.1 Commercial applications of membrane gas separation ................................................................... 15

Table 2.2 State of the art SO2 gas transport in membranes ............................................................................ 26



Table 3.1 Mechanical properties of membranes .............................................................................................. 42

Table 3.2 Thermal properties of membranes ................................................................................................... 43

Table 3.3 Chemicals used ............................................................................................................................... 47

Table 3.4 Gases used ..................................................................................................................................... 47

Table 3.5 Equipment list and specifications ..................................................................................................... 49

Table 3.6 Process flow streams (Adapted from Gorensek & Summers, (2009:4108)) ..................................... 62

Table 3.7 Single permeation experimental range and variables ...................................................................... 65

Table 3.8 Binary permeation experimental range and variables ...................................................................... 65

Table 4.1 Characteristics of different membrane types .................................................................................... 74

Table 4.2 Intrinsic properties of selected membranes ..................................................................................... 76

Table 4.3 Properties of gases ......................................................................................................................... 76

Table 4.4 Ideal selectivity of gases against O2 ................................................................................................ 80

Table 4.5 Normalized gas flux values per 1 micrometer thick hypothetical film at diverse trans-membrane

pressures ........................................................................................................................................................ 81

Table 4.6 SO2 partial pressure points ............................................................................................................ 116

Table 4.7 Summary of overall membrane performance ................................................................................. 121

Table B.1 Raw data for permeate volume calculation for Hyflon M, Halar, Nafion 117 & UPS permeation .... 139

Table B.2 Raw data for permeate volume calculation for Hyflon F permeation .............................................. 140

Table B.3 Raw data for permeate volume calculation for Teflon AF 2400 permeation ................................... 141

Table B.4 Permeate chamber volumes for single permeation ....................................................................... 142

Table C.1 SO2 permeate composition plotting points for (25:75, SO2:O2) wt % feed in Nafion 117 at pSO2 = 1.7

bar (pSO2 feed = 2.4 bar) ................................................................................................................................ 156

Table C.2 SO2 permeate composition at 25C and pSO2 = 0.8 bar (pSO2 = 1.4 bar feed) in Nafion 117 ......... 156

Table C.3 SO2 permeate composition plotting points SO2 permeate composition plotting points for (25:75,

SO2:O2) wt % feed in Udel Polysulfone at pSO2 = 1.45 bar (pSO2 feed = 2.2 bar) .......................................... 159

Table C.4 SO2 permeate composition at 25C and pSO2 = 0.6385 bar (pSO2 = 1.3 bar feed) in Udel Polysulfone

..................................................................................................................................................................... 159

Table C.5 Atomic contributions ..................................................................................................................... 162

Table D.1 SO2 permeability in Hyflon F Raw Data ...................................................................................... 168

Table D.2 SO2 permeability in Hyflon F Calculated Data ............................................................................ 168

LIST OF TABLES

xiv

Table D.3 O2 permeability in Hyflon F Raw Data ........................................................................................ 171

Table D.4 O2 permeability in Hyflon F Calculated Data .............................................................................. 171

Table D.5 N2 permeability in Hyflon F Raw Data ........................................................................................ 174

Table D.6 N2 permeability in Hyflon F Calculated Data ............................................................................... 174

Table D.7 CO2 permeability in Hyflon F Raw Data ..................................................................................... 177

Table D.8 CO2 permeability in Hyflon F Calculated Data ............................................................................ 177

Table D.9 SO2 permeability in Hyflon M Raw Data ..................................................................................... 180

Table D.10 SO2 permeability in Hyflon M Calculated Data ........................................................................ 180

Table D.11 O2 permeability in Hyflon M Raw Data .................................................................................... 183

Table D.12 O2 permeability in Hyflon M Calculated Data ........................................................................... 183

Table D.13 N2 permeability in Hyflon M Raw Data .................................................................................... 186

Table D.14 N2 permeability in Hyflon M Calculated Data ........................................................................... 186

Table D.15 CO2 permeability in Hyflon M Raw Data ................................................................................. 188

Table D.16 CO2 permeability in Hyflon M Calculated Data ........................................................................ 188

Table D.17 SO2 permeability in Halar Raw Data ........................................................................................ 191

Table D.18 SO2 permeability in Halar Calculated Data .............................................................................. 191

Table D.19 O2 permeability in Halar Raw Data ........................................................................................... 193

Table D.20 O2 permeability in Halar Calculated Data ................................................................................. 193

Table D.21 CO2 permeability in Halar Raw Data ....................................................................................... 195

Table D.22 CO2 permeability in Halar Calculated Data .............................................................................. 195

Table D.23 SO2 permeability in Udel Polysulfone Raw Data ..................................................................... 197

Table D.24 SO2 permeability in Udel Polysulfone Calculated Data ........................................................... 197

Table D.25 O2 permeability in Udel Polysulfone Raw Data ......................................................................... 200

Table D.26 O2 permeability in Udel Polysulfone Calculated Data .............................................................. 200

Table D.27 N2 permeability in Udel Polysulfone Raw Data ......................................................................... 203

Table D.28 N2 permeability in Udel Polysulfone Calculated Data ............................................................... 203

Table D.29 CO2 permeability in Udel Polysulfone Raw Data ..................................................................... 205

Table D.30 CO2 permeability in Udel Polysulfone Calculated Data............................................................. 205

Table D.31 SO2 permeability in Teflon AF 2400 Raw Data ........................................................................ 208

Table D.32 SO2 permeability in Teflon AF 2400 Calculated Data ............................................................... 208

Table D.33 O2 permeability in Teflon AF 2400 Raw Data .......................................................................... 211

Table D.34 O2 permeability in Teflon AF 2400 Calculated Data ................................................................. 211

Table D.35 N2 permeability in Teflon AF 2400 Raw Data ........................................................................... 214

Table D.36 N2 permeability in Teflon AF 2400 Calculated Data .................................................................. 214

Table D.37 CO2 permeability in Teflon AF 2400 Raw Data ....................................................................... 217

LIST OF TABLES

xv

Table D.38 CO2 permeability in Teflon AF 2400 Calculated Data ............................................................. 217

Table D.39 SO2 permeability in Nafion 117 Raw Data ................................................................................ 220

Table D.40 SO2 permeability in Nafion 117 Calculated Data ..................................................................... 220

Table D.41 O2 permeability in Nafion 117 Raw Data .................................................................................. 223

Table D.42 O2 permeability in Nafion 117 Calculated Data ....................................................................... 223

Table D.43 CO2 permeability in Nafion 117 Raw Data ............................................................................... 226

Table D.44 CO2 permeability in Nafion 117 Calculated Data .................................................................... 226

Table D.45 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 15C & 2.4 bar pSO2 Raw Data ........... 229

Table D.46 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 15C & 2.4 bar pSO2 Calculated Data . 229

Table D.47 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 15C & 2.4 bar pSO2 GC area reports (1st,

2nd & 3rd trials) ............................................................................................................................................... 229




2nd & 3rd trials) ............................................................................................................................................... 230




2nd & 3rd trials) ............................................................................................................................................... 231




2nd & 3rd trials) ............................................................................................................................................... 232




2nd & 3rd trials) ............................................................................................................................................... 233




2nd & 3rd trials) ............................................................................................................................................... 234




2nd & 3rd trials) ............................................................................................................................................... 235

LIST OF TABLES

xvi




2nd & 3rd trials) ............................................................................................................................................... 236




2nd & 3rd trials) ............................................................................................................................................... 237




2nd & 3rd trials) ............................................................................................................................................... 238




2nd & 3rd trials) ............................................................................................................................................... 239




2nd & 3rd trials) ............................................................................................................................................... 240




2nd & 3rd trials) ............................................................................................................................................... 241




2nd & 3rd trials) ............................................................................................................................................... 242




2nd & 3rd trials) ............................................................................................................................................... 243

Table D.90 Binary permeation of 25:75 (SO2:O2) in Udel Polysolfone @ 15C & 2.2 bar pSO2 Raw Data .. 244

Table D.91 Binary permeation of 25:75 (SO2:O2) in Udel Polysulfone @ 15C & 2.2 bar pSO2 Calculated

Data .............................................................................................................................................................. 244

LIST OF TABLES

xvii

Table D.92 Binary permeation of 25:75 (SO2:O2) in Udel Polysulfone @15C & 2.2 bar pSO2 GC area reports

(1st, 2nd & 3rd trials) ........................................................................................................................................ 244



Data .............................................................................................................................................................. 245

Table D.95 Binary permeation of 25:75 (SO2:O2) in Udel Polysulfone @ 25C & 2.2 bar pSO2 GC area

reports (1st, 2nd & 3rd trials) ............................................................................................................................ 245



Data .............................................................................................................................................................. 246





Data .............................................................................................................................................................. 247



Table D.102 Binary permeation of 25:75 (SO2:O2) in Udel Polysolfone @ 55C & 2.2 bar pSO2 Raw Data 248


Data .............................................................................................................................................................. 248





Data .............................................................................................................................................................. 249





Data .............................................................................................................................................................. 250





Data .............................................................................................................................................................. 251

LIST OF TABLES

xviii





Data .............................................................................................................................................................. 252





Data .............................................................................................................................................................. 253





Data .............................................................................................................................................................. 254





Data .............................................................................................................................................................. 255





Data .............................................................................................................................................................. 256





Data .............................................................................................................................................................. 257





Data .............................................................................................................................................................. 258

LIST OF TABLES

xix



Table D.135 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 25C & 2.4 bar pSO2 Raw Data ......... 259

Table D.136 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 25C & 2.4 bar pSO2 Calculated Data 259

Table D.137 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 25C & 2.4 bar pSO2 GC area reports

(1st, 2nd & 3rd trials) ........................................................................................................................................ 259




(1st, 2nd & 3rd trials) ........................................................................................................................................ 260




(1st, 2nd & 3rd trials) ........................................................................................................................................ 261




(1st, 2nd & 3rd trials) ........................................................................................................................................ 262




(1st, 2nd & 3rd trials) ........................................................................................................................................ 263




(1st, 2nd & 3rd trials) ........................................................................................................................................ 264




(1st, 2nd & 3rd trials) ........................................................................................................................................ 265




(1st, 2nd & 3rd trials) ........................................................................................................................................ 266


LIST OF TABLES

xx



(1st, 2nd & 3rd trials) ........................................................................................................................................ 267

Table D.162 Binary permeation of 25:75 (SO2:O2) in Udel Polysulfone @ 25C & 2.2 bar pSO2 Raw Data 268


Data .............................................................................................................................................................. 268





Data .............................................................................................................................................................. 269





Data .............................................................................................................................................................. 270





Data .............................................................................................................................................................. 271





Data .............................................................................................................................................................. 272





Data .............................................................................................................................................................. 273




LIST OF TABLES

xxi


Data .............................................................................................................................................................. 274





Data .............................................................................................................................................................. 275





Data .............................................................................................................................................................. 276



Table D.189 Binary flux results of 75:25 wt (SO2:O2) in Nafion 117 @ 15C & 1.2 bar pSO2 Raw Data ... 277

Table D.190 Binary flux results of 75:25 wt (SO2:O2) in Nafion 117 @ 15C & 1.2 bar pSO2 Calculated Data

..................................................................................................................................................................... 277



..................................................................................................................................................................... 278



..................................................................................................................................................................... 279



..................................................................................................................................................................... 280



..................................................................................................................................................................... 281

Table D.199 Binary flux results of 75:25 wt (SO2:O2) in Udel Polysulfone @ 15C & 1.0 bar pSO2 Raw Data

..................................................................................................................................................................... 282

Table D.200 Binary flux results of 75:25 wt (SO2:O2) in Udel Polysulfone @ 15C & 1.0 bar pSO2

Calculated Data ............................................................................................................................................ 282


..................................................................................................................................................................... 283

LIST OF TABLES

xxii


Calculated Data ............................................................................................................................................ 283


..................................................................................................................................................................... 284


Calculated Data ............................................................................................................................................ 284


..................................................................................................................................................................... 285


Calculated Data ............................................................................................................................................ 285


..................................................................................................................................................................... 286


Calculated Data ............................................................................................................................................ 286



..................................................................................................................................................................... 287



..................................................................................................................................................................... 288



..................................................................................................................................................................... 289



..................................................................................................................................................................... 290



..................................................................................................................................................................... 291


..................................................................................................................................................................... 292


Calculated Data ............................................................................................................................................ 292


..................................................................................................................................................................... 293

LIST OF TABLES

xxiii


Calculated Data ............................................................................................................................................ 293


..................................................................................................................................................................... 294


Calculated Data ............................................................................................................................................ 294


..................................................................................................................................................................... 295


Calculated Data ............................................................................................................................................ 295


..................................................................................................................................................................... 296


Calculated Data ............................................................................................................................................ 296



..................................................................................................................................................................... 297

Table D.231 Binary flux results of 25:75 wt (SO2:O2) in Nafion 117 @ 25C & 1.2 bar pSO2 Raw Data .. 298

Table D.232 Binary flux results of 25:75 wt (SO2:O2) in Nafion 117 @ 25C & 1.2 bar pSO2 Calculated

Data .............................................................................................................................................................. 298

Table D.233 Binary flux results of 25:75 wt (SO2:O2) in Nafion 117 @ 35C & 1.2 bar pSO2 Raw Data .. 299


..................................................................................................................................................................... 299



Data .............................................................................................................................................................. 300



Data .............................................................................................................................................................. 301


..................................................................................................................................................................... 302


Calculated Data ............................................................................................................................................ 302


..................................................................................................................................................................... 303

LIST OF TABLES

xxiv


Calculated Data ............................................................................................................................................ 303


..................................................................................................................................................................... 304


Calculated Data ............................................................................................................................................ 304


..................................................................................................................................................................... 305


Calculated Data ............................................................................................................................................ 305


..................................................................................................................................................................... 306


Calculated Data ............................................................................................................................................ 306



Data .............................................................................................................................................................. 307



Data .............................................................................................................................................................. 308



Data .............................................................................................................................................................. 309


..................................................................................................................................................................... 310


Calculated Data ............................................................................................................................................ 310


..................................................................................................................................................................... 311


Calculated Data ............................................................................................................................................ 311


..................................................................................................................................................................... 312


Calculated Data ............................................................................................................................................ 312

LIST OF TABLES

xxv



..................................................................................................................................................................... 313



..................................................................................................................................................................... 314


Table D.266 Bina

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