Separation of SO
2/O
2using 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),
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 µm 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 25°C 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 25°C. 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 µm 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 µm 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 15°C to 55°C 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 15°C 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 µm 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 µm 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.
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
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
2.1.1HISTORY OF MEMBRANE SEPARATION PROCESSES ...11
2.1.2COMMERCIAL APPLICATIONS OF MEMBRANE GAS SEPARATION ...15
2.2 PRINCIPLES OF GAS SEPARATION THROUGH MEMBRANES ...16
2.2.1POLYMERIC MEMBRANES IN GAS SYSTEMS ...16
2.2.2FUNDAMENTALS 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
2.3.1TEMPERATURE ...22
2.3.2PRESSURE ...23
TABLE OF CONTENTS
vi
2.4.1SIGNIFICANCE OF SO2 MEMBRANE SEPARATION RESEARCH ...29
2.4.2SO2 MEMBRANE SEPARATION RESEARCH OBJECTIVES ...30
2.4.3SO2 MEMBRANE SEPARATION RESEARCH APPROACH ...30
2.4.4SO2 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
3.1.1HYFLON PFA/MFA ...44
3.1.2HALAR ECTFE(ETHYLENE-CHLOROTRIFLUOROETHYLENE) ...44
3.1.3UDEL POLYSULFONE ...45
3.1.4TEFLON AF2400 ...45
3.1.5NAFION 117 ...46
3.2 CHEMICALS AND GASES USED ...47
3.3 EXPERIMENTAL METHODOLOGY ...48
3.3.1INTRODUCTION ...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
3.3.3VALIDATION OF EXPERIMENTAL METHOD ...57
3.4 EXPERIMENTAL DESIGN AND PLANNING ...61
3.4.1PROCESS CONDITIONS IN THE HYBRID SULPHUR PROCESS ...61
3.4.2EXPERIMENTAL RANGE ...65
3.5 ANALYTICAL EQUIPMENT AND CALIBRATION CURVES ...66
3.5.1GAS CHROMATOGRAPH SPECIFICATIONS ...66
3.5.2GAS CHROMATOGRAPH CALIBRATION ...67
3.6 REFERENCES ...69
TABLE OF CONTENTS
vii
OVERVIEW ...71
4.1 MEMBRANE SELECTION ...72
4.1.1CHOICE OF MEMBRANE BASED ON MATERIAL TYPE ...72
4.1.2CHOICE OF MEMBRANES BASED ON INTRINSIC PROPERTIES ...75
4.1.3CHOICE 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
4.2.2SINGLE PERMEATION IN NAFION 117 ...86
4.2.3COMPARISON 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
4.3.1BINARY PERMEATION IN NAFION 117 ...92
4.3.2BINARY PERMEATION IN UDEL POLYSULFONE ... 103
4.3.3COMPARISON 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
5.1.1SINGLE PERMEATION ... 128
5.1.2BINARY 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
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
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
LIST OF SYMBOLS AND ABBREVIATIONS
x
LIST OF SYMBOLS AND ABBREVIATIONS
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
C’H 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 Henry’s law constant mole.cm-3.pa-1
l Membrane thickness µm
NaOH Sodium Hydroxide -
N2 Nitrogen -
P, PA Permeability coefficient Barrer
patm Atmospheric pressure Pa, Bar, atmosphere
LIST OF SYMBOLS AND ABBREVIATIONS
xi
Greek symbol Description Unit
α 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
LIST OF SYMBOLS AND ABBREVIATIONS
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
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 2.3 State of the art SO2 gas transport in membranes ... 27
Table 2.4 State of the art SO2 gas transport in membranes ... 28
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 25°C 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 25°C 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
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
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 @ 15°C & 2.4 bar pSO2 – Raw Data ... 229
Table D.46 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 15°C & 2.4 bar pSO2 – Calculated Data . 229 Table D.47 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 15°C & 2.4 bar pSO2 – GC area reports (1st , 2nd & 3rd trials) ... 229
Table D.48 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 25°C & 2.4 bar pSO2 – Raw Data ... 230
Table D.49 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 25°C & 2.4 bar pSO2 – Calculated Data . 230 Table D.50 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 25°C & 2.4 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 230
Table D.51 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 35°C & 2.4 bar pSO2 – Raw Data ... 231
Table D.52 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 35°C & 2.4 bar pSO2 – Calculated Data . 231 Table D.53 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 35°C & 2.4 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 231
Table D.54 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 45°C & 2.4 bar pSO2 – Raw Data ... 232
Table D.55 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 45°C & 2.4 bar pSO2 – Calculated Data . 232 Table D.56 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 45°C & 2.4 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 232
Table D.57 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 55°C & 2.4 bar pSO2 – Raw Data ... 233
Table D.58 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 55°C & 2.4 bar pSO2 – Calculated Data . 233 Table D.59 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 55°C & 2.4 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 233
Table D.60 Binary permeation of 50:50 (SO2:O2) in Nafion 117 @ 15°C & 1.8 bar pSO2 – Raw Data ... 234
Table D.61 Binary permeation of 50:50 (SO2:O2) in Nafion 117 @ 15°C & 1.8 bar pSO2 – Calculated Data . 234 Table D.62 Binary permeation of 50:50 (SO2:O2) in Nafion 117 @ 15°C & 1.8 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 234
Table D.63 Binary permeation of 50:50 (SO2:O2) in Nafion 117 @ 25°C & 1.8 bar pSO2 – Raw Data ... 235
Table D.64 Binary permeation of 50:50 (SO2:O2) in Nafion 117 @ 25°C & 1.8 bar pSO2 – Calculated Data . 235 Table D.65 Binary permeation of 50:50 (SO2:O2) in Nafion 117 @ 25°C & 1.8 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 235
LIST OF TABLES
xvi
Table D.66 Binary permeation of 50:50 (SO2:O2) in Nafion 117 @ 35°C & 1.8 bar pSO2 – Raw Data ... 236 Table D.67 Binary permeation of 50:50 (SO2:O2) in Nafion 117 @ 35°C & 1.8 bar pSO2 – Calculated Data . 236 Table D.68 Binary permeation of 50:50 (SO2:O2) in Nafion 117 @ 35°C & 1.8 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 236 Table D.69 Binary permeation of 50:50 (SO2:O2) in Nafion 117 @ 45°C & 1.8 bar pSO2 – Raw Data ... 237 Table D.70 Binary permeation of 50:50 (SO2:O2) in Nafion 117 @ 45°C & 1.8 bar pSO2 – Calculated Data . 237 Table D.71 Binary permeation of 50:50 (SO2:O2) in Nafion 117 @ 45°C & 1.8 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 237 Table D.72 Binary permeation of 50:50 (SO2:O2) in Nafion 117 @ 55°C & 1.8 bar pSO2 – Raw Data ... 238 Table D.73 Binary permeation of 50:50 (SO2:O2) in Nafion 117 @ 55°C & 1.8 bar pSO2 – Calculated Data . 238 Table D.74 Binary permeation of 50:50 (SO2:O2) in Nafion 117 @ 55°C & 1.8 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 238 Table D.75 Binary permeation of 75:25 (SO2:O2) in Nafion 117 @ 15°C & 2.0 bar pSO2 – Raw Data ... 239 Table D.76 Binary permeation of 75:25 (SO2:O2) in Nafion 117 @ 15°C & 2.0 bar pSO2 – Calculated Data . 239 Table D.77 Binary permeation of 75:25 (SO2:O2) in Nafion 117 @ 15°C & 2.0 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 239 Table D.78 Binary permeation of 75:25 (SO2:O2) in Nafion 117 @ 25°C & 2.0 bar pSO2 – Raw Data ... 240 Table D.79 Binary permeation of 75:25 (SO2:O2) in Nafion 117 @ 25°C & 2.0 bar pSO2 – Calculated Data . 240 Table D.80 Binary permeation of 75:25 (SO2:O2) in Nafion 117 @ 25°C & 2.0 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 240 Table D.81 Binary permeation of 75:25 (SO2:O2) in Nafion 117 @ 35°C & 2.0 bar pSO2 – Raw Data ... 241 Table D.82 Binary permeation of 75:25 (SO2:O2) in Nafion 117 @ 35°C & 2.0 bar pSO2 – Calculated Data . 241 Table D.83 Binary permeation of 75:25 (SO2:O2) in Nafion 117 @ 35°C & 2.0 bar pSO2 – GC area reports (1st
, 2nd & 3rd trials) ... 241 Table D.84 Binary permeation of 75:25 (SO2:O2) in Nafion 117 @ 45°C & 2.0 bar pSO2 – Raw Data ... 242 Table D.85 Binary permeation of 75:25 (SO2:O2) in Nafion 117 @ 45°C & 2.0 bar pSO2 – Calculated Data . 242 Table D.86 Binary permeation of 75:25 (SO2:O2) in Nafion 117 @ 45°C & 2.0 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 242 Table D.87 Binary permeation of 75:25 (SO2:O2) in Nafion 117 @ 55°C & 2.0 bar pSO2 – Raw Data ... 243 Table D.88 Binary permeation of 75:25 (SO2:O2) in Nafion 117 @ 55°C & 2.0 bar pSO2 – Calculated Data . 243 Table D.89 Binary permeation of 75:25 (SO2:O2) in Nafion 117 @ 55°C & 2.0 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 243 Table D.90 Binary permeation of 25:75 (SO2:O2) in Udel Polysolfone @ 15°C & 2.2 bar pSO2 – Raw Data .. 244 Table D.91 Binary permeation of 25:75 (SO2:O2) in Udel Polysulfone @ 15°C & 2.2 bar pSO2 – Calculated Data ... 244
LIST OF TABLES
xvii
Table D.92 Binary permeation of 25:75 (SO2:O2) in Udel Polysulfone @15°C & 2.2 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 244 Table D.93 Binary permeation of 25:75 (SO2:O2) in Udel Polysolfone @ 25°C & 2.2 bar pSO2 – Raw Data .. 245 Table D.94 Binary permeation of 25:75 (SO2:O2) in Udel Polysulfone @ 25°C & 2.2 bar pSO2 – Calculated Data ... 245 Table D.95 Binary permeation of 25:75 (SO2:O2) in Udel Polysulfone @ 25°C & 2.2 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 245 Table D.96 Binary permeation of 25:75 (SO2:O2) in Udel Polysolfone @ 35°C & 2.2 bar pSO2 – Raw Data .. 246 Table D.97 Binary permeation of 25:75 (SO2:O2) in Udel Polysulfone @ 35°C & 2.2 bar pSO2 – Calculated Data ... 246 Table D.98 Binary permeation of 25:75 (SO2:O2) in Udel Polysulfone @ 35°C & 2.2 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 246 Table D.99 Binary permeation of 25:75 (SO2:O2) in Udel Polysolfone @ 45°C & 2.2 bar pSO2 – Raw Data .. 247 Table D.100 Binary permeation of 25:75 (SO2:O2) in Udel Polysulfone @ 45°C & 2.2 bar pSO2 – Calculated Data ... 247 Table D.101 Binary permeation of 25:75 (SO2:O2) in Udel Polysulfone @ 45°C & 2.2 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 247 Table D.102 Binary permeation of 25:75 (SO2:O2) in Udel Polysolfone @ 55°C & 2.2 bar pSO2 – Raw Data 248 Table D.103 Binary permeation of 25:75 (SO2:O2) in Udel Polysulfone @ 55°C & 2.2 bar pSO2 – Calculated Data ... 248 Table D.104 Binary permeation of 25:75 (SO2:O2) in Udel Polysulfone @ 55°C & 2.2 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 248 Table D.105 Binary permeation of 50:50 (SO2:O2) in Udel Polysolfone @ 15°C & 1.6 bar pSO2 – Raw Data 249 Table D.106 Binary permeation of 50:50 (SO2:O2) in Udel Polysulfone @ 15°C & 1.6 bar pSO2 – Calculated Data ... 249 Table D.107 Binary permeation of 50:50 (SO2:O2) in Udel Polysulfone @ 15°C & 1.6 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 249 Table D.108 Binary permeation of 50:50 (SO2:O2) in Udel Polysolfone @ 25°C & 1.6 bar pSO2 – Raw Data 250 Table D.109 Binary permeation of 50:50 (SO2:O2) in Udel Polysulfone @ 25°C & 1.6 bar pSO2 – Calculated Data ... 250 Table D.110 Binary permeation of 50:50 (SO2:O2) in Udel Polysulfone @ 25°C & 1.6 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 250 Table D.111 Binary permeation of 50:50 (SO2:O2) in Udel Polysolfone @ 35°C & 1.6 bar pSO2 – Raw Data 251 Table D.112 Binary permeation of 50:50 (SO2:O2) in Udel Polysulfone @ 35°C & 1.6 bar pSO2 – Calculated Data ... 251
LIST OF TABLES
xviii
Table D.113 Binary permeation of 50:50 (SO2:O2) in Udel Polysulfone @ 35°C & 1.6 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 251 Table D.114 Binary permeation of 50:50 (SO2:O2) in Udel Polysolfone @ 45°C & 1.6 bar pSO2 – Raw Data 252 Table D.115 Binary permeation of 50:50 (SO2:O2) in Udel Polysulfone @ 45°C & 1.6 bar pSO2 – Calculated Data ... 252 Table D.116 Binary permeation of 50:50 (SO2:O2) in Udel Polysulfone @ 45°C & 1.6 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 252 Table D.117 Binary permeation of 50:50 (SO2:O2) in Udel Polysolfone @ 55°C & 1.6 bar pSO2 – Raw Data 253 Table D.118 Binary permeation of 50:50 (SO2:O2) in Udel Polysulfone @ 55°C & 1.6 bar pSO2 – Calculated Data ... 253 Table D.119 Binary permeation of 50:50 (SO2:O2) in Udel Polysulfone @ 55°C & 1.6 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 253 Table D.120 Binary permeation of 75:25 (SO2:O2) in Udel Polysolfone @ 15°C & 1.8 bar pSO2 – Raw Data 254 Table D.121 Binary permeation of 75:25 (SO2:O2) in Udel Polysulfone @ 15°C & 1.8 bar pSO2 – Calculated Data ... 254 Table D.122 Binary permeation of 75:25 (SO2:O2) in Udel Polysulfone @ 15°C & 1.8 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 254 Table D.123 Binary permeation of 75:25 (SO2:O2) in Udel Polysolfone @ 25°C & 1.8 bar pSO2 – Raw Data 255 Table D.124 Binary permeation of 75:25 (SO2:O2) in Udel Polysulfone @ 25°C & 1.8 bar pSO2 – Calculated Data ... 255 Table D.125 Binary permeation of 75:25 (SO2:O2) in Udel Polysulfone @ 25°C & 1.8 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 255 Table D.126 Binary permeation of 75:25 (SO2:O2) in Udel Polysolfone @ 35°C & 1.8 bar pSO2 – Raw Data 256 Table D.127 Binary permeation of 75:25 (SO2:O2) in Udel Polysulfone @ 35°C & 1.8 bar pSO2 – Calculated Data ... 256 Table D.128 Binary permeation of 75:25 (SO2:O2) in Udel Polysulfone @ 35°C & 1.8 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 256 Table D.129 Binary permeation of 75:25 (SO2:O2) in Udel Polysolfone @ 45°C & 1.8 bar pSO2 – Raw Data 257 Table D.130 Binary permeation of 75:25 (SO2:O2) in Udel Polysulfone @ 45°C & 1.8 bar pSO2 – Calculated Data ... 257 Table D.131 Binary permeation of 75:25 (SO2:O2) in Udel Polysulfone @ 45°C & 1.8 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 257 Table D.132 Binary permeation of 75:25 (SO2:O2) in Udel Polysolfone @ 55°C & 1.8 bar pSO2 – Raw Data 258 Table D.133 Binary permeation of 75:25 (SO2:O2) in Udel Polysulfone @ 55°C & 1.8 bar pSO2 – Calculated Data ... 258
LIST OF TABLES
xix
Table D.134 Binary permeation of 75:25 (SO2:O2) in Udel Polysulfone @ 55°C & 1.8 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 258 Table D.135 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 25°C & 2.4 bar pSO2 – Raw Data ... 259 Table D.136 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 25°C & 2.4 bar pSO2 – Calculated Data 259 Table D.137 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 25°C & 2.4 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 259 Table D.138 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 25°C & 1.4 bar pSO2 – Raw Data ... 260 Table D.139 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 25°C & 1.4 bar pSO2 – Calculated Data 260 Table D.140 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 25°C & 1.4 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 260 Table D.141 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 25°C & 1.3 bar pSO2 – Raw Data ... 261 Table D.142 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 25°C & 1.3 bar pSO2 – Calculated Data 261 Table D.143 Binary permeation of 25:75 (SO2:O2) in Nafion 117 @ 25°C & 1.3 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 261 Table D.144 Binary permeation of 50:50 (SO2:O2) in Nafion 117 @ 25°C & 1.8 bar pSO2 – Raw Data ... 262 Table D.145 Binary permeation of 50:50 (SO2:O2) in Nafion 117 @ 25°C & 1.8 bar pSO2 – Calculated Data 262 Table D.146 Binary permeation of 50:50 (SO2:O2) in Nafion 117 @ 25°C & 1.8 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 262 Table D.147 Binary permeation of 50:50 (SO2:O2) in Nafion 117 @ 25°C & 1.2 bar pSO2 – Raw Data ... 263 Table D.148 Binary permeation of 50:50 (SO2:O2) in Nafion 117 @ 25°C & 1.2 bar pSO2 – Calculated Data 263 Table D.149 Binary permeation of 50:50 (SO2:O2) in Nafion 117 @ 25°C & 1.2 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 263 Table D.150 Binary permeation of 50:50 (SO2:O2) in Nafion 117 @ 25°C & 1.0 bar pSO2 – Raw Data ... 264 Table D.151 Binary permeation of 50:50 (SO2:O2) in Nafion 117 @ 25°C & 1.0 bar pSO2 – Calculated Data 264 Table D.152 Binary permeation of 50:50 (SO2:O2) in Nafion 117 @ 25°C & 1.0 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 264 Table D.153 Binary permeation of 75:25 (SO2:O2) in Nafion 117 @ 25°C & 2.0 bar pSO2 – Raw Data ... 265 Table D.154 Binary permeation of 75:25 (SO2:O2) in Nafion 117 @ 25°C & 2.0 bar pSO2 – Calculated Data 265 Table D.155 Binary permeation of 75:25 (SO2:O2) in Nafion 117 @ 25°C & 2.0 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 265 Table D.156 Binary permeation of 75:25 (SO2:O2) in Nafion 117 @ 25°C & 1.5 bar pSO2 – Raw Data ... 266 Table D.157 Binary permeation of 75:25 (SO2:O2) in Nafion 117 @ 25°C & 1.5 bar pSO2 – Calculated Data 266 Table D.158 Binary permeation of 75:25 (SO2:O2) in Nafion 117 @ 25°C & 1.5 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 266 Table D.159 Binary permeation of 75:25 (SO2:O2) in Nafion 117 @ 25°C & 1.1 bar pSO2 – Raw Data ... 267
LIST OF TABLES
xx
Table D.160 Binary permeation of 75:25 (SO2:O2) in Nafion 117 @ 25°C & 1.1 bar pSO2 – Calculated Data 267 Table D.161 Binary permeation of 75:25 (SO2:O2) in Nafion 117 @ 25°C & 1.1 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 267 Table D.162 Binary permeation of 25:75 (SO2:O2) in Udel Polysulfone @ 25°C & 2.2 bar pSO2 – Raw Data 268 Table D.163 Binary permeation of 25:75 (SO2:O2) in Udel Polysulfone @ 25°C & 2.2 bar pSO2 – Calculated Data ... 268 Table D.164 Binary permeation of 25:75 (SO2:O2) in Udel Polysulfone @ 25°C & 2.2 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 268 Table D.165 Binary permeation of 25:75 (SO2:O2) in Udel Polysulfone @ 25°C & 1.8 bar pSO2 – Raw Data 269 Table D.166 Binary permeation of 25:75 (SO2:O2) in Udel Polysulfone @ 25°C & 1.8 bar pSO2 – Calculated Data ... 269 Table D.167 Binary permeation of 25:75 (SO2:O2) in Udel Polysulfone @ 25°C & 1.8 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 269 Table D.168 Binary permeation of 25:75 (SO2:O2) in Udel Polysulfone @ 25°C & 1.3 bar pSO2 – Raw Data 270 Table D.169 Binary permeation of 25:75 (SO2:O2) in Udel Polysulfone @ 25°C & 1.3 bar pSO2 – Calculated Data ... 270 Table D.170 Binary permeation of 25:75 (SO2:O2) in Udel Polysulfone @ 25°C & 1.3 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 270 Table D.171 Binary permeation of 50:50 (SO2:O2) in Udel Polysulfone @ 25°C & 1.6 bar pSO2 – Raw Data 271 Table D.172 Binary permeation of 50:50 (SO2:O2) in Udel Polysulfone @ 25°C & 1.6 bar pSO2 – Calculated Data ... 271 Table D.173 Binary permeation of 50:50 (SO2:O2) in Udel Polysulfone @ 25°C & 1.6 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 271 Table D.174 Binary permeation of 50:50 (SO2:O2) in Udel Polysulfone @ 25°C & 1.3 bar pSO2 – Raw Data 272 Table D.175 Binary permeation of 50:50 (SO2:O2) in Udel Polysulfone @ 25°C & 1.3 bar pSO2 – Calculated Data ... 272 Table D.176 Binary permeation of 50:50 (SO2:O2) in Udel Polysulfone @ 25°C & 1.3 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 272 Table D.177 Binary permeation of 50:50 (SO2:O2) in Udel Polysulfone @ 25°C & 1.0 bar pSO2 – Raw Data 273 Table D.178 Binary permeation of 50:50 (SO2:O2) in Udel Polysulfone @ 25°C & 1.0 bar pSO2 – Calculated Data ... 273 Table D.179 Binary permeation of 50:50 (SO2:O2) in Udel Polysulfone @ 25°C & 1.0 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 273 Table D.180 Binary permeation of 75:25 (SO2:O2) in Udel Polysulfone @ 25°C & 1.8 bar pSO2 – Raw Data 274
LIST OF TABLES
xxi
Table D.181 Binary permeation of 75:25 (SO2:O2) in Udel Polysulfone @ 25°C & 1.8 bar pSO2 – Calculated Data ... 274 Table D.182 Binary permeation of 75:25 (SO2:O2) in Udel Polysulfone @ 25°C & 1.8 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 274 Table D.183 Binary permeation of 75:25 (SO2:O2) in Udel Polysulfone @ 25°C & 1.5 bar pSO2 – Raw Data 275 Table D.184 Binary permeation of 75:25 (SO2:O2) in Udel Polysulfone @ 25°C & 1.5 bar pSO2 – Calculated Data ... 275 Table D.185 Binary permeation of 75:25 (SO2:O2) in Udel Polysulfone @ 25°C & 1.5 bar pSO2 – GC area reports (1st, 2nd & 3rd trials) ... 275 Table D.186 Binary permeation of 75:25 (SO2:O2) in Udel Polysulfone @ 25°C & 1.1 bar pSO2 – Raw Data 276 Table D.187 Binary permeation of 75:25 (SO2:O2) in Udel Polysulfone @ 25°C & 1.1 bar pSO2 – Calculated Data ... 276 Table D.188 Binary permeation of 75:25 (SO2:O2) in Udel Polysulfone @ 25°C & 1.1 bar pSO2– GC area reports (1st, 2nd & 3rd trials) ... 276 Table D.189 Binary flux results of 75:25 wt (SO2:O2) in Nafion 117 @ 15°C & 1.2 bar ∆pSO2 – Raw Data ... 277 Table D.190 Binary flux results of 75:25 wt (SO2:O2) in Nafion 117 @ 15°C & 1.2 bar ∆pSO2 – Calculated Data ... 277 Table D.191 Binary flux results of 75:25 wt (SO2:O2) in Nafion 117 @ 25°C & 1.2 bar ∆pSO2 – Raw Data ... 278 Table D.192 Binary flux results of 75:25 wt (SO2:O2) in Nafion 117 @ 25°C & 1.2 bar ∆pSO2 – Calculated Data ... 278 Table D.193 Binary flux results of 75:25 wt (SO2:O2) in Nafion 117 @ 35°C & 1.2 bar ∆pSO2 – Raw Data ... 279 Table D.194 Binary flux results of 75:25 wt (SO2:O2) in Nafion 117 @ 35°C & 1.2 bar ∆pSO2 – Calculated Data ... 279 Table D.195 Binary flux results of 75:25 wt (SO2:O2) in Nafion 117 @ 45°C & 1.2 bar ∆pSO2 – Raw Data ... 280 Table D.196 Binary flux results of 75:25 wt (SO2:O2) in Nafion 117 @ 45°C & 1.2 bar ∆pSO2 – Calculated Data ... 280 Table D.197 Binary flux results of 75:25 wt (SO2:O2) in Nafion 117 @ 55°C & 1.2 bar ∆pSO2 – Raw Data ... 281 Table D.198 Binary flux results of 75:25 wt (SO2:O2) in Nafion 117 @ 55°C & 1.2 bar ∆pSO2 – Calculated Data ... 281 Table D.199 Binary flux results of 75:25 wt (SO2:O2) in Udel Polysulfone @ 15°C & 1.0 bar ∆pSO2 – Raw Data ... 282 Table D.200 Binary flux results of 75:25 wt (SO2:O2) in Udel Polysulfone @ 15°C & 1.0 bar ∆pSO2 –
Calculated Data ... 282 Table D.201 Binary flux results of 75:25 wt (SO2:O2) in Udel Polysulfone @ 25°C & 1.0 bar ∆pSO2 – Raw Data ... 283
LIST OF TABLES
xxii
Table D.202 Binary flux results of 75:25 wt (SO2:O2) in Udel Polysulfone @ 25°C & 1.0 bar ∆pSO2 –
Calculated Data ... 283 Table D.203 Binary flux results of 75:25 wt (SO2:O2) in Udel Polysulfone @ 35°C & 1.0 bar ∆pSO2 – Raw Data ... 284 Table D.204 Binary flux results of 75:25 wt (SO2:O2) in Udel Polysulfone @ 35°C & 1.0 bar ∆pSO2 –
Calculated Data ... 284 Table D.205 Binary flux results of 75:25 wt (SO2:O2) in Udel Polysulfone @ 45°C & 1.0 bar ∆pSO2 – Raw Data ... 285 Table D.206 Binary flux results of 75:25 wt (SO2:O2) in Udel Polysulfone @ 45°C & 1.0 bar ∆pSO2 –
Calculated Data ... 285 Table D.207 Binary flux results of 75:25 wt (SO2:O2) in Udel Polysulfone @ 55°C & 1.0 bar ∆pSO2 – Raw Data ... 286 Table D.208 Binary flux results of 75:25 wt (SO2:O2) in Udel Polysulfone @ 55°C & 1.0 bar ∆pSO2 –
Calculated Data ... 286 Table D.209 Binary flux results of 50:50 wt (SO2:O2) in Nafion 117 @ 15°C & 1.1 bar ∆pSO2 – Raw Data ... 287 Table D.210 Binary flux results of 50:50 wt (SO2:O2) in Nafion 117 @ 15°C & 1.1 bar ∆pSO2 – Calculated Data ... 287 Table D.211 Binary flux results of 50:50 wt (SO2:O2) in Nafion 117 @ 25°C & 1.1 bar ∆pSO2 – Raw Data ... 288 Table D.212 Binary flux results of 50:50 wt (SO2:O2) in Nafion 117 @ 25°C & 1.1 bar ∆pSO2 – Calculated Data ... 288 Table D.213 Binary flux results of 50:50 wt (SO2:O2) in Nafion 117 @ 35°C & 1.1 bar ∆pSO2 – Raw Data ... 289 Table D.214 Binary flux results of 50:50 wt (SO2:O2) in Nafion 117 @ 35°C & 1.1 bar ∆pSO2 – Calculated Data ... 289 Table D.215 Binary flux results of 50:50 wt (SO2:O2) in Nafion 117 @ 45°C & 1.1 bar ∆pSO2 – Raw Data ... 290 Table D.216 Binary flux results of 50:50 wt (SO2:O2) in Nafion 117 @ 45°C & 1.1 bar ∆pSO2 – Calculated Data ... 290 Table D.217 Binary flux results of 50:50 wt (SO2:O2) in Nafion 117 @ 55°C & 1.1 bar ∆pSO2 – Raw Data ... 291 Table D.218 Binary flux results of 50:50 wt (SO2:O2) in Nafion 117 @ 55°C & 1.1 bar ∆pSO2 – Calculated Data ... 291 Table D.219 Binary flux results of 50:50 wt (SO2:O2) in Udel Polysulfone @ 15°C & 0.8 bar ∆pSO2 – Raw Data ... 292 Table D.220 Binary flux results of 50:50 wt (SO2:O2) in Udel Polysulfone @ 15°C & 0.8 bar ∆pSO2 –
Calculated Data ... 292 Table D.221 Binary flux results of 50:50 wt (SO2:O2) in Udel Polysulfone @ 25°C & 0.8 bar ∆pSO2 – Raw Data ... 293
LIST OF TABLES
xxiii
Table D.222 Binary flux results of 50:50 wt (SO2:O2) in Udel Polysulfone @ 25°C & 0.8 bar ∆pSO2 –
Calculated Data ... 293 Table D.223 Binary flux results of 50:50 wt (SO2:O2) in Udel Polysulfone @ 35°C & 0.8 bar ∆pSO2 – Raw Data ... 294 Table D.224 Binary flux results of 50:50 wt (SO2:O2) in Udel Polysulfone @ 35°C & 0.8 bar ∆pSO2 –
Calculated Data ... 294 Table D.225 Binary flux results of 50:50 wt (SO2:O2) in Udel Polysulfone @ 45°C & 0.8 bar ∆pSO2 – Raw Data ... 295 Table D.226 Binary flux results of 50:50 wt (SO2:O2) in Udel Polysulfone @ 45°C & 0.8 bar ∆pSO2 –
Calculated Data ... 295 Table D.227 Binary flux results of 50:50 wt (SO2:O2) in Udel Polysulfone @ 55°C & 0.8 bar ∆pSO2 – Raw Data ... 296 Table D.228 Binary flux results of 50:50 wt (SO2:O2) in Udel Polysulfone @ 55°C & 0.8 bar ∆pSO2 –
Calculated Data ... 296 Table D.229 Binary flux results of 25:75 wt (SO2:O2) in Nafion 117 @ 15°C & 1.2 bar ∆pSO2 – Raw Data ... 297 Table D.230 Binary flux results of 25:75 wt (SO2:O2) in Nafion 117 @ 15°C & 1.2 bar ∆pSO2 – Calculated Data ... 297 Table D.231 Binary flux results of 25:75 wt (SO2:O2) in Nafion 117 @ 25°C & 1.2 bar ∆pSO2 – Raw Data .. 298 Table D.232 Binary flux results of 25:75 wt (SO2:O2) in Nafion 117 @ 25°C & 1.2 bar ∆pSO2 – Calculated Data ... 298 Table D.233 Binary flux results of 25:75 wt (SO2:O2) in Nafion 117 @ 35°C & 1.2 bar ∆pSO2 – Raw Data .. 299 Table D.234 Binary flux results of 25:75 wt (SO2:O2) in Nafion 117 @ 35°C & 1.2 bar ∆pSO2 – Calculated Data ... 299 Table D.235 Binary flux results of 25:75 wt (SO2:O2) in Nafion 117 @ 45°C & 1.2 bar ∆pSO2 – Raw Data ... 300 Table D.236 Binary flux results of 25:75 wt (SO2:O2) in Nafion 117 @ 45°C & 1.2 bar ∆pSO2 – Calculated Data ... 300 Table D.237 Binary flux results of 25:75 wt (SO2:O2) in Nafion 117 @ 55°C & 1.2 bar ∆pSO2 – Raw Data ... 301 Table D.238 Binary flux results of 25:75 wt (SO2:O2) in Nafion 117 @ 55°C & 1.2 bar ∆pSO2 – Calculated Data ... 301 Table D.239 Binary flux results of 25:75 wt (SO2:O2) in Udel Polysulfone @ 15°C & 1.2 bar ∆pSO2 – Raw Data ... 302 Table D.240 Binary flux results of 25:75 wt (SO2:O2) in Udel Polysulfone @ 15°C & 1.2 bar ∆pSO2 –
Calculated Data ... 302 Table D.241 Binary flux results of 25:75 wt (SO2:O2) in Udel Polysulfone @ 25°C & 1.2 bar ∆pSO2 – Raw Data ... 303
LIST OF TABLES
xxiv
Table D.242 Binary flux results of 25:75 wt (SO2:O2) in Udel Polysulfone @ 25°C & 1.2 bar ∆pSO2 –
Calculated Data ... 303 Table D.243 Binary flux results of 25:75 wt (SO2:O2) in Udel Polysulfone @ 35°C & 1.2 bar ∆pSO2 – Raw Data ... 304 Table D.244 Binary flux results of 25:75 wt (SO2:O2) in Udel Polysulfone @ 35°C & 1.2 bar ∆pSO2 –
Calculated Data ... 304 Table D.245 Binary flux results of 25:75 wt (SO2:O2) in Udel Polysulfone @ 45°C & 1.2 bar ∆pSO2 – Raw Data ... 305 Table D.246 Binary flux results of 25:75 wt (SO2:O2) in Udel Polysulfone @ 45°C & 1.2 bar ∆pSO2 –
Calculated Data ... 305 Table D.247 Binary flux results of 25:75 wt (SO2:O2) in Udel Polysulfone @ 55°C & 1.2 bar ∆pSO2 – Raw Data ... 306 Table D.248 Binary flux results of 25:75 wt (SO2:O2) in Udel Polysulfone @ 55°C & 1.2 bar ∆pSO2 –
Calculated Data ... 306 Table D.249 Binary flux results of 75:25 wt (SO2:O2) in Nafion 117 @ 25°C & 1.2 bar ∆pSO2 – Raw Data ... 307 Table D.250 Binary flux results of 75:25 wt (SO2:O2) in Nafion 117 @ 25°C & 1.2 bar ∆pSO2 – Calculated Data ... 307 Table D.251 Binary flux results of 75:25 wt (SO2:O2) in Nafion 117 @ 25°C & 0.7 bar ∆pSO2 – Raw Data ... 308 Table D.252 Binary flux results of 75:25 wt (SO2:O2) in Nafion 117 @ 25°C & 0.7 bar ∆pSO2 – Calculated Data ... 308 Table D.253 Binary flux results of 75:25 wt (SO2:O2) in Nafion 117 @ 25°C & 0.3 bar ∆pSO2 – Raw Data ... 309 Table D.254 Binary flux results of 75:25 wt (SO2:O2) in Nafion 117 @ 25°C & 0.3 bar ∆pSO2 – Calculated Data ... 309 Table D.255 Binary flux results of 75:25 wt (SO2:O2) in Udel Polysulfone @ 25°C & 1.0 bar ∆pSO2 – Raw Data ... 310 Table D.256 Binary flux results of 75:25 wt (SO2:O2) in Udel Polysulfone @ 25°C & 1.0 bar ∆pSO2 –
Calculated Data ... 310 Table D.257 Binary flux results of 75:25 wt (SO2:O2) in Udel Polysulfone @ 25°C & 0.7 bar ∆pSO2 – Raw Data ... 311 Table D.258 Binary flux results of 75:25 wt (SO2:O2) in Udel Polysulfone @ 25°C & 0.7 bar ∆pSO2 –
Calculated Data ... 311 Table D.259 Binary flux results of 75:25 wt (SO2:O2) in Udel Polysulfone @ 25°C & 0.4 bar ∆pSO2 – Raw Data ... 312 Table D.260 Binary flux results of 75:25 wt (SO2:O2) in Udel Polysulfone @ 25°C & 0.4 bar ∆pSO2 –
LIST OF TABLES
xxv
Table D.261 Binary flux results of 50:50 wt (SO2:O2) in Nafion 117 @ 25°C & 1.1 bar ∆pSO2 – Raw Data ... 313 Table D.262 Binary flux results of 50:50 wt (SO2:O2) in Nafion 117 @ 25°C & 1.1 bar ∆pSO2 – Calculated Data ... 313 Table D.263 Binary flux results of 50:50 wt (SO2:O2) in Nafion 117 @ 25°C & 0.5 bar ∆pSO2 – Raw Data ... 314 Table D.264 Binary flux results of 50:50 wt (SO2:O2) in Nafion 117 @ 25°C & 0.5 bar ∆pSO2 – Calculated Data ... 314 Table D.265 Binary flux results of 50:50 wt (SO2:O2) in Nafion 117 @ 25°C & 0.3 bar ∆pSO2 – Raw Data ... 315 Table D.266 Binary flux results of 50:50 wt (SO2:O2) in Nafion 117 @ 25°C & 0.3 bar ∆pSO2 – Calculated Data ... 315 Table D.267 Binary flux results of 50:50 wt (SO2:O2) in Udel Polysulfone @ 25°C & 0.8 bar ∆pSO2 – Raw Data ... 316 Table D.268 Binary flux results of 50:50 wt (SO2:O2) in Udel Polysulfone @ 25°C & 0.8 bar ∆pSO2 –
Calculated Data ... 316 Table D.269 Binary flux results of 50:50 wt (SO2:O2) in Udel Polysulfone @ 25°C & 0.6 bar ∆pSO2 – Raw Data ... 317 Table D.270 Binary flux results of 50:50 wt (SO2:O2) in Udel Polysulfone @ 25°C & 0.6 bar ∆pSO2 –
Calculated Data ... 317 Table D.271 Binary flux results of 50:50 wt (SO2:O2) in Udel Polysulfone @ 25°C & 0.3 bar ∆pSO2 – Raw Data ... 318 Table D.272 Binary flux results of 50:50 wt (SO2:O2) in Udel Polysulfone @ 25°C & 0.3 bar ∆pSO2 –
Calculated Data ... 318 Table D.273 Binary flux results of 25:75 wt (SO2:O2) in Nafion 117 @ 25°C & 1.2 bar ∆pSO2 – Raw Data ... 319 Table D.274 Binary flux results of 25:75 wt (SO2:O2) in Nafion 117 @ 25°C & 1.2 bar ∆pSO2 – Calculated Data ... 319 Table D.275 Binary flux results of 25:75 wt (SO2:O2) in Nafion 117 @ 25°C & 0.8 bar ∆pSO2 – Raw Data ... 320 Table D.276 Binary flux results of 25:75 wt (SO2:O2) in Nafion 117 @ 25°C & 0.8 bar ∆pSO2 – Calculated Data ... 320 Table D.277 Binary flux results of 25:75 wt (SO2:O2) in Nafion 117 @ 25°C & 0.3 bar ∆pSO2 – Raw Data ... 321 Table D.278 Binary flux results of 25:75 wt (SO2:O2) in Nafion 117 @ 25°C & 0.3 bar ∆pSO2 – Calculated Data ... 321 Table D.279 Binary flux results of 25:75 wt (SO2:O2) in Udel Polysulfone @ 25°C & 1.2 bar ∆pSO2 – Raw Data ... 322 Table D.280 Binary flux results of 25:75 wt (SO2:O2) in Udel Polysulfone @ 25°C & 1.2 bar ∆pSO2 –
LIST OF TABLES
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Table D.281 Binary flux results of 25:75 wt (SO2:O2) in Udel Polysulfone @ 25°C & 0.7 bar ∆pSO2 – Raw Data
... 323
Table D.282 Binary flux results of 25:75 wt (SO2:O2) in Udel Polysulfone @ 25°C & 0.7 bar ∆pSO2 – Calculated Data ... 323
Table D.283 Binary flux results of 25:75 wt (SO2:O2) in Udel Polysulfone @ 25°C & 0.3 bar ∆pSO2 – Raw Data ... 324
Table D.284 Binary flux results of 25:75 wt (SO2:O2) in Udel Polysulfone @ 25°C & 0.3 bar ∆pSO2 – Calculated Data ... 324
Table F.1 O2 permeability in Hyflon M raw data for calculation of experimental error (Source: Table D11 & Table D12) ... 329
Table F.2 O2 Permeability in Hyflon M calculated data for calculation of experimental error (Source: Table D11 & Table D12) ... 329
Table G.1 Gas chromatograph raw and calculated data for 25 wt% SO2: 75 wt% O2 ... 334
Table G.2 Gas chromatograph peak areas for 25 wt% SO2: 75 wt% O2 ... 334
Table G.3 Gas chromatograph raw and calculated data for 50 wt% SO2: 50 wt% O2 ... 335
Table G.4 Gas chromatograph peak areas for 50 wt% SO2: 50 wt% O2 ... 335
Table G.5 Gas chromatograph raw and calculated data for 75 wt% SO2: 25 wt% O2 ... 336
Table G.6 Gas chromatograph peak areas for 75 wt% SO2: 25 wt% O2 ... 336
Table H.1 Vapor liquid properties of the streams ... 340
Table H.2 Vapor liquid properties of the streams ... 341
Table H.3 Vapor liquid properties of the vapor phase stream ... 342
Table H.4 Vapor liquid properties of the liquid phase stream ... 343
LIST OF FIGURES
xxvii
LIST OF FIGURES
Figure 1.1 Hybrid sulphur process... 3
Figure 1.2 Scope of the study ... 7
Figure 2.1 Membrane gas separation timeline (Adapted from Baker, (2002:1394)) ... 14
Figure 2.2 Concentration dependence of diffusion coefficient (Adapted from Dhingra (1997 :47)) ... 19
Figure 2.3 Sorption modes (Adapted from Park & Lee (2008:636)) ... 21
Figure 2.4 Pressure dependence of permeability (adapted from Koros & Chern, (1987:885)) ... 24
Figure 3.1 Molecular structure of Hyflon F (perfluoroalkoxy fluorocarbon) ... 44
Figure 3.2 Molecular structure of Halar ... 45
Figure 3.3 Molecular structure of Udel Polysulfone ... 45
Figure 3.4 Molecular structure of Teflon AF 2400 ... 46
Figure 3.5 Molecular structure of Nafion 117 ... 46
Figure 3.6 Experimental design setup – single permeation ... 50
Figure 3.7 Experimental design setup – binary permeation ... 51
Figure 3.8 Pressure-Time graph for constant volume variable pressure method (Adapted from Koros & Chern, (1987:890)) ... 58
Figure 3.9 Maximum allowable permeate pressure ... 59
Figure 3.10 Change of dp/dt with increased maximum allowable permeate pressure... 60
Figure 3.11 Flow sheet of streams converging on absorber ( Adapted from Gorensek & Summers, (2009:4106)) ... 63
Figure 3.12 Typical G.C. Peak areas for a gas mixture constituting of more SO2 ... 67
Figure 3.13 Gas chromatograph calibration curve ... 68
Figure 4.1 Membrane classification ... 73
Figure 4.2 Membrane permeability against pressure ... 79
Figure 4.3 Pressure dependence of O2 permeability in UPS ... 83
Figure 4.4 Pressure dependence of SO2 permeability in UPS ... 84
Figure 4.5 Effect of O2 feed pressure on normalized gas flux in UPS ... 85
Figure 4.6 Effect of SO2 feed pressure on normalized gas flux in UPS ... 85
Figure 4.7 Pressure dependence of O2 permeability in Nafion 117 ... 86
Figure 4.8 Weight loss of Nafion 117 due to water evaporation ... 87
Figure 4.9 Pressure dependence of SO2 permeability in Nafion 117 ... 88
Figure 4.10 Effect of O2 feed pressure on normalized gas flux through Nafion 117 ... 89
Figure 4.11 Effect of SO2 feed pressure on normalized gas flux through Nafion117 ... 90
LIST OF FIGURES
xxviii
Figure 4.13 Effect of temperature on SO2 permeate composition & SO2/O2 real selectivity in Nafion 117 at ∆pSO2 of 1.1 bar ± 0.1 with (a) 25 wt % feed SO2, (b) 50 wt % feed SO2 (c) 75 wt % feed SO2 ... 94 Figure 4.14 Effect of temperature on SO2 and O2 pseudo permeability in Nafion 117 at ∆pSO2 of 1.1 bar ± 0.1 with (a) 25 wt % feed SO2, (b) 50 wt % feed SO2 (c) 75 wt % feed SO2 ... 95 Figure 4.15 Effect of temperature on SO2 and O2 molar flux in Nafion 117 at ∆pSO2 of 1.1 bar ± 0.1 with (a) 25 wt % feed SO2, (b) 50 wt % feed SO2 (c) 75 wt % feed SO2 ... 96 Figure 4.16 Effect of SO2 feed partial pressure on SO2 permeate composition in Nafion 117 at 25°C with (a) 25 wt % feed SO2, (b) 50 wt % feed SO2 and (c) 75 wt % feed SO2 ... 100 Figure 4.17 Effect of total trans-membrane pressure on SO2 and O2 pseudo permeability in Nafion 117 at 25°C with (a) 25 wt % feed SO2, (b) 50 wt % feed SO2 (c) 75 wt % feed SO2 ... 101 Figure 4.18 Effect of total trans-membrane pressure on SO2 and O2 molar flux in Nafion 117 at 25°C with (a) 25 wt % feed SO2, (b) 50 wt % feed SO2 (c) 75 wt % feed SO2 ... 102 Figure 4.19 Effect of temperature on SO2 permeate composition and SO2/O2 real selectivity in Udel
Polysulfone at ∆pSO2 1 bar ± 0.2 with (a) 25 wt % feed SO2, (b) 50 wt % feed SO2 (c) 75 wt % feed SO2 ... 105 Figure 4.20 Effect of temperature on SO2 and O2 pseudo permeability in Udel Polysulfone at ∆pSO2 1 bar ± 0.2 with (a) 25 wt % feed SO2, (b) 50 wt % feed SO2 (c) 75 wt % feed SO2 ... 106 Figure 4.21 Effect of temperature on SO2 and O2 molar flux in Udel Polysulfone at ∆pSO2 1 bar ± 0.2 with (a) 25 wt % feed SO2, (b) 50 wt % feed SO2 (c) 75 wt % feed SO2 ... 107 Figure 4.22 Effect of SO2 feed partial pressure on SO2 permeate composition and SO2/O2 real selectivity in Udel Polysulfone at 25°C with (a) 25 wt % feed SO2, (b) 50 wt % feed SO2 (c) 75 wt % feed SO2 ... 109 Figure 4.23 Effect of total trans-membrane pressure on SO2 and O2 pseudo permeability in Udel Polysulfone at 25°C with (a) 25 wt % feed SO2, (b) 50 wt % feed SO2 (c) 75 wt % feed SO2 ... 110 Figure 4.24 Effect of total trans-membrane pressure on SO2 and O2 molar flux in Udel Polysulfone at 25°C with (a) 25 wt % feed SO2, (b) 50 wt % feed SO2 (c) 75 wt % feed SO2 ... 111 Figure 4.25 SO2/O2 separation potential of Nafion 117 and Udel Polysulfone at ∆pSO2 1.1 bar ± 0.2 and 5 different temperatures ... 114 Figure 4.26 SO2/O2 selectivity in Udel Polysulfone and Nafion 117 at ∆pSO2 1 bar ± 0.2 and 5 different
temperatures with (a) 25 wt % feed SO2, (b) 50 wt % feed SO2 (c) 75 wt % feed SO2 ... 115 Figure 4.27 SO2/O2 separation potential of Nafion 117 and Udel Polysulfone at 25°C and at SO2 feed partial pressures of pSO2(1), pSO2(2) and pSO2(3) ... 116 Figure 4.28 Comparison of SO2/O2 selectivity in Udel Polysulfone and Nafion 117 at diverse SO2 feed partial pressures at 25°C with (a) 25 wt % feed SO2, (b) 50 wt % feed SO2 (c) 75 wt % feed SO2 ... 117 Figure 4.29 Comparison of SO2 and O2 molar flux in Udel Polysulfone and Nafion 117 at varying temperatures and at ∆pSO2 1 bar ± 0.2 with (a) 25 wt % feed SO2, (b) 50 wt % feed SO2 (c) 75 wt % feed SO2 ... 118
LIST OF FIGURES
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Figure 4.30 Comparison of SO2 and O2 molar flux in Udel Polysulfone and Nafion 117 at varying total
trans-membrane pressures and 25°C with (a) 25 wt % feed SO2, (b) 50 wt % feed SO2 (c) 75 wt % feed SO2 ... 119
Figure A.1 Membrane cell (Effective diameter of membrane available for permeation = 42 mm) ... 131
Figure A.2 Hyflon F film thickness (81.93µm ± 3µm) ... 132
Figure A.3 Hyflon M film thickness (89.19µm ± 3µm) ... 133
Figure A.4 Halar film thickness (63.36µm ± 3µm) ... 134
Figure A.5 Udel Polysulfone film thichkness (75 µm ± 3µm) ... 135
Figure A.6 Teflon AF 2400 film thickness (30 µm ± 3µm) ... 136
Figure A.7 Nafion 117 film thickness (177.8 µm ± 3µm) ... 137
Figure C.1 Nature of expected results ( Adapted from Koros & Chern, (1987:885)) ... 149
Figure C.2 SO2 molar permeate composition at ∆pSO2 = 1.7 bar (pSO2 feed = 2.4 bar) for (25:75, SO2:O2) wt % feed in Nafion 117 ... 155
Figure C.3 SO2 molar permeate composition at ∆pSO2 = 1.45 bar (pSO2 feed = 2.2 bar) for (25:75, SO2:O2) wt % feed in Udel Polysulfone ... 158
Figure C.4 Halar repeat unit ... 161
Figure C.5 Hyflon M repeat unit ... 163
Figure D.1 Permeate pressure-time graphs for SO2 in Hyflon F at 3.85 Bar feed pressure, 1st, 2nd & 3rd trials ... 169
Figure D.2 Permeate pressure-time graphs for SO2 in Hyflon F at 2.85 Bar feed pressure, 1st, 2nd & 3rd trials ... 169
Figure D.3 Permeate pressure-time graphs for SO2 in Hyflon F at 1.85 Bar feed pressure, 1st, 2nd & 3rd trials ... 170
Figure D.4 Permeate pressure-time graphs for O2 in Hyflon F at 3.85 Bar feed pressure, 1st, 2nd & 3rd trials . 172 Figure D.5 Permeate pressure-time graphs for O2 in Hyflon F at 2.85 Bar feed pressure, 1st, 2nd & 3rd trials 172 Figure D.6 Permeate pressure-time graphs for O2 in Hyflon F at 1.85 Bar feed pressure, 1st, 2nd & 3rd trials 173 Figure D.7 Permeate pressure-time graphs for N2 in Hyflon F at 3.85 Bar feed pressure, 1st, 2nd & 3rd trials 175 Figure D.8 Permeate pressure-time graphs for N2 in Hyflon F at 2.85 Bar feed pressure, 1st, 2nd & 3rd trials 175 Figure D.9 Permeate pressure-time graphs for N2 in Hyflon F at 1.85 Bar feed pressure, 1st, 2nd & 3rd trials 176 Figure D.10 Permeate pressure-time graphs for CO2 in Hyflon F at 3.85 Bar feed pressure, 1st, 2nd & 3rd trials ... 178
Figure D.11 Permeate pressure-time graphs for CO2 in Hyflon F at 2.85 Bar feed pressure, 1st, 2nd & 3rd trials ... 178
Figure D.12 Permeate pressure-time graphs for CO2 in Hyflon F at 1.85 Bar feed pressure, 1st, 2nd & 3rd trials ... 179 Figure D.13 Permeate pressure-time graphs for SO2 in Hyflon M at 3 Bar feed pressure, 1st, 2nd & 3rd trials 181
LIST OF FIGURES
xxx
Figure D.14 Permeate pressure-time graphs for SO2 in Hyflon M at 2 Bar feed pressure, 1st, 2nd & 3rd trials 181 Figure D.15 Permeate pressure-time graphs for SO2 in Hyflon M at 1 Bar feed pressure, 1st, 2nd & 3rd trials . 182 Figure D.16 Permeate pressure-time graphs for O2 in Hyflon M at 3 Bar feed pressure, 1st, 2nd & 3rd trials .. 184 Figure D.17 Permeate pressure-time graphs for O2 in Hyflon M at 2 Bar feed pressure, 1st, 2nd & 3rd trials ... 184 Figure D.18 Permeate pressure-time graphs for O2 in Hyflon M at 1 Bar feed pressure, 1st, 2nd & 3rd trials ... 185 Figure D.19 Permeate pressure-time graphs for N2 in Hyflon M at 3 Bar feed pressure, 1st, 2nd & 3rd trials ... 187 Figure D.20 Permeate pressure-time graphs for CO2 in Hyflon M at 3 Bar feed pressure, 1st, 2nd & 3rd trials . 189 Figure D.21 Permeate pressure-time graphs for CO2 in Hyflon M at 2 Bar feed pressure, 1st, 2nd & 3rd trials . 189 Figure D.22 Permeate pressure-time graphs for CO2 in Hyflon M at 1 Bar feed pressure, 1st, 2nd & 3rd trials 190 Figure D.23 Permeate pressure-time graphs for SO2 in Halar at 3 Bar feed pressure, 1st, 2nd & 3rd trials ... 192 Figure D.24 Permeate pressure-time graphs for O2 in Halar at 3 Bar feed pressure, 1st, 2nd & 3rd trials ... 194 Figure D.25 Permeate pressure-time graphs for CO2 in Halar at 3 Bar feed pressure, 1st, 2nd & 3rd trials .... 196 Figure D.26 Permeate pressure-time graphs for SO2 in Udel Polysulfone at 3 Bar feed pressure, 1st, 2nd & 3rd trials ... 198 Figure D.27 Permeate pressure-time graphs for SO2 in Udel Polysulfone at 2 Bar feed pressure, 1st, 2nd & 3rd trials ... 198 Figure D.28 Permeate pressure-time graphs for SO2 in Udel Polysulfone at 1 Bar feed pressure, 1st, 2nd & 3rd trials ... 199 Figure D.29 Permeate pressure-time graphs for O2 in Udel Polysulfone at 3 Bar feed pressure, 1st, 2nd & 3rd trials ... 201 Figure D.30 Permeate pressure-time graphs for O2 in Udel Polysulfone at 2 Bar feed pressure, 1st, 2nd & 3rd trials ... 201 Figure D.31 Permeate pressure-time graphs for O2 in Udel Polysulfone at 1 Bar feed pressure, 1st, 2nd & 3rd trials ... 202 Figure D.32 Permeate pressure-time graphs for N2 in Udel Polysulfone at 3 Bar feed pressure, 1st, 2nd & 3rd trials ... 204 Figure D.33 Permeate pressure-time graphs for CO2 in Udel Polysulfone at 3 Bar feed pressure, 1st, 2nd & 3rd trials ... 206 Figure D.34 Permeate pressure-time graphs for CO2 in Udel Polysulfone at 2 Bar feed pressure, 1st, 2nd & 3rd trials ... 206 Figure D.35 Permeate pressure-time graphs for CO2 in Udel Polysulfone at 1 Bar feed pressure, 1st, 2nd & 3rd trials ... 207 Figure D.36 Permeate pressure-time graphs for SO2 in Teflon AF 2400 at 3 Bar feed pressure, 1st, 2nd & 3rd trials ... 209
LIST OF FIGURES
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Figure D.37 Permeate pressure-time graphs for SO2 in Teflon AF 2400 at 2 Bar feed pressure, 1st, 2nd & 3rd trials ... 209 Figure D.38 Permeate pressure-time graphs for SO2 in Teflon AF 2400 at 1 Bar feed pressure, 1st, 2nd & 3rd trials ... 210 Figure D.39 Permeate pressure-time graphs for O2 in Teflon AF 2400 at 3 Bar feed pressure, 1st, 2nd & 3rd trials ... 212 Figure D.40 Permeate pressure-time graphs for O2 in Teflon AF 2400 at 2 Bar feed pressure, 1st, 2nd & 3rd trials ... 212 Figure D.41 Permeate pressure-time graphs for O2 in Teflon AF 2400 at 1 Bar feed pressure, 1st, 2nd & 3rd trials ... 213 Figure D.42 Permeate pressure-time graphs for N2 in Teflon AF 2400 at 3 Bar feed pressure, 1st, 2nd & 3rd trials ... 215 Figure D.43 Permeate pressure-time graphs for N2 in Teflon AF 2400 at 2 Bar feed pressure, 1st, 2nd & 3rd trials ... 215 Figure D.44 Permeate pressure-time graphs for N2 in Teflon AF 2400 at 1 Bar feed pressure, 1st, 2nd & 3rd trials ... 216 Figure D.45 Permeate pressure-time graphs for CO2 in Teflon AF 2400 at 3 Bar feed pressure, 1st, 2nd & 3rd trials ... 218 Figure D.46 Permeate pressure-time graphs for CO2 in Teflon AF 2400 at 2 Bar feed pressure, 1st, 2nd & 3rd trials ... 218 Figure D.47 Permeate pressure-time graphs for CO2 in Teflon AF 2400 at 1 Bar feed pressure, 1st, 2nd & 3rd trials ... 219 Figure D.48 Permeate pressure-time graphs for SO2 in Nafion 117 at 3 Bar feed pressure, 1st, 2nd & 3rd trials ... 221 Figure D.49 Permeate pressure-time graphs for SO2 in Nafion 117 at 2 Bar feed pressure, 1st, 2nd & 3rd trials ... 221 Figure D.50 Permeate pressure-time graphs for SO2 in Nafion 117 at 1 Bar feed pressure, 1st, 2nd & 3rd trials ... 222 Figure D.51 Permeate pressure-time graphs for O2 in Nafion 117 at 3 Bar feed pressure, 1st, 2nd & 3rd trials 224 Figure D.52 Permeate pressure-time graphs for O2 in Nafion 117 at 2 Bar feed pressure, 1st, 2nd & 3rd trials 224 Figure D.53 Permeate pressure-time graphs for O2 in Nafion 117 at 1 Bar feed pressure, 1st, 2nd & 3rd trials 225 Figure D.54 Permeate pressure-time graphs for O2 in Nafion 117 at 3 Bar feed pressure, 1st, 2nd & 3rd trials ... 227 Figure D.55 Permeate pressure-time graphs for CO2 in Nafion 117 at 2 Bar feed pressure, 1st, 2nd & 3rd trials ... 227
LIST OF FIGURES
xxxii
Figure D.56 Permeate pressure-time graphs for CO2 in Nafion 117 at 1 Bar feed pressure, 1st, 2nd & 3rd trials ... 228 Figure D.57 Permeate pressure-time graphs for 75:25 wt (SO2:O2) in Nafion 117 @ 15°C & 1.2 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 277 Figure D.58 Permeate pressure-time graphs for 75:25 wt (SO2:O2) in Nafion 117 @ 25°C & 1.2 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 278 Figure D.59 Permeate pressure-time graphs for 75:25 wt (SO2:O2) in Nafion 117 @ 35°C & 1.2 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 279 Figure D.60 Permeate pressure-time graphs for 75:25 wt (SO2:O2) in Nafion 117 @ 45°C & 1.2 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 280 Figure D.61 Permeate pressure-time graphs for 75:25 wt (SO2:O2) in Nafion 117 @ 55°C & 1.2 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 281 Figure D.62 Permeate pressure-time graphs for 75:25 wt (SO2:O2) in Udel Polysulfone @ 15°C & 1.0 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 282 Figure D.63 Permeate pressure-time graphs for 75:25 wt (SO2:O2) in Udel Polysulfone @ 25°C & 1.0 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 283 Figure D.64 Permeate pressure-time graphs for 75:25 wt (SO2:O2) in Udel Polysulfone @ 35°C & 1.0 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 284 Figure D.65 Permeate pressure-time graphs for 75:25 wt (SO2:O2) in Udel Polysulfone @ 45°C & 1.0 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 285 Figure D.66 Permeate pressure-time graphs for 75:25 wt (SO2:O2) in Udel Polysulfone @ 55°C & 1.0 bar ∆pSO2, 1st, 2nd & 3rd trials ... 286 Figure D.67 Permeate pressure-time graphs for 50:50 wt (SO2:O2) in Nafion 117 @ 15°C & 1.1 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 287 Figure D.68 Permeate pressure-time graphs for 50:50 wt (SO2:O2) in Nafion 117 @ 25°C & 1.1 bar ∆pSO2 , 1st
, 2nd & 3rd trials ... 288 Figure D.69 Permeate pressure-time graphs for 50:50 wt (SO2:O2) in Nafion 117 @ 35°C & 1.1 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 289 Figure D.70 Permeate pressure-time graphs for 50:50 wt (SO2:O2) in Nafion 117 @ 45°C & 1.1 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 290 Figure D.71 Permeate pressure-time graphs for 50:50 wt (SO2:O2) in Nafion 117 @ 55°C & 1.1 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 291 Figure D.72 Permeate pressure-time graphs for 50:50 wt (SO2:O2) in Udel Polysulfone @ 15°C & 0.8 bar ∆pSO2, 1st, 2nd & 3rd trials ... 292
LIST OF FIGURES
xxxiii
Figure D.73 Permeate pressure-time graphs for 50:50 wt (SO2:O2) in Udel Polysulfone @ 25°C & 0.8 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 293 Figure D.74 Permeate pressure-time graphs for 50:50 wt (SO2:O2) in Udel Polysulfone @ 35°C & 0.8 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 294 Figure D.75 Permeate pressure-time graphs for 50:50 wt (SO2:O2) in Udel Polysulfone @ 45°C & 0.8 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 295 Figure D.76 Permeate pressure-time graphs for 50:50 wt (SO2:O2) in Udel Polysulfone @ 55°C & 0.8 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 296 Figure D.77 Permeate pressure-time graphs for 25:75 wt (SO2:O2) in Nafion 117 @ 15°C & 1.2 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 297 Figure D.78 Permeate pressure-time graphs for 25:75 wt (SO2:O2) in Nafion 117 @ 25°C & 1.2 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 298 Figure D.79 Permeate pressure-time graphs for 25:75 wt (SO2:O2) in Nafion 117 @ 35°C & 1.2 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 299 Figure D.80 Permeate pressure-time graphs for 25:75 wt (SO2:O2) in Nafion 117 @ 45°C & 1.2 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 300 Figure D.81 Permeate pressure-time graphs for 25:75 wt (SO2:O2) in Nafion 117 @ 55°C & 1.2 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 301 Figure D.82 Permeate pressure-time graphs for 25:75 wt (SO2:O2) in Udel Polysulfone @ 15°C & 1.2 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 302 Figure D.83 Permeate pressure-time graphs for 25:75 wt (SO2:O2) in Udel Polysulfone @ 25°C & 1.2 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 303 Figure D.84 Permeate pressure-time graphs for 25:75 wt (SO2:O2) in Udel Polysulfone @ 35°C & 1.2 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 304 Figure D.85 Permeate pressure-time graphs for 25:75 wt (SO2:O2) in Udel Polysulfone @ 45°C & 1.2 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 305 Figure D.86 Permeate pressure-time graphs for 25:75 wt (SO2:O2) in Udel Polysulfone @ 55°C & 1.2 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 306 Figure D.87 Permeate pressure-time graphs for 75:25 wt (SO2:O2) in Nafion 117 @ 25°C & 1.2 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 307 Figure D.88 Permeate pressure-time graphs for 75:25 wt (SO2:O2) in Nafion 117 @ 25°C & 0.7 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 308 Figure D.89 Permeate pressure-time graphs for 75:25 wt (SO2:O2) in Nafion 117 @ 25°C & 0.3 bar ∆pSO2 , 1st, 2nd & 3rd trials ... 309
