Xu YM

DESIGN AND DEVELOPMENT OF PERVAPORATION
MEMBRANES FOR DEHYDRATION OF ALCOHOLS
XU YIMING
(B.Eng. Dalian University of Technology)
A THESIS SUBMITED
FOR THE DEGREE OF DOCTOR OF PHILOSOPHY
DEPARTMENT OF CHEMICAL AND
BIOMOLECULAR ENGINEERING
NATIONAL UNIVERSITY OF SINGAPORE
2017
Supervisor:
Professor Neal Tai-Shung Chung
Examiners:
Associate Professor Jianwen Jiang
Associate Professor Jianping Xie
Professor Xianshe Feng, University of Waterloo
DECLARATION
I hereby declare that this thesis is my original work and it has been written by
me in its entirety. I have duly acknowledged all the sources of information
which have been used in the thesis.
This thesis has also not been submitted for any degree in any university
previously.
Xu Yiming
21 August 2017
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ACKNOWLEDGEMENTS
First of all, I would like express my sincere appreciation and token of thanks
to my supervisor, Prof. Chung Tai-Shung who provided me a great
opportunity and inspired me to work in the field of membrane science and
technology. His passion towards research gave me enthusiastic encouragement
and consistent support throughout the journey of my research tenure. His
trustful guidance and valuable suggestions provided me inspirations and
confidence to overcome the difficulties during my Doctoral study. I have
learned a lot from him not only in terms of research but also in terms of hard
working attitude, which will definitely lead me to a bright future in coming
days.
I would also like to gratefully acknowledge my mentor, Dr. Le Ngoc Lieu and
Dr. Zuo Jian who gave me their unselfish encouragements and detailed
guidance patiently. Special thanks are given to the other members of
pervaporation group including Dr. Ong Yee Kang, Dr. Shi Guimin, Dr. Tang
Yupan, Dr. Hua Dan and Mr. Peyman Salehian for sharing their research
knowledge and help in pervaporation. I also extend my sincere thanks to all
other research staffs and students in the research group who provided me their
kind help and shared with me all the joys and sorrows. Their company made
my 4-year stay at NUS memorable, colorful and stunning.
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I would like to sincerely thank my thesis advisory committee (TAC) members,
Prof. Jiang Jianwen and Prof. Xie Jianping, who gave me their valuable
suggestions during my oral qualification exam.
I would also like extend my sincere gratitude to NUS for providing the
research scholarship for the whole duration of my PhD study. My heartiest
thanks go to all lab technologists and staffs in Department of Chemical and
Biomolecular Engineering, who helped me a lot in characterization techniques,
laboratory services and administrative related matters.
Last but not the least, I want to express my thanks to my parents and family
members from the core of my heart. Thanks for their love and care during the
past twenty-six years. No matter what happens, I know they are always
standing by my side with complete understanding and unwavering support.
Because of them, I could be able to put all my efforts in research without any
worries about other matters.
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Table of Contents
ACKNOWLEDGEMENTS ................................................................................ i
SUMMARY…………………………………………………………………viii
LIST OF TABLES ............................................................................................ xi
LIST OF FIGURES .........................................................................................xii
LIST OF SYMBOLS ...................................................................................... xvi
CHAPTER 1: INTRODUCTION ..................................................................... 1
1.1 Membrane pervaporation .................................................................... 1
1.2 Current applications of membrane pervaporation ............................... 2
1.2.1 Dehydration of organic solvents .................................................. 2
1.2.2 Removal of organics from aqueous solutions .............................. 4
1.2.3 Separation of organics mixtures................................................... 5
1.3 Main challenges of pervaporation ....................................................... 6
1.4 Comparison with other separation technologies ................................. 8
1.5 Research objectives and thesis organization ..................................... 10
1.6 References ......................................................................................... 14
CHAPTER 2: LITERATURE REVIEW ........................................................ 18
2.1 Mass transport mechanism ................................................................ 18
2.1.1 Solution-diffusion model ........................................................... 18
2.1.2 Pore flow model ......................................................................... 20
2.2 Evaluation of pervaporation membrane performance ....................... 21
2.3 Pervaporation membranes for alcohol dehydration .......................... 23
2.3.1 Membrane materials................................................................... 24
2.3.2 Membrane morphology and configuration ................................ 32
2.4 References ......................................................................................... 34
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CHAPTER 3: EXPERIMENTAL ................................................................... 42
3.1 Materials ............................................................................................ 42
3.1.1 Polymers .................................................................................... 42
3.1.2 Chemicals for polyimide syntheses ........................................... 42
3.1.3 Chemicals for UiO-66-Type MOFs syntheses ........................... 42
3.1.4 Organic solvents......................................................................... 43
3.2 Polyimide syntheses .......................................................................... 43
3.3 UiO-66-Type MOFs syntheses ......................................................... 44
3.4 Membrane fabrication ....................................................................... 45
3.4.1 Fabrication of polyarylether membranes by knife casting ......... 45
3.4.2 Fabrication of polyimide dense membranes by ring casting ..... 46
3.4.3 Fabrication of crosslinked polybenzoxazole membranes by
thermal treatment ..................................................................................... 46
3.4.4 Fabrication of mixed matrix membranes by ring casting .......... 47
3.5 Characterizations ............................................................................... 47
3.5.1 Fourier transform infrared spectrometer (FTIR)........................ 47
3.5.2 Wide angle X-ray diffraction (XRD) ......................................... 48
3.5.3 Themogravimetric analyses (TGA) ........................................... 48
3.5.4 Themogravimetric analyses-Fourier transform infrared
spectrometer (TGA-FTIR) ....................................................................... 49
3.5.5 Scanning electron microscope (SEM) ....................................... 49
3.5.6 Energy-dispersive X-ray spectroscopy (EDX) .......................... 49
3.5.7 Density measurements ............................................................... 50
3.5.8 Contact angle tests ..................................................................... 50
3.5.9 Solvent uptake analyses ............................................................. 51
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3.5.10 Positron annihilation lifetime spectroscopy (PALS) ................. 51
3.6 Pervaporation studies ........................................................................ 52
3.7 References ......................................................................................... 54
CHAPTER 4: POLYARYLERHER MEMBRANES FOR DEHYDRATION
OF ETHANOL AND METHANOL VIA PERVAPORATION ..................... 56
4.1 Introduction ....................................................................................... 56
4.2 Experimental ..................................................................................... 59
4.3 Results and discussion....................................................................... 60
4.3.1 Characterizations of membranes ................................................ 60
4.3.3 PALS analyses ........................................................................... 64
4.3.4 Ethanol and methanol performance ........................................... 66
4.3.5 Long-term stability tests ............................................................ 73
4.4 Conclusions ....................................................................................... 74
4.5 References ......................................................................................... 75
CHAPTER 5: POLYIMDE AND CROSSLINKED THERMALLY
REARRANGED POLY(BENZOXAZOLE-CO-IMIDE) MEMBRANES FOR
ISOPROPANOL DEHYFRATION VIA PERVAPORATION ...................... 83
5.1 Introduction ....................................................................................... 83
5.2 Experimental ..................................................................................... 87
5.3 Results and discussion....................................................................... 88
5.3.1 Characterizations of PI and C-TR membranes .......................... 88
5.3.3 Positron annihilation lifetime spectroscopy analyses ................ 93
5.3.4 Pervaporation performance of PI and C-TR membranes ........... 95
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5.3.5 Performance benchmarking and stability of C-TR membranes . 98
5.4 Conclusions ..................................................................................... 100
5.5 References ....................................................................................... 101
CHAPTER 6: UiO-66/POLYIMIDE MIXED MATRIX MEMBRANES FOR
ETHANOL, ISOPROPANOL AND N-BUTANOL DEHYDRATION VIA
PERVAPORATION ...................................................................................... 108
6.1 Introduction ..................................................................................... 108
6.2 Experimental ................................................................................... 111
6.3 Results and discussion..................................................................... 112
6.3.1 Characterizations of UiO-66 and mixed matrix membranes ... 112
6.3.2 Solvent uptake analyses ........................................................... 117
6.3.3 Positron annihilation lifetime spectroscopy analyses .............. 118
6.3.4 Pervaporation performance ...................................................... 119
6.3.5 Pervaporation benchmarking ................................................... 126
6.4 Conclusions ..................................................................................... 129
6.5 References ....................................................................................... 130
CHAPTER 7: FUNCTIONALIZED UiO-66-TYPE MOFS FOR 6FDA-
POLYIMIDE BASED MIXED MATRIX MEMBRANES FOR
DEHYDRATION OF C1-C3 ALCOHOLS VIA PERVAPORATION ........ 137
7.1 Introduction ..................................................................................... 137
7.2 Experimental ................................................................................... 140
7.3 Results and discussion..................................................................... 140
7.3.1 Characterizations of particles and mixed matrix membranes .. 140
7.3.2 Solvent uptake analyses ........................................................... 145
7.3.3 Positron annihilation lifetime spectroscopy analyses .............. 147
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7.3.4 Pervaporation performance ...................................................... 148
7.3.5 Long stability of UiO-66-NH2 based MMMs .......................... 154
7.3.6 Performance benchmarking ..................................................... 155
7.4 Conclusions ..................................................................................... 157
7.5 References ....................................................................................... 159
CHAPTER 8: CONCLUSIONS AND ECOMMENDATIONS ................... 166
8.1 Conclusions ..................................................................................... 166
8.1.1 Polyarylether membranes for dehydration of ethanol and
methanol via pervaporation.................................................................... 166
8.1.2 Polyimide and Crosslinked Thermally Rearranged
Poly(benzoxazole-co-imide) Membranes for Isopropanol Dehydration via
Pervaporation ......................................................................................... 168
8.1.3 UiO-66/Polyimide Mixed Matrix Membranes for Ethanol,
Isopropanol and n-Butanol Dehydration via Pervaporation .................. 169
8.1.4 Functionalized UiO-66-Type MOFs for 6FDA-Polyimide based
Mixed Matrix Membranes for Dehydration of C1-C3 Alcohols via
Pervaporation ......................................................................................... 170
8.2 Recommendations ........................................................................... 171
BIBLIOGRAPHY .......................................................................................... 176
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SUMMARY
Pervaporation is a prospective candidate to separate azeotropic mixtures or
close boiling point mixtures due to its advantages of low energy consumption,
environmental benignity, small footprint and mild operating conditions.
Membrane is the heart of pervaporation separation. In this thesis, novel
polymeric and mixed matrix membranes (MMMs) with high separation
performance and good stability have been developed for alcohol dehydration
via pervaporation.
Firstly, pervaporation membranes made from four polyarylether (PAE)
polymers were developed for methanol and ethanol dehydrations.
Fundamental characteristics like free volume, d-spacing, water contact angle,
solvent uptakes were investigated. The hydrophilic polyethersulfone-co-
Pluronic (H-PESU) membrane shows the best ethanol dehydration
performance with the highest water permeability of 0.322 mg m-1 h-1 kPa-1,
which is 2-6 times higher than other three membranes and comparable mole-
based selectivity of 685. Long-term tests reveal the good operating stability of
H-PESU and polyethersulfone (PESU) membranes. Moreover, methanol
dehydration performance of these PAE membranes is superior compared with
other works. The water in the permeate can be concentrated to 86.8%.
Secondly, novel polyimide and crosslinked thermally rearranged
polybenzoxazole (C-TR-PBO) membranes were developed. Fundamental
chemical and thermal properties were characterized. Solvent uptake analyses
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and positron annihilation lifetime spectroscopy measures were also carried
out. The synergistic effects of crosslinking and thermal rearrangement on the
physicochemical properties of the membranes were studied. C-TR-PBO
membrane shows an obvious improvement in flux compared to their
polyimide precursors. C-TR-5-5 exhibits the best pervaporation performance
with a comparable water permeability of 0.15 mgm-1h-1kPa-1 and an
impressively high mole-based selectivity of 4019. Besides, long-term tests
show C-TR-PBO membrane has stable isopropanol dehydration performance.
Thirdly, MMMs with UiO-66 nanoparticles and 6FDA-HAB/DABA
polyimide were designed for dehydration of ethanol, isopropanol and n-
butanol. Uniform UiO-66 nanoparticles with a particle size of around 100nm
were synthesized and subsequently added into MMMs. UiO-66 nanoparticles
can be evenly dispersed in MMMs without visible agglomerations. Results
show that the incorporation of UiO-66 greatly improves the normalized flux of
MMMs. The MMMs show excellent separation performance for the
dehydration of isopropanol and n-butanol. At the highest loading of 30wt%,
the MMMs have the water permeability of 0.329 and 0.292 mg m-1 h-1 kPa-1
and mole-based selectivity of 2209 and 14214 respectively for
isopropanol/water and n-butanol/water systems. Furthermore, dehydration
performances for different alcohol/water systems were compared. The effects
of feed temperatures and compositions on pervaporation performance were
systematically studied.
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Last but not the least, MMMs consisting of two different functionalized UiO-
66-Type MOFs (UiO-66-NH2 and UiO-66-F4) and 6FDA-HAB/DABA
polyimide were further developed for methanol, ethanol, isopropanol
dehydration. UiO-66-NH2 (80-90nm) and UiO-66-F4 (90-130nm) were
successfully synthesized. The effects of functional groups of the MOFs
particles and the effects of particle loading on the dehydration performance
were systematically investigated. Results suggest UiO-66-NH2 based MMMs
have better separation performance than UiO-66-F4 based MMMs. Adding
UiO-66-NH2 nanoparticles can greatly improve normalized flux of the MMMs
and at the same time enhance separation factor within the particle loading
range of 0-20wt%. The UiO-66-NH2 based MMMs have stable long-term
isopropanol dehydration performance due to good compatibility between UiO-
66-NH2 and polyimide.
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LIST OF TABLES
Table 1.1 Potential liquid separations by pervaporation process ............................ 2
Table 4.1 Densities and water contact angles of PESU, T-PESU, PPSU and H-
PESU membranes .................................................................................................. 62
Table 4.2 Solvent uptake results for PESU, T-PESU, PPSU and H-PESU
membranes ............................................................................................................. 63
Table 4.3 PALS data of dry PESU, T-PESU, PPSU and H-PESU membranes .... 64
Table 4.4 PALS data of wet PESU, T-PESU, PPSU and H-PESU membranes .... 65
Table 4.5 Ethanol dehydration performance of PESU, T-PESU, PPSU and H-
PESU membranes .................................................................................................. 66
Table 4.6 A comparison of pervaporation performance for ethanol dehydration.. 69
Table 4.7 Methanol dehydration performance of PESU, T-PESU, PPSU and H-
PESU membranes .................................................................................................. 70
Table 4.8 A comparison of pervaporation performance for methanol dehydration
................................................................................................................................ 71
Table 5.1 A comparison of pervaporation performance of dense membranes for
isopropanol dehydration......................................................................................... 99
Table 6.1 Solvent uptake analyses for the pristine PI membrane and MMMs .... 117
Table 6.2 PALS data for the pristine PI membrane and MMMs ......................... 118
Table 6.3 Thermodynamic properties of feed mixtures as a function of operating
temperature .......................................................................................................... 125
Table 6.4 Thermodynamic properties of feed mixtures as a function of isopropanol
concentration ........................................................................................................ 126
Table 6.5 A comparison of pervaporation performance of membranes for
isopropanol dehydration....................................................................................... 127
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Table 6.6 A comparison of pervaporation performance of membranes for n-
butanol dehydration ............................................................................................. 128
Table 6.7 A comparison of pervaporation performance of membranes for ethanol
dehydration .......................................................................................................... 128
Table 7.1 Solvent uptake ratios of the pristine PI membrane and UiO-66-NH2
based MMMs ....................................................................................................... 146
Table 7.2 Comparison of solvent uptake ratio among different UiO-66 MOF based
MMMs ................................................................................................................. 146
Table 7.3 PALS data of the pristine PI membrane and UiO-66-NH2 based MMMs
.............................................................................................................................. 147
Table 7.4 Comparison of PALS data between UiO-66-NH2 and UiO-66-F4 based
MMMs ................................................................................................................. 148
Table 7.5 Ethanol dehydration performance of UiO-66-NH2 and UiO-66-F4 based
MMMs ................................................................................................................. 149
Table 7.6 A comparison of pervaporation performance for methanol dehydration
.............................................................................................................................. 156
Table 7.7 A comparison of pervaporation performance of membranes for ethanol
dehydration .......................................................................................................... 156
isopropanol dehydration....................................................................................... 157
Table 8.1 A comparison of pervaporation performance of dense membranes for
ethanol dehydration .............................................................................................. 172
LIST OF FIGURES
Figure 1.1 Schematic diagram of pervaporation process ......................................... 1
Figure 2.1 Schematic diagram of solution-diffusion transport model ................... 19
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Figure 2.2 Schematic diagram of pore flow model................................................ 21
Figure 2.3 Typical membrane morphologies ......................................................... 32
Figure 3.1 Synthesis scheme of polyimide and crosslinked poly(benzoxazole-co-
imide) ..................................................................................................................... 44
Figure 3.2 The ligand structures of UiO-66-Type MOFs ...................................... 45
Figure 4.1 Chemical structures of PESU, T-PESU, PPSU and H-PESU .............. 59
Figure 4.2 TGA curves of PESU, T-PESU, PPSU and H-PESU membranes ....... 61
Figure 4.3 XRD patterns of PESU, T-PESU, PPSU and H-PESU membranes..... 61
Figure 4.4 Comparison of FFVs at dry and wet states measured by PALS........... 66
Figure 4.5 (a) Water and (b) ethanol/methanol normalized flux of H-PESU
membranes at different feed concentrations at 60 ºC ............................................ 72
Figure 4.6 Ethanol dehydration performance of H-PESU membranes at different
feed concentrations at 60 ºC................................................................................... 72
Figure 4.7 Methanol dehydration performance of H-PESU membranes at different
feed concentrations at 60 ºC................................................................................... 73
Figure 4.8 Long-term stability of the PESU and H-PESU membranes for ethanol
dehydration at 60 ºC with the feed composition of 85wt%/15wt% ethanol/water 74
Figure 5.1 Crosslinking mechanism of the polyimide containing carboxylic groups
under thermal treatment ......................................................................................... 87
Figure 5.2 FTIR spectra of synthesized polyimides .............................................. 88
Figure 5.3 FTIR spectra of poly(benzoxazole-co-imide) ...................................... 89
Figure 5.4 TGA curves of polyimide precursors ................................................... 90
Figure 5.5 (a) Top-view 3D TGA-FTIR analyses of the polyimide precursor PI-
10-0 and (b) Heating time of TGA and weight percentage vs. temperature
correlation .............................................................................................................. 91
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Figure 5.6 (a) Top-view 3D TGA-FTIR analyses of the polyimide precursor PI-9-
1 and (b) Heating time of TGA and weight percentage vs. temperature correlation
................................................................................................................................ 91
Figure 5.7 Solvent uptake analyses for PI and C-TR membranes ......................... 93
Figure 5.8 PALS data of PI membranes and C-TR membranes ............................ 94
Figure 5.9 Fractional free volumes of PI and C-TR membranes ........................... 95
Figure 5.10 Isopropanol dehydration performance of PI and C-TR membranes at
60 ºC....................................................................................................................... 96
Figure 5.11 Long-term stability of the C-TR-5-5 membrane for isopropanol
dehydration at 60 ºC ............................................................................................... 99
Figure 6.1 A comparison of XRD patterns of UiO-66 and MMMs..................... 113
Figure 6.2 FESEM images of (a) UiO-66 nanoparticles and cross-sectional
morphologies of (b) the pristine PI membrane and MMMs containing (c) 10wt%
UiO-66, (d) 20wt% UiO-66, (e) 30wt% UiO-66 ................................................. 113
Figure 6.3 (a) SEM image and (b) EDX mapping of Zr on the cross-section of
MMMs containing 30wt% UiO-66 ...................................................................... 114
Figure 6.4 (a) Top-view of 3D TGA-FTIR analyses of UiO-66 and (b) its
temperature vs. weight percentage and heating time ........................................... 115
Figure 6.5 (a) Top-view of 3D TGA-FTIR analyses of the MMM containing 20wt%
UiO-66 and (b) its temperature vs. weight percentage and heating time............. 115
Figure 6.6 TGA curves of the pristine PI membrane and MMMs ....................... 116
Figure 6.7 Ethanol dehydration performance of the pristine PI membrane and
MMMs at 60 ºC using ethanol/water (85/15wt%) as the feed ............................. 119
Figure 6.8 Isopropanol dehydration performance of the pristine PI membrane and
MMMs at 60 ºC using isopropanol/water (85/15wt%) as the feed ...................... 120
xiv
Figure 6.9 n-Butanol dehydration performance of the pristine PI membrane and
MMMs at 60 ºC using n-butanol/water (85/15wt%) as the feed ......................... 121
Figure 6.10 Dehydration performance of the pristine PI membrane and MMMs for
C2–C4 alcohols at 60 ºC using alcohol/water (85/15wt%) as the feed: (a) Total
normalized flux and (b) Water concentration in the permeate vs. carbon number
.............................................................................................................................. 123
Figure 6.11 Isopropanol dehydration performance of the MMM containing 20 wt%
UiO-66 using isopropanol /water (85/15wt%) as the feed................................... 124
Figure 6.12 Isopropanol dehydration of the MMM containing 20 wt% UiO-66 at
60 ºC..................................................................................................................... 126
Figure 7.1 XRD spectra of UiO-66-NH2 and UiO-66-F4 .................................... 141
Figure 7.2 FESEM images of (a) UiO-66-NH2 and (b) UiO-66-F4 nanoparticles
.............................................................................................................................. 142
Figure 7.3 FESEM images cross-sectional morphologies of (a) the pristine PI
membrane (b) MMM containing 10wt% UiO-66-F4 and MMMs containing (c)
10wt%, (d) 20wt%, (e) 30wt% UiO-66-NH2 ....................................................... 142
MMMs containing 30wt% UiO-66-NH2 ............................................................. 143
MMMs containing 10wt% UiO-66-F4 ................................................................. 143
Figure 7.6 TGA curves of UiO-66-NH2, pristine PI membrane and UiO-66-NH2
based MMMs under air atmosphere .................................................................... 144
Figure 7.7 TGA curves of UiO-66-F4, pristine PI membrane and UiO-66-F4 based
MMMs under air atmosphere............................................................................... 145
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Figure 7.8 Methanol dehydration performance of the pristine PI membrane and
MMMs at 60 ºC with feed composition of methanol/water (85/15wt%) ............. 150
MMMs at 60 ºC with feed composition of ethanol/water (85/15wt%) ................ 150
Figure 7.10 Isopropanol dehydration performance of the pristine PI membrane and
MMMs at 60 ºC with feed composition of isopropanol/water (85/15wt%) ........ 151
Figure 7.11 Dehydration performance of the pristine PI membrane and UiO-66-
NH2 based MMMs for C1–C3 alcohols at 60 ºC with feed composition of alcohol
/water (85/15wt%): (a) Normalized flux and (b) Water concentration in the
permeate vs. carbon number ................................................................................ 153
Figure 7.12 Long-term stability performance of 10wt% UiO-66-NH2 MMMs for
isopropanol dehydration at 60 ºC with feed composition of isopropanol/water
(85/15wt%) .......................................................................................................... 154
Figure 8.1 Hydrophilic surface modification ....................................................... 173
Figure 8.2 Structures of four hydrophilic chemicals ........................................... 174
LIST OF SYMBOLS
 separation factor (water/alcohol)
 mole-based selectivity (water/alcohol)
i activity coefficient of component i
δ effective length of cylindrical pores
δ1 distance filled with liquid
δ2 distance filled with vapor
θ incident angle
𝜆 wavelength of radiation beam
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𝜌𝑒 density of hexane
𝜌0 density of membrane
τ3 o-Ps lifetime
d d-spacing
l membrane thickness
𝑚0 mass of membrane in air
𝑚0′ mass of membrane in hexane
𝑛 any integer
t time interval during sample collections
xwi , xwj weight fraction of the component i or j in the feed
xi mole fraction of the component i in the feed
y wi , y wj weight fraction of the component i or j in the permeate
yi mole fraction of the component i in the permeate
A effective membrane area
I3 o-Ps intensity
J flux of a membrane
𝑀𝑤𝑒𝑡 weight of swollen membrane strip at the equilibrium condition
𝑀𝑑𝑟𝑦 weight of initial membrane strip at dry state
Pi permeability of component i
Pj permeability of component j
pP total pressure at the permeate side
pif partical vapor pressure of component i in the feed
piP partical vapor pressure of component i in the permeate
xvii
pisat saturated vapor pressure of component i
Q total weight of permeate
R mean free-volume radius
ΔR an empirical constant (1.66 Å)
ATR attenuated total reflectance
BDC 1,4-benzene-dicarboxylate
C-TR crosslinked thermal rearrangement
DABA 3,5-diaminobenzoicacid
DMAC N,N-dimethylacetamide
DMF N,N-dimethylformamide
DMSO N,N-dimethylsulfoxide
EDX energy-dispersive X-ray spectroscopy
FESEM field emission scanning electron microscopy
FFV fractional free volume
FTIR fourier transform infrared spectroscopy
GO graphene oxide
HAB 3,3’-dihydroxybenzidine diamine
H-PESU hydrophilic PESU-co-Pluronic
IPA isopropanol
MMMs mixed matrix membranes
MOFs metal organic frameworks
NMP N-methyl-2-pyrrolidone
PAA poly(acrylic acid)
PAE polyarylether
xviii
PALS positron annihilation lifetime spectroscopy
PBI polybenzimidazole
PBO polybenzoxazole
PBOZ polybenzoxazinone
PDMS polydimethylsiloxane
PESU polyethersulfone
PI polyimide
POSS polyhedral oligomeric silsesquioxane
PPSU polyphenylsulfone
PTFE polytetrafluoroethylene
PVA polyvinyl alcohol
PVDF poly(vinylidene fluoride)
SEM scanning electron microscopy
TGA thermogravimetric analyses
T-PESU polytrimethylphenylethersulfone
TR thermal rearrangement
UiO-66 Zr (IV) terephthalate metal-organic framework
UiO-66-F4 fluorine functionalized UiO-66
UiO-66-NH2 amine functionalized UiO-66
XRD X-ray diffraction
6FDA 4,4’-(hexafluoroisopropylidene) diphthalic anhydride
xix
CHAPTER 1: INTRODUCTION
1.1 Membrane pervaporation
A membrane is a semi-permeable barrier that preferentially allows certain
molecules to pass while retains others and therefore achieves separation [1].
Membrane technology becomes very important as an alternative to
conventional separation techniques, such as distillation and extraction because
of its advantages of environmental benignity, high energy efficiency and low
cost. Nowadays, membrane separation processes are widely applied in
different fields such as gas separation, waste water treatment, sea water
desalination, production of pharmaceuticals, separation of pharmaceutical
wastes, fuel cells applications etc.
Pervaporation, a kind of membrane technologies that combines the process of
permeation and vaporization of the permeate. Figure 1.1 shows the schematic
diagram of pervaporation process. In pervaporation process, liquid mixture to
be separated (feed) contacts with the membrane on one side and permeating
product (permeate) is removed in vapor state from the other side.
Figure 1.1 Schematic diagram of pervaporation process
1
1.2 Current applications of membrane pervaporation
The current applications of pervaporation can be classified into three major
categories: (i) dehydration of organic solvents, (ii) removal of organic
compounds from aqueous solutions, and (iii) separation of organic mixtures.
Table 1.1 lists some potential liquids separations that request technological
breakthroughs and also some existing pervaporation applications supported by
commercially available membranes based on the three categories [2].
Table 1.1 Potential liquid separations by pervaporation process
1.2.1 Dehydration of organic solvents
Among the three application categories, dehydration of organic solvents is the
main application in the industry. Some organics, such as alcohols with low
2
molecular weight, ethers, and ketones, can be completely miscible with water
at any ratio and easily form azeotropes. Traditional separation technologies
such as distillation usually need high energy thus are not economic.
Sometimes, the traditional separation technologies have difficulties or are
impossible to break the azeotropes. However, pervaporation can overcome these
problems because it is not restricted by the vapor-liquid equilibrium thus can
easily break the azeotropes. Pervaporation is a clean technology because it does
not need third component to break the azeotropes and can avoid cross-
contamination. Moreover, pervaporation process is energy-saving because only
the permeating component consumes the latent heat and operating condition of
pervaporation is mild with low pressures and temperatures. Therefore,
dehydration of organics by pervaporation has gained a considerable market.
One typical example is to remove water from concentrated alcohol solutions to
produce high-purity alcohols. The most important alcohols are ethanol and
isopropanol (IPA) due to their great demand in various industries. Ethanol is
considered as an alternative fuel to alleviate global warming and slow down
the depletion of fossil fuels and ethanol is also largely used in
biopharmaceutical and medical industries [3, 4]. IPA can be used as an
effective cleaner for electronic and optical devices because of its non-toxicity,
fast evaporation and ability to dissolve a wide range of non-polar compounds.
Moreover, IPA is also a chemical intermediate for the production of isopropyl
acetate, rubbing alcohol, vitamin B12 and a pharmaceutical additive used in
hand sanitizer and disinfecting pads [5, 6]. The production of ethanol and IPA
needs the removal of water, thus pervaporation dehydration attracts significant
3
attention. Besides, the dehydration of other solvents, such as glycerol, acetone
and acetic acid has also been gradually developed.
The first commercial pervaporation membrane to remove water from
concentrated alcohol solutions was developed by Gesellschaft für
Trenntechnik (GFT) Co., Germany in early 1980s, which is considered as a
milestone in dehydration of alcohols [7]. The membrane consists of a thin
layer of crosslinked polyvinyl alcohol (PVA) and a porous polyacrylonitrile
(PAN) substrate. Since then, more pervaporation systems for dehydration of
organic solvents were commercialized and installed worldwide [8].
1.2.2 Removal of organics from aqueous solutions
Removal or recovery of organic compounds from a dilute aqueous solution is
another application of pervaporation. It is applied in wastewater treatment,
recycle of expensive organics and pollution control. This application first
developed by Membrane Technology and Research (MTR) [9]. After that, the
process was further expanded to various areas: (1) removal of trace amount of
volatile organic compounds (VOCs) from water stream [10]; (2) recovery of
valuable organics from aqueous solutions [11]; (3) removal of certain product
from a fermentation broth, which is helpful to improve the conversion rate and
productivity and to maintain a continuous flow. This application has gained
great attention in recent years for bioethanol or biobutanol recovery [12].
4
In this application, membrane materials need to be organophilic and
hydrophobic which have preferential sorption of organic compounds. Therefore,
most of the commercial available membranes are made from elastomers or
rubbery materials such as polydimethylsiloxane (PDMS) and polybutadiene or
highly hydrophobic materials such as poly(vinylidene fluoride) (PVDF). So far,
this application still remains at the state of laboratory-scale-demonstration.
Further studies on novel materials are still in need.
1.2.3 Separation of organics mixtures
Organic/organic separation is another potential application of pervaporation in
chemical, petrochemical and pharmaceutical industries. In recent years, using
pervaporation technology for organic/organic mixtures separation has received
significant attention [13]. However, comparing the above mentioned two
applications, the development of organic/organic separation is more limited. To
date, there are no commercially available polymeric membranes for this
application with widespread industrial acceptance due to degradation of
membrane performance in organic mixtures which is caused by swelling and loss
of membrane integrity. Nowadays, pervaporation based separation of the
following four categories of organic mixtures including polar/non-polar
mixtures, aromatic/alicyclic mixtures, aromatic/aliphatic mixtures and
aromatic isomers, have been demonstrated [14-16]. Separation of organic
mixtures is based on the differences of steric effects, polarity, and affinity to
membrane materials of different organic molecules. Currently, typical
membrane materials for this application includes polyethylene,
5
poly(tetrafluoro ethylene) (PTFE), and cellulose acetate [13, 14, 17]. The main
limitation for its wide application is lack of suitable membranes and modules
with good long-term stability in organic solvents. Crosslinking or blending may
be effective ways to improve membrane stability. Another promising method
is to develop robust inorganic membranes with controlled pore size.
1.3 Main challenges of pervaporation
Based on the above review, it can be found that one of the major obstacles for
the development of pervaporation is the lack of membranes with high
productivity, high selectivity and good stability. Polymeric membranes are
worthy of study due to their advantages such as compactness, ease of
fabrication and scale-up, lower material costs. However, there is a trade-off
between permeability and selectivity which restricts their separation
performance. Inorganic materials usually exhibit higher separation
performance than polymeric membranes because of their superior thermal and
solvent stability. However, their brittleness, complicated production process
and high costs limit their applications. Researchers have tried to integrate
inorganic and organic components together to develop membranes with
combined advantages and superior separation performance. But compatibility
between polymeric and inorganic components is an issue to be considered and
addressed. Overall, the development of membrane material is critical for
pervaporation to compete with other separation techniques. In general,
desirable membrane materials should have outstanding productivity and
separation efficiency. Besides, satisfying physicochemical properties such as
6
good mechanical stability, thermal stability and chemical resistance are also
necessary to maintain good long-term stability and reduce solvent-induced
swelling in harsh environment [18]. The other challenge is due to the fact that
a certain material often can only show good separation performance for a
specific mixture but not for other types of mixtures. In other words, different
mixtures require different types of membranes. Thus, evaluation on material
selection and tests of membrane materials must be done for different mixture
pairs.
There are two strategies to develop suitable membranes for pervaporation.
One is the molecular design of chemistry of membrane material with desired
physicochemical properties while the other is the macromolecular engineering
of membrane structure with desired morphology, ultrathin and defect free
selective layers [2]. The former method aims to tune membranes’
thermodynamic and/or kinetic responses to the permeate, while the latter
reduces defects and minimize transport resistance [2]. Based on the second
strategy, an asymmetric membrane structure with a very thin selective layer on
a porous supporting layer is desired to achieve high permeance. There are two
types of asymmetric pervaporation membranes: (1) asymmetric membranes
made of the same material [19] and (2) composite membranes consisting of
different materials for the dense selective layer and the porous substrate [20].
The second type membranes show great potential for commercialization due to
cost effective advantage. The composite membranes only need a small amount
of expensive material with high performance for the ultrathin selective layer
and the porous substrate can be made from cheap materials. However, the
7
compatibility of these different materials and the defect-free requirement for
the ultra-thin selective layer are the main challenges of composite membranes.
Besides, the mechanical properties also need be enhanced to maintain a longer
durability.
The success of membrane development not only depends on the improvements
of membrane materials and fabrication techniques but also needs a proper
understanding of the mass transport mechanism across the membrane.
Fundamental studies on mass transport mechanism can provide in-depth
knowledge in membrane structure design, process operation optimization, and
separation performance prediction.
1.4 Comparison with other separation technologies
In the industry, there are three major separation technologies for alcohol
dehydration i.e. distillation, adsorption, and pervaporation. The following
discussion compares these technologies including pros and cons.
• Distillation
As one of the most widely used technologies in the industry, distillation is
very effective at low alcohol concentrations and can provide a high separation
factor by multiple stages of vapor-liquid equilibrium (VLE). It performs well
at large-scale and is easier for mass and energy integration [5]. However, it
8
becomes difficult for azeotrope separation without adding in additional
separation steps or a third component. What’s more, it operates at high
temperature which consumes high energy and may cause deactivation of
thermally sensitive compounds such as proteins and enzymes. In addition, the
heat and mass integration becomes very difficult at small scales [5].
• Adsorption
In alcohol dehydration adsorption systems, a variety of hydrophilic adsorbents
have been developed including molecular sieves e.g. zeolites and bio-based
materials such as starch, corn cobs, cellulose and activated palm stone [5, 21].
Both liquid and vapor phase adsorptions are technically feasible, but the vapor
phase adsorption is usually practiced and it consumes lower energy than
distillation because only one-time vaporization is required. Zeolite molecular
sieves provide a high selectivity, but water is very strongly adsorbed thus high
temperature or low pressures are needed to regenerate them. What’s more,
molecular sieves are more expensive than bio-based adsorbents.
• Pervaporation
So far, pervaporation is the most significant competitor to distillation and
molecular sieve adsorption for alcohol dehydration. Compared with
conventional separation technologies, pervaporation offers several unique
advantages. First, pervaporation is not limited by the vapor-liquid equilibrium,
and thus expected to have surpassing separation efficiency, particularly in
9
separating azeotropic and close boiling point liquid mixtures [22]. Second, it is
a clean technology and can avoid cross-contamination because it does not
need third components, which are commonly employed in the so-called
“azeotropic distillations” [13]. Third, pervaporation is an energy-saving
process because only the permeating component consumes the latent heat [23,
24]. Moreover, pervaporation has a mild operation condition by using low
feed pressures and temperatures [22, 25]. Last, the compactness in module
fabrication as well as simplicity in process control are also advantageous
characteristics of pervaporation [18]. However, as discussed in previous part,
one of the major obstacles for the development of pervaporation is the lack of
membranes with high productivity, high selectivity and good stability. The
other challenge is due to the fact that a certain material often can only show
good separation performance for some specific mixtures but not for other
types of mixtures. In other words, different mixtures require different types of
membranes. Thus, evaluation on material selection and tests of membrane
materials must be done for different mixture pairs.
1.5 Research objectives and thesis organization
The objective of this thesis is to explore various new membrane materials with
high productivity, high selectivity and good stability, including polymers and
inorganic materials for alcohols dehydration via pervaporation. To achieve this
objective, novel membrane materials including commercial polymer
polyarylether and self-synthesized polymer polyimide were first developed
because they have good mechanical strength, excellent thermal and chemical
10
stability. A fundamental study of polymer properties and a systematic study
of various effects of polymer structures and operating conditions on separation
performance were conducted. After that, to further improve membrane
separation performance, thermal crosslinking and thermal rearrangement
reactions were carried out to convert polyimide into crosslinked
poly(benzoxazole-co-imide) and UiO-66-Type MOFs with different functional
groups were synthesized and incorporated into polyimide to make mixed
matrix membrane. The effects of particle loading and functional groups on
separation performance were investigated.
The detailed research objectives are as follows:
(1) To investigate the potential of polyarylether for dehydration of ethanol and
methanol and to study the influence of main-chain structure on mass transport
phenomena and pervaporation performance;
(2) To explore the potential of polyimide for isopropanol dehydration and
improve its separation performance by thermal crosslinking and thermal
rearrangement;
(3) To enhance separation performance for ethanol, isopropanol and n-butanol
dehydration by incorporating UiO-66 into polyimide to make mixed matrix
membranes;
(4) To further improve separation performance by developing mixed matrix
membranes containing polyimide and UiO-66-Type MOFs with different
functional groups and to study the effect of functional groups of UiO-66-Type
MOFs on membrane swelling and separation performance.
11
The dissertation is organized into eight chapters. Chapter one gives the
introduction of this thesis, including a brief introduction of pervaporation, the
major applications of pervaporation and the main challenges in the
development of pervaporation.
Chapter two presents the fundamentals of mass transport mechanisms, and the
parameters of performance evaluation for pervaporation membranes. Besides,
a comprehensive literature review on pervaporation membranes for alcohol
dehydration is also provided in this chapter. Membrane material, morphology
and configurations are also discussed in detail.
Chapter three provides the experimental details involved in the research,
including the materials used, the methods of fabricating membranes,
pervaporation tests and a detailed description of different characterization
techniques.
Chapter four shows pervaporation membranes made from polyethersulfone
(PESU), polyphenylsulfone (PPSU), polytrimethylphenylethersulfone (T-
PESU) and hydrophilic PESU-co-Pluronic (H-PESU) polymers for
dehydration of ethanol and methanol. Fundamental characteristics of pore
structure, free volume, d-spacing, water contact angle, water and ethanol
uptakes were investigated and correlated with their dehydration performance.
Long-term stability tests were carried out for both H-PESU and PESU
membranes.
12
Chapter five reports the synthesis of novel polyimide and the development of
crosslinked thermally rearranged polybenzoxazole (C-TR-PBO) membranes
for isopropanol dehydration. Fundamental chemical and thermal properties
were characterized by FTIR, TGA, TGA-IR. Solvent uptake analyses and
positron annihilation lifetime spectroscopy measures were also carried out to
know the solubility and permeability information. The synergistic effects of
crosslinking and thermal rearrangement on the physicochemical properties of
the membranes were studied. Long-term stability of C-TR membranes were
also studied.
Chapter six shows the design of novel mixed matrix membranes consisting of
UiO-66 nanoparticles and 6FDA-HAB/DABA polyimide for the dehydration
of ethanol, isopropanol and n-butanol via pervaporation. Uniform UiO-66
nanoparticles with a relatively small particle size were synthesized and
subsequently employed to prepare UiO-66/6FDA-HAB/DABA polyimide
MMMs with different particle loadings. Membranes and nanoparticle
morphologies, crystallographic structure, thermal properties were investigated.
Solvent uptakes and free volume properties were characterized to reveal the
actual mechanisms for the performance enhancement. The effects of UiO-66
loading, feed temperatures and feed compositions on pervaporation
performance were systematically studied.
Chapter seven shows a further development of mixed matrix membrane
consisting of two different functionalized UiO-66-type MOFs (UiO-66-NH2
and UiO-66-F4) and polyimide for alcohol dehydration via pervaporation.
13
UiO-66-NH2 and UiO-66-F4 nanoparticles with similar particle size were
synthesized and incorporated in to mixed matrix membranes. FESEM, SEM-
EDX, XRD, TGA characterizations were conducted to study morphologies,
crystallographic structure and thermal properties of nanoparticles and
membranes. Solvent uptake analyses and positron annihilation lifetime
spectroscopy test were carried out to reveal the actual mechanisms for the
improvements of separation performance. The effects of functional groups of
the MOFs particles and the effects of particle loading on the alcohol separation
performance were systematically investigated. Three different alcohols:
methanol, ethanol, isopropanol dehydration performances were studied and
compared. Long-term stability test of the UiO-66-NH2 based mixed matrix
membranes was also demonstrated.
Chapter eight draws the conclusions of the current research work and proposes
some recommendations for future work.
1.6 References
[1] R.W. Baker, Membrane technology and applications, J. Wiley, Chichester;
New York, 2004.
[2] L.Y. Jiang, Y. Wang, T.S. Chung, X.Y. Qiao, J.Y. Lai, Polyimides
membranes for pervaporation and biofuels separation, Prog. Polym. Sci. 34
(2009) 1135-1160.
[3] S. Atsumi, J.C. Liao, Metabolic engineering for advanced biofuels
production from Escherichia coli, Curr. Opin. Biotechnol. 19 (2008) 414-419.
14
[4] T. Jojima, M. Inui, H. Yukawa, Production of isopropanol by
metabolically engineered Escherichia coli, Appl. Microbiol. Biotechnol. 77
(2008) 1219-1224.
[5] L.M. Vane, Separation technologies for the recovery and dehydration of
alcohols from fermentation broths, Biofuels Bioprod. Biorefining, 2 (2008)
553-588.
[6] L.Y. Jiang, T.S. Chung, Homogeneous polyimide/cyclodextrin composite
membranes for pervaporation dehydration of isopropanol, J. Membr. Sci. 346
(2010) 45-58.
[7] G. Tusel, H. Brüschke, Use of pervaporation systems in the chemical
industry, Desalination, 53 (1985) 327-338.
[8] A. Jonquieres, R. Clément, P. Lochon, J. Néel, M. Dresch, B. Chrétien,
Industrial state-of-the-art of pervaporation and vapour permeation in the
western countries, J. Membr. Sci. 206 (2002) 87-117.
[9] I. Blume, J. Wijmans, R. Baker, The separation of dissolved organics from
water by pervaporation, J. Membr. Sci. 49 (1990) 253-286.
[10] L.M. Vane, F.R. Alvarez, Full-scale vibrating pervaporation membrane
unit: VOC removal from water and surfactant solutions, J. Membr. Sci. 202
(2002) 177-193.
[11] J. Willemsen, B. Dijkink, A. Togtema, Organophilic pervaporation for
aroma isolation—industrial and commercial prospects, Membr. Technol.
2004 (2004) 5-10.
[12] L.M. Vane, A review of pervaporation for product recovery from biomass
fermentation processes, J. Chem. Technol. Biot. 80 (2005) 603-629.
15
[13] B. Smitha, D. Suhanya, S. Sridhar, M. Ramakrishna, Separation of
organic–organic mixtures by pervaporation—a review, J. Membr. Sci. 241
(2004) 1-21.
[14] S. Sridhar, B. Smitha, A. Shaik, Pervaporation‐Based Separation of
Methanol/MTBE Mixtures—A Review, Sep. Purif. Rev. 34 (2005) 1-33.
[15] M. Yoshikawa, T. Yoshioka, J. Fujime, A. Murakami, Pervaporation
separation of MeOH/MTBE through agarose membranes, J. Membr. Sci. 178
(2000) 75-78.
[16] S.Y. Nam, Y.M. Lee, Pervaporation separation of methanol/methyl t-
butyl ether through chitosan composite membrane modified with surfactants, J.
Membr. Sci. 157 (1999) 63-71.
[17] J.G. Villaluenga, A. Tabe-Mohammadi, A review on the separation of
benzene/cyclohexane mixtures by pervaporation processes, J. Membr. Sci. 169
(2000) 159-174.
[18] X.S. Feng, R.Y.M. Huang, Liquid separation by membrane
pervaporation: a review, Ind. Eng. Chem. Res. 36 (1997) 1048-1066.
[19] L.Y. Jiang, T.S. Chung, R. Rajagopalan, Dehydration of alcohols by
pervaporation through polyimide Matrimid® asymmetric hollow fibers with
various modifications, Chem. Eng. Sci. 63 (2008) 204-216.
[20] Y. Huang, J. Ly, D. Nguyen, R.W. Baker, Ethanol dehydration using
hydrophobic and hydrophilic polymer membranes, Ind. Eng. Chem. Res. 49
(2010) 12067-12073.
[21] M.R. LADISCH, K. DYCK, Dehydration of Ethanol: New Approach
Gives Positive Energy Balance, Science, 205 (1979) 898-900.
16
[22] P. Shao, R.Y.M. Huang, Polymeric membrane pervaporation, J. Membr.
Sci. 287 (2007) 162-179.
[23] Y. Huang, R.W. Baker, L.M. Vane, Low-energy distillation-membrane
separation process, Ind. Eng. Chem. Res. 49 (2010) 3760-3768.
[24] G. Liu, W.S. Hung, J. Shen, Q. Li, Y.H. Huang, W. Jin, K.R. Lee, J.Y.
Lai, Mixed matrix membranes with molecular-interaction-driven tunable free
volumes for efficient bio-fuel recovery, J. Mater. Chem. A, 3 (2015) 4510-
4521.
[25] F. Lipnizki, R.W. Field, P.-K. Ten, Pervaporation-based hybrid process: a
review of process design, applications and economics, J. Membr. Sci. 153
(1999) 183-210.
17
CHAPTER 2: LITERATURE REVIEW
2.1 Mass transport mechanism
A proper understanding of mass transport mechanism may give useful
information and guidelineson the development of appropriate membranes.
Pervaporation process involves a phase transition from liquid to vapor phase
during mass transport through the membrane. The driving force of mass transport
in pervaporation is chemical potential difference across the membrane. The
separation performance is affected by various factors, including (1) the
physicochemical properties of feed mixtures and their interactions, (2) the
affinities of feed components to the membrane material, and (3) the membrane
morphology and structure. Because of the complicated interactions between
permeant and permeant as well as penetrants and membranes, it is hard to
formulate one single explanation for the sophisticated transport process. There
are principally two widespread approaches to describe mass transport in
pervaporation: (i) the solution-diffusion model and (ii) the pore flow model.
2.1.1 Solution-diffusion model
The solution-diffusion model is accepted by the majority of membrane
researchers describe the mass transport through a non-porous membrane [1]. The
solution-diffusion model assumes that the pressure within a membrane is uniform
while a concentration gradient across the membrane leads to the chemical
potential difference, which provides the driving force. According to this
mechanism, pervaporation consists of three consecutive steps: (i) sorption of
18
the permeant from the feed liquid onto the membrane surface, (ii) diffusion of
the permeant in the membrane, and (iii) desorption of the permeant in a vapor
phase on the downstream side of the membrane [2]. This process is illustrated
in Figure 2.1. The first two steps are the rate-controlling steps and the difference
in solubility and diffusivity of each species in the mixtures determines the final
separation performance. Thus, to pursue high performance, a desirable
membrane should have higher solubility and diffusivity towards the permeate
components.
Generally, sorption step prefers more condensable molecules or molecules with
special interaction and/or high affinity with membrane materials, which could be
estimated by solubility parameter [3]. On the other hand, the diffusivity is
significantly affected by the molecular size and shape of the permeate, the
mobility of polymer chains, the interstitial space between polymer chains or the
fractional free volume properties of the membrane, as well as the interactions
between the permeate components and membrane [4].
Figure 2.1 Schematic diagram of solution-diffusion transport model
19
2.1.2 Pore flow model
Pore flow model is proposed more recently by Okada and Matsuura [5].
Figure 2.2 illustrates the schematic diagram of the pore-flow mechanism.
Different from solution-diffusion model which is applied for non-porous
membranes, pore flow model assumes there are straight and cylindrical pores
with an effective length of δ, penetrating in the selective layer of membranes.
The pores are perpendicular to the membrane surface and all the pores are
under an isothermal condition. Moreover, it also hypothesizes that the pores
are filled with liquid with a distance of δ1 while the rest part of the pores is
filled with vapor with a length of δ2. In other words, there is a liquid/vapor
phase boundary somewhere in the middle of the membrane pores. In this
model, the mass transport process also includes three steps: (i) the permeates
transport through the liquid-filled portion of the pores from feed solution, (ii) a
liquid-to-vapor phase transition happens at the phase interface and (iii) the
permeates transport through the vapor-filled portion of the pores to
downstream. In other words, this model suggests that the mass transport can
be viewed as a combination of liquid-phase and vapor-phase transport in series.
Thus, this model simplifies the membrane structure. Pore flow model has been
studied and applied for various membranes and different separating mixtures
[6-9]. However, pore flow model may neglect the membrane-permeant
interaction and might not be suitable if the membrane is severely swelled by
the feed solution.
20
Figure 2.2 Schematic diagram of pore flow model
Solution-diffusion model and pore flow model employ different approaches to
describe pervaporation process and they can be used to explain and predict
membrane performance in different conditions.
2.2 Evaluation of pervaporation membrane performance
The selection of a pervaporation membrane is generally based on its capability
to separate mixtures. There are typically two sets of inter-connected systems to
define membrane performance, which are flux-separation factor system and
permeability-selectivity system. The flux-separation factor system is used to
evaluate the apparent membrane performance obtained under a certain
operation condition, while the permeability-selectivity system is employed to
describe the intrinsic membrane performance which is independent of the
operation conditions.
The flux (J) was determined by the total mass of permeate (Q) divided by the
product of the effective membrane area (A) and interval time (t).
21
Q
J (2.1)
A t
The separation factor α is defined by the equation below:
ywi / ywj
 (2.2)
xwi / xwj
Wherein, y w and x w are the weight fractions of the component in the
permeate and feed, respectively; the subscripts i and j refer to components of
water and alcohol in this work, respectively.
Flux and separation factor are usually reported in most studies, and are widely
used in the comparison with literature date. However, flux and separation
factor lie on both the intrinsic properties of membrane material and operation
parameters (e.g. film thickness and temperature, feed compositions). Hence, to
get intrinsic properties of membranes, flux and separation factor could be
converted to permeability (P) and selectivity (β) based on the solution-
diffusion model [10]. The permeability Pi can be calculated by:
Ji  l
Pi  (2.3)
pif  pip
Wherein, l is the membrane thickness. J i is the flux of component i . While
pif and pip are the partial vapor pressure of component i in feed and permeate,
respectively. Feed solutions in pevaporation process is in liquid state.
f
Therefore, pi represents the partial vapor pressure of component i in a
hypothetical vapor phase in equilibrium with the feed liquid, which can be
determined using the Raoult’s Law:
pif  xi i pisat (2.4)
22
Wherein, xi is the mole fraction of component i in the feed.  i and pi are the
sat
activity coefficient and the saturated vapor pressure of component i ,
respectively. Both  i and pisat can be determined using the AspenTech
Process Modelling software (version 7.2) based on the Wilson equation and
the Antoine equation. The partial vapor pressure of component i in the
permeate pip is calculated by:
pip  yi p p (2.5)
Wherein, yi represents the mole fraction of component i in the permeate. p p
is the total pressure at permeate side, was assumed to be zero due to the
vacuum condition at permeate side. As a result, the value of pip is also
determined to be zero. Therefore, permeability could be defined by the
following equation:
Ji  l
Pi  (2.6)
xi i pisat
Ideal selectivity of the membrane (β) was expressed as the ratio of the
permeability of components i and j:

𝑃
β = 𝑃𝑖 (2.7)
𝑗
2.3 Pervaporation membranes for alcohol dehydration
Since dehydration of organics, particularly alcohol dehydration is the most
significant application of pervaporation in the industry as aforementioned, a
thorough review of pervaporation membranes is focused on this application.
23
The two important aspects of pervaporation membrane development are
included: (1) membrane materials selection and (2) membrane morphology,
structure and configurations.
2.3.1 Membrane materials
To design a pervaporation membrane with good separation performance, two
aspects should be considered. One is affinity between the feed components
and membrane material. For alcohol dehydration, hydrophilic materials are
usually used due to their preferential sorption for water molecules. However,
higher hydrophilicity may cause higher degree of membrane swelling, which
results in an increase of permeation flux but a deterioration of separation
factor. Therefore, a balanced hydrophilicity and hydrophobicity is needed. The
other is the free-volume property of the membrane material. Normally a higher
fractional free volume gives rise to a higher diffusivity but a lower diffusivity
selectivity. Besides, the general evaluation criteria for pervaporation
membrane materials also includes high chemical stability and good
mechanical strength.
The materials available for pervaporation mainly include polymeric and
inorganic materials. Generally, polymeric membranes are easy to fabricate and
relatively cheap but often encounter the trade-off between permeability and
selectivity. While inorganic membranes have good mechanical stability and
high performance, but are limited by the expensive costs and fragility. In the
24
following part, both polymeric and inorganic materials as well as mixed
matrix membrane are review.
• Polymeric materials
In the early development stage, highly hydrophilic polymers, such as
polyvinyl alcohol (PVA) [11], cellulose, chitosan [12] and alginate [13], have
been widely used to dehydrate alcohols. The high hydrophilicity of these
polymers would enhance water transport and improve solubility selectivity of
water through hydrogen bonding interactions. However, these membranes are
susceptible to swell, which leads to both unstable long-term performance and
low mechanical strengths. To stabilize the membranes, various modifications
have been applied, such as chemical cross-linking, UV irradiation crosslinking
and plasma grafting [1, 14].
In recent years, research focus of pervaporation membranes for solvent
dehydration has transferred to the exploration of new materials with good
chemical and thermal stable materials to dehydrate aggressive solvents at high
operating temperatures. Therefore, polymers with stiff and rigid chains have
been subsequently developed in this application [15]. These polymers have
excellent solvent resistance, good thermal stability and high mechanical
strength due to the rigid polymer chains. Moreover, the glassy characteristic of
these polymers could help to improve the diffusivity selectivity of the
membranes.
25
Polyimides have been viewed as a kind of promising polymers due to its
excellent thermal stability, high chemical resistance and good mechanical
strength, as well as good film forming property [15]. There are some
commercially available polyimide materials such as P84, Matrimid, Ultem and
Torlon, which have been used widely in recent years. Usually, polyimides are
synthesized by a two-step approach including polycondensation between
amine monomer and anhydride monomer to form poly(amic acid) and
imidization of poly(amic acid) to form polyimide. The easy synthesis
procedures and plenty choices of amine and anhydride monomers as well as
simple modification techniques make it versatile and flexibile to tailor the
structures and physiochemical properties of polyimides. Recently, a lot of
work have been done by Chung’s research group using commercial
polyimides or self-synthesized polyimides for alcohol dehydration [16-19].
Liu et al. successfully applied P84 co-polyimide hollow fiber membranes for
IPA dehydration [16] and modifications including silicon rubber coating and
post heat treatment are used to enhance membrane performance. Jiang and
Chung developed polyimide/cyclodextrin composite membranes using a
commercial polyimide Matrimid® for IPA dehydration [17]. Le et al.
synthesized co-polyimide using 1,5-naphthalene, 3,5-benzoicacid and 2,2′-
bis(3,4-dicarboxyphenyl) hexafluoro-propanedimide and fabricated dual-layer
hollow fiber membranes using this co-polyimide as the selective layer [18].
Xu et al. successfully synthesized co-polyimide using three monomers
including 4,4’-(hexafluoroisopropylidene) diphthalic anhydride, 3,3’-
dihydroxybenzidine diamine and 3,5-diaminobenzoic acid and the polyimide
26
membrane shows a good separation efficiency with water concentration in
permeate of 99.9% [19].
Polyamides known as Nylon are another kind of heat resistance materials with
good chemical and mechanical stability [20-22]. Polyamides can be
synthesized by step-growth polymerization, such as interfacial polymerization.
Usually, polyamide dense membranes have extremely low flux. Therefore,
polyamides are often used as a thin selective layer in composite membranes to
minimize the transport resistance and improve separation performance.
Interfacial polymerization has been demonstrated to be an effective way to
form a thin layer of polyamide on a substrate.
Amorphous perfluoropolymer such as Teflon AF, Hyflon AD and Cytop is
another class of promising membrane materials with high free-volume. They
have extraordinary thermal and chemical stability thus can effectively resist
aggressive chemicals including acids, bases, organic solvents, oils and strong
oxidizers. Despite of their intrinsic hydrophobicity, the perfluoropolymer-
based membranes have been applied for dehydration of butanol, isopropanol,
ethanol, N,N-dimethylformamide (DMF), N,N-dimethylsulfoxide (DMSO),
N,N-dimethylacetamide (DMAc) and hydrogen peroxide (H2O2) [23-26] based
on size exclusion mechanism. Studies reveal that perfluoropolymer-based
membranes have a very low sorption of alcohol/water mixtures. They have
high permeability due to the large free volumes but relatively low selectivity.
27
In addition, aromatic polymers such as polybenzoxazole (PBO),
polybenzoxazinone (PBOZ) and polybenzimidazole (PBI) have also been
developed with a great potential in solvent dehydration due to their excellent
chemical and thermal stability. Both PBO and PBOZ membranes were
synthesized by the thermal rearrangement process from their respective
precursors and were applied in dehydration of alcohols [19, 27, 28]. Ong et al.
and Xu et al. found that the thermally rearranged PBO membranes show a
stable performance in dehydration of isopropanol throughout long-term period
of 200-250h [19, 27] whereas Pulyalin A et al. found that water diffusivity
was greatly improved in the PBOZ membrane compared to its precursor [28].
On the other hand, PBI-based pervaporation membranes were pioneered by
Chung and co-workers [29-32]. They have developed PBI membranes both in
flat-sheet and hollow fiber configurations for dehydration of different solvents
such as alcohols, glycols and acetone. In addition, PBI was also used as a filler
to improve the performance of Matrimid® membranes by polymer blending
[33].
• Inorganic materials
Inorganic materials possess some unique advantages of outstanding over
polymeric materials such as outstanding chemical resistance and high
temperature stability. They usually do not have solvent-induced swelling issue,
and can thus be applied in harsh chemical environment. Because of the ability to
be used at high temperature, inorganic membranes show high flux with a stable
long-term performance. However, inorganic membranes have weaknesses of
28
brittleness, high cost and complicated processbility, which restrict their wide
applications in industry. The separation of inorganic membranes is mainly
achieved by size exclusion mechanism. Inorganic membranes developed for
alcohol dehydration include zeolite, silica, ceramic, carbon, graphene oxide
and metal organic frameworks (MOFs) etc. [34-39]. Currently, most of the
commercialized inorganic membranes are made of zeolites and silica. Other
inorganic materials are still at the development stage.
Zeolites membranes have high permeability and selectivity due to the highly
ordered and well-defined structure. Zeolites have various structures with different
pore sizes thus can have molecular sieving property for different pairs of mixtures.
Recently developed zeolite membranes, such as zeolite A, zeolite T and zeolite X,
have remarkable separation performances, better than traditional polymeric
membranes. Moreover, zeolite membranes can overcome the problem of swelling
and have stable performance under harsh environments. Morigami et al. first
reported the industrial application of zeolite membranes in an ethanol production
plant [40]. This shows the feasibility of large-scale use of zeolite membranes in
industry.
Carbon membranes made from polymeric precursors have shown promising
performance in dehydration of alcohols. However, the fragility and poor
mechanical strength limit their further development. Graphene oxide (GO)
membranes, which can be viewed as a novel type of carbon-based membrane,
recently have attracted a lot of attention since it is reported to have ultra-high
water permeability but almost no permeation of organic vapor [41].
Furthermore, GO membranes possess exceptionally good mechanical
29
properties and high stability in water due to the hydrogen-bonding interactions
between GO nanosheets. Recently, Yeh et al. and Hung et al. applied the GO
membranes for the dehydration of ethanol and isopropanol, respectively [42, 43].
These membranes show remarkable permeability and high selectivity. However,
there are still some issues that need to be addressed to further develop GO
membranes such as fabrication of an ultra-thin and defect-free membrane to
achieve higher separation performance and stability in feed solutions,
particularly at flowing mode or high temperature.
Besides, metal organic frameworks (MOFs) are also an emerging family of
inorganic materials due to their unique characteristics such as large porosity,
controllable window size, high adsorption capacity and tuneable chemical
properties [44]. It has been a hot topic for gas separation [45]. In recent years,
MOFs membranes have also been applied in pervaporation. However, some
MOFs are not stable in water, therefore very few research works develop pure
MOFs membranes for alcohol-water separation. Nonetheless, MOFs are still
very promising to be used as fillers to enhance the separation performance of
polymeric membranes. In 2008, Cavka et al. successfully synthesized UiO-66
by ZrCl4 and 1,4-benzene-dicarboxylate (BDC) [46]. UiO-66-Type MOFs
have received significant attention because of the high stability in various
solvents, which makes it very hopeful to be used in solvent dehydration via
pervaporation.
30
• Mixed matrix membranes
In order to combine the strengths of both polymeric and inorganic materials,
mixed matrix membranes (MMMs) were first developed by Kulprathipanja et
al. in 1988 [47]. Afterwards, numerous inorganic fillers including zeolites,
carbon molecular sieves, silica, metal oxides, carbon nanotubes, silicate, metal
organic frameworks (MOFs), graphene oxide (GO), porous organic cages,
covalent organic frameworks and many others have been investigated and
employed in mixed matrix membranes to improve pervaporation performance
[14, 44, 45, 48]. Among them, MOFs, have been demonstrated as promising
materials for MMMs due to their advantages such as large surface areas,
tuneable porosity, high adsorption capacity and good affinity with polymer
chains, as well as the controllable chemical properties [44, 45, 48].
The incorporation of inorganic fillers has different effects on the performance
of MMMs: some works reported an enhancement of flux but a sacrifice of
separation factor [49], while others observed improvements of both flux and
separation factor [50]. The different results can be ascribed to several factors,
including the compatibility between inorganic fillers and the polymeric matrix,
the hydrophilicity of inorganic fillers, the pore size of inorganic fillers and the
rigidity of polymer chains etc.
One challenge faced by MMMs is the agglomeration of inorganic fillers in the
polymeric matrix which generates defects and results in a decrease in
selectivity [14]. To improve the compatibility between the polymeric and the
31
inorganic phases and achieve an even dispersion of inorganic fillers, following
approaches have been developed recently: (1) modifying inorganic fillers with
coupling agents which have strong bondings with polymeric phase [51]; (2)
coating inorganic fillers with a thin polymeric layer [52, 53]; (3) employing
hybrid particles with both organic and inorganic components, such as
polyhedral oligomeric silsesquioxane (POSS) [18, 54] or MOFs [49, 50, 55];
and (4) developing new MMMs fabrication methods [56].
2.3.2 Membrane morphology and configuration
Besides membrane materials, membrane morphology and configuration also
greatly affect the separation performance of a membrane. Therefore, it is
important to design a suitable membrane structure with desired morphology
and configuration according to different separation requirements. Based on
morphology, membranes can be classified into two categories: (1) symmetric
and (2) asymmetric membranes, as illustrated in Figure 2.3.
Figure 2.3 Typical membrane morphologies
32
Asymmetric membranes are developed to reduce thickness of selective layer
of membranes thus to achieve a high flux. Generally, an asymmetric
membrane possesses an ultra-thin dense selective layer and a porous substrate
as mechanical support. Based on materials used, there are two types of
asymmetric membranes: (1) wholly integral asymmetric membranes made from
the same material for selective layer and porous substrate and (2) composite
membranes with different materials for selective layer and porous substrate.
Usually, the wholly integral asymmetric membranes are prepared by non-
solvent phase inversion method. In this method, a homogeneous polymer
solution is precipitated in a non-solvent coagulation bath then a continuous
porous solid phase and a dense skin layer are formed. This phase inversion
process is quite complicated therefore fabricating conditions needs to be well
designed to obtain a desired structure. Composite membranes have more
freedom in designing and fabricating. They can be fabricated by direct coating,
casting on the substrate, layer-by-layer assembly, in-situ surface polymerization
such as interfacial polymerization and plasma polymerization [57, 58]. A small
amount of expensive materials with outstanding separation performance can
be used for the ultra-thin selective layer, while the porous substrate can be
made from cheap materials. Therefore, composite membranes are cost-
efficient and promising for industrialization.
Based on configuration, membranes can be divided into flat sheet, hollow
fiber or tubular membranes. Among them, hollow fiber membranes have been
widely used because hollow fiber membranes have superior advantages such
as high surface area, high packing density, self-support structure, excellent
33
flexibility and ease of fabrication as well as scale-up [1, 59]. Conventional
hollow fiber membranes have single-bore geometry. Recently, multi-bore
hollow fiber membranes have been widely developed [60, 61]. Multi-bore
hollow fiber membranes show higher mechanical properties compared with
traditional single-bore hollow fiber membranes thus can reduce the chances of
fiber breakage and increase operation stability. Currently, multi-bore hollow
fiber membranes are still in the developing stage and are only commercialized
for ultrafiltration application.
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polyetherimide (PEI) membranes for isopropanol dehydration via
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solvent/water mixtures, J. Membr. Sci. 352 (2010) 41-49.
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membranes with improved selectivity, Ind. Eng. Chem. Res. 52 (2012) 1141-
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of thermally rearranged acetate-containing polyimide membranes in
dehydration of biofuels via pervaporation, Chem. Eng. Sci. 79 (2012) 41-53.
[28] A. Pulyalina, G. Polotskaya, M. Goikhman, I. Podeshvo, L. Kalyuzhnaya,
M. Chislov, A. Toikka, Study on polybenzoxazinone membrane in
pervaporation processes, J. Appl. Polym. Sci. 130 (2013) 4024-4031.
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tetrafluoropropanol (TFP) by pervaporation via novel PBI/BTDA-TDI/MDI
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37
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ethylene glycol through polybenzimidazole (PBI)-based membranes. 1.
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engineering of pervaporation dehydration of ethylene glycol via dual-layer
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378 (2011) 339-350.
[32] G.M. Shi, Y. Wang, T.S. Chung, Dual‐layer PBI/P84 hollow fibers for
pervaporation dehydration of acetone, AIChE J.58 (2012) 1133-1145.
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pervaporation by homogenous blends with polybenzimidazole (PBI), J.
Membr. Sci. 271 (2006) 221-231.
[34] N. Itoh, J. Ishida, Y. Kikuchi, T. Sato, Y. Hasegawa, Continuous
dehydration of IPA–water mixture by vapor permeation using Y type zeolite
membrane in a recycling system, Sep. Purif. Technol.147 (2015) 346-352.
[35] A. Verkerk, P. Van Male, M. Vorstman, J. Keurentjes, Description of
dehydration performance of amorphous silica pervaporation membranes, J.
Membr. Sci. 193 (2001) 227-238.
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flux ceramic pervaporation membranes for dehydration of alcohol/water
mixtures, Sep. Purif. Technol. 22 (2001) 689-695.
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membranes for biofuel separation, Carbon, 49 (2011) 369-375.
38
[38] Y.P. Tang, D.R. Paul, T.S. Chung, Free-standing graphene oxide thin
films assembled by a pressurized ultrafiltration method for dehydration of
ethanol, J. Membr. Sci. 458 (2014) 199-208.
[39] A. Kasik, Y. Lin, Organic solvent pervaporation properties of MOF-5
membranes, Sep. Purif. Technol. 121 (2014) 38-45.
[40] Y. Morigami, M. Kondo, J. Abe, H. Kita, K. Okamoto, The first large-
scale pervaporation plant using tubular-type module with zeolite NaA
membrane, Sep. Purif. Technol.25 (2001) 251-260.
[41] D.R. Dreyer, S. Park, C.W. Bielawski, R.S. Ruoff, The chemistry of
graphene oxide, Chem. Soc. Rev. 39 (2010) 228-240.
[42] T.M. Yeh, Z. Wang, D. Mahajan, B.S. Hsiao, B. Chu, High flux ethanol
dehydration using nanofibrous membranes containing graphene oxide barrier
layers, J. Mater. Chem. A, 1 (2013) 12998-13003.
[43] W.S. Hung, Q.F. An, M. De Guzman, H.Y. Lin, S.H. Huang, W.R. Liu,
C.C. Hu, K.R. Lee, J.Y. Lai, Pressure-assisted self-assembly technique for
fabricating composite membranes consisting of highly ordered selective
laminate layers of amphiphilic graphene oxide, Carbon, 68 (2014) 670-677.
[44] Z. Jia, G. Wu, Metal-organic frameworks based mixed matrix membranes
for pervaporation, Microporous Mesoporous Mat.235 (2016) 151-159.
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advances in MOF-polymer composite membranes for gas separation, Inorg.
Chem. Front. 3 (2016) 896-909.
[46] J.H. Cavka, S. Jakobsen, U. Olsbye, N. Guillou, C. Lamberti, S. Bordiga,
K.P. Lillerud, A new zirconium inorganic building brick forming metal
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13850-13851.
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[48] J. Caro, Are MOF membranes better in gas separation than those made of
zeolites?, Curr. Opin. Chem. Eng. 1 (2011) 77-83.
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imidazolate frameworks (ZIF-8) mixed matrix membranes for pervaporation
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41
CHAPTER 3: EXPERIMENTAL
3.1 Materials
3.1.1 Polymers
Four kinds of polyarylether polymers: PESU (Ultrason® E6020P), PPSU
(Ultrason® P3010), T-PESU (GM1324-0016/0059) and H-PESU (GM584/P-
0302/1) were obtained from BASF SE, Germany.
3.1.2 Chemicals for polyimide syntheses
The 6FDA-HAB/DABA co-polyimides were synthesized from monomers
6FDA, HAB and DABA with four various diamine HAB to DABA ratios of
10:0, 9:1, 7:3 and 5:5 (abbreviated as PI-10-0, PI-9-1, PI-7-3 and PI-5-5) via
the imidization reaction. The monomers 4,4’-(hexafluoroisopropylidene)
diphthalic anhydride (6FDA, Clariant) and 3,5-diaminobenzoicacid (DABA,
Aldrich) were purified by vacuum sublimation while 3,3’-dihydroxybenzidine
diamine (HAB, Tokyo Chemical Industry) was used without further treatments.
Acetic anhydride and pyridine from Aldrich of the reagent grade or higher,
were used as received.
3.1.3 Chemicals for UiO-66-Type MOFs syntheses
For UiO-66-Type MOFs synthesis, zirconium (IV) chloride from Merck
(Germany), terephthalic acid and 2-aminoterephthalic acid from Aldrich
42
(Singapore), tetrafluorobenzene-1,4-dicarboxylic acid from Matrix Scientific
and acetic acid (glacial) from Merck (Germany) were obtained and used as
received.
3.1.4 Organic solvents
N-methyl-2-pyrrolidone (NMP, analytical grade) from Merck (Germany) was
purified by vacuum distillation as solvent for polyimide syntheses.
Dimethylformamide (DMF) of the reagent grade or higher, from Fisher
Scientific (UK) was used as solvents for UiO-66-Type MOFs syntheses and
for membrane casting. Methanol, ethanol, isopropanol and n-butanol from
Fisher Scientific (UK) of the reagent grade or higher, were used to prepare the
aqueous feed solutions for pervaporation studies. Hexane (HPLC grade) from
Merck (Germany) was used for density measurements.
3.2 Polyimide syntheses
HAB and DABA at ratios of 10:0, 9:1, 7:3 and 5:5 were accurately weighed
and dissolved in freshly distilled NMP under a nitrogen environment. The
mixture was then cooled to 0 °C and an equimolar amount of 6FDA
dianhydride was added. The reaction mixture was stirred for half an hour at
0 °C followed by one day at room temperature to form a viscous poly(amic
acid) solution. Subsequently, in order to transform the poly(amic acid) to a
polyimide, acetic anhydride and pyridine were poured into the solution.
Further stirring in one day was conducted to achieve the complete imidization.
43
The synthesis scheme is shown in Figure 3.1. The polyimide solution was then
precipitated in methanol, washed several times with methanol and dried in an
oven at 120 °C for 12 h.
Figure 3.1 Synthesis scheme of polyimide and crosslinked poly(benzoxazole-

co-imide)
3.3 UiO-66-Type MOFs syntheses
To synthesize UiO-66-Type MOFs, 0.080g ZrCl4, 0.057g terephthalic acid
(for UiO-66) or 0.062g 2-aminoterephthalic acid (for UiO-66-NH2) or 0.082g
tetrafluorobenzene-1,4-dicarboxylic acid (for UiO-66-F4) and 0.6mL acetic
acid (glacial) were added into 20mL DMF in a well-sealed blue cap bottle.
The mixture was stirred at 100°C (for UiO-66 and UiO-66-NH2) or at room
temperature (for UiO-66-F4) for 24h. After cooling to room temperature, the
44
UiO-66-Type MOFs particles were obtained by centrifugation and further
purified by washing with fresh DMF for several times. After that, the UiO-66-
Type MOFs particles were immersed in fresh DMF prior to use. The ligand
structures of UiO-66-Type MOFs are presented in Figure 3.2.
Figure 3.2 The ligand structures of UiO-66-Type MOFs
3.4 Membrane fabrication
3.4.1 Fabrication of polyarylether membranes by knife casting
The flat dense membranes were prepared by the knife casting and solvent
evaporation method. Prior to use, all polymers were dried overnight in a
vacuum oven at 120°C. Firstly, the polymer was dissolved in NMP to prepare
a 20 wt% dope solution. After completely dissolving and degassing, the
solution was cast on a glass plate using a casting knife with a gap thickness of
200μm. The as-cast membrane was dried in a vacuum oven at 55°C to
guarantee a slow solvent evaporation. After peeled off from the glass plate,
the membrane was further dried in a vacuum oven at 250°C for 15h to remove
the residual solvent and then naturally cooled down.
45
3.4.2 Fabrication of polyimide dense membranes by ring casting
The synthesized polyimide was dissolved in DMF to prepare a 3wt% polymer
solution. The solution was then filtered through a 1µm polytetrafluoroethylene
(PTFE) syringe filter and poured onto silicon wafers. The solution was left to
dry at 80 °C with a monitored condition to ensure slow evaporation of the
solvent. The formed membranes were then removed carefully. In order to
totally remove the residual solvent, the membranes were further dried under
vacuum using a gradient heating procedure: kept at 75 °C for 1h, raised to
200 °C at a rate of 25 °C/h, kept at 200 °C for 12h and naturally cooled down
to room temperature. The thickness of the resultant membrane was about 20-
30 mm measured by a Mitutoyo micrometer.
3.4.3 Fabrication of crosslinked polybenzoxazole membranes by thermal
treatment
In order to obtain a crosslinked polybenzoxazole membrane, the polyimide
dense membrane was thermally treated in a Lenton horizontal vacuum tube
furnace (Model VTF12/50/550) at a vacuum level of ~10 -6 mbar. The heating
protocol was to increase temperature to 450 °C at a rate of 5 °C/min and then
to keep isothermally for half an hour in a high vacuum level. After thermal
treatment, the membrane was naturally cooled down to room temperature in
the furnace before tests. The resultant membranes are abbreviated as C-TR-10-
0, C-TR-9-1, C-TR-7-3 and C-TR-5-5. It should be noted that C-TR-10-0
means there is no crosslinking due to the absence of DABA moiety.
46
3.4.4 Fabrication of mixed matrix membranes by ring casting
The mixed matrix membranes in this study were made by the solution casting
and solvent evaporation method. Firstly, the synthesized polyimide was
dissolved in DMF to prepare a 5 wt% polymer solution. Then, the solution
was filtered using a 5 µm PTFE syringe filter before mixing with the UiO-66-
Type nanoparticles. After centrifugation and washing, the wet-state UiO-66-
Type nanoparticles were re-dispersed in fresh DMF and sonicated for 1h to
achieve good dispersion. After that, the UiO-66-Type nanoparticles were
directly mixed with the polymer solution. The mixture was stirred for another
30min and cast onto a silicon wafer. The casting solution was put in an oven at
80°C to ensure slow evaporation of the solvent. After one to two days, the
mixed matrix membranes were peeled off from the silicon wafer. To totally
remove the residual solvent, the membranes were further dried in a vacuum
oven at 200°C for 12h and naturally cooled down.
3.5 Characterizations
3.5.1 Fourier transform infrared spectrometer (FTIR)
The chemical structures of the newly synthesized polyimide and
poly(benzoxazole-co-imide) were analyzed by Fourier transform infrared
spectroscopy (Bio-Rad FTS 135) (FTIR) in the range of 500-4000 cm-1 in both
attenuated total reflectance (ATR) and transmission modes.
47
3.5.2 Wide angle X-ray diffraction (XRD)
Wide-angle X-ray diffraction (XRD) measurements were carried out by a
Bruker D8 Advance X-ray diffractometer using Cu Kα with a wavelength of
1.54 Å as the radiation source. The d-spacing (𝑑), representing the average
intersegmental distance of polymer chains, was determined by the Bragg's law:
2𝑑𝑠𝑖𝑛𝜃 = 𝑛𝜆 (3.1)
where, 𝜃 is the incident angle, 𝑛 is the any integer and 𝜆 is the wavelength of
the beam.
3.5.3 Themogravimetric analyses (TGA)
To examine the membranes’ thermal stability, thermogravimetric analyses
(TGA) were employed with a Shimadzu Thermal Analyzer (DTG-60A/TA-
60WS/FC-60A) with a heating rate of 5 °C/min from 50 to 800 °C under
nitrogen atmosphere (for polyarylether membranes, PI membranes, C-TR
membranes) or air atmosphere (for PI membranes and MMMs) with a flow
rate of 30 mL min-1. The MOFs loading in the mixed matrix membranes was
calculated by the following equation:
𝑃𝑎𝑡𝑖𝑐𝑙𝑒 𝑤𝑒𝑖𝑔ℎ𝑡
𝑃𝑎𝑟𝑡𝑖𝑐𝑙𝑒 𝑙𝑜𝑎𝑑𝑖𝑛𝑔 = ∗ 100% (3.2)
𝑃𝑎𝑟𝑡𝑖𝑐𝑙𝑒 𝑤𝑒𝑖𝑔ℎ𝑡+𝑝𝑜𝑙𝑦𝑚𝑒𝑟 𝑤𝑒𝑖𝑔ℎ𝑡
48
3.5.4 Themogravimetric analyses-Fourier transform infrared spectrometer
(TGA-FTIR)
In order to investigate the reactions during the thermal treatment, TGA-IR was
also carried out, which consisted of a Shimadzu Thermal Analyzer (DTG-
60A/TA-60WS/FC-60A) and a Shimadzu IRPrestige-21 under nitrogen
atmosphere (for PI membranes, C-TR membranes) or air atmosphere (for PI
membranes and MMMs) with a flow rate of 50 mL min-1. All samples were
pretreated from room temperature to 50 °C to remove moisture; after which,
the temperature was increased to 800 °C with a rate of 10 °C.min-1. The
released vapor was online analyzed by a scanning interval of 60s.
3.5.5 Scanning electron microscope (SEM)
The morphologies of the hollow fiber substrates and TFC membranes were
observed by scanning electron microscopy (SEM JEOL JSM-5600LV) and field
emission scanning electron microscopy (FESEM JEOL JSM-6700F). For cross-
section observation, all samples were made by cryogenically cracking in liquid
N2 to obtain proper cross-sections and coated with platinum using a JEOL JFC-
1200 ion sputtering device.
3.5.6 Energy-dispersive X-ray spectroscopy (EDX)
Elemental mapping of MMMs was carried out by X-ray energy dispersive
spectrometry (EDX) to examine the distribution of zirconium element in
49
MMMs using an Oxford INCA energy dispersion of X-ray system together
with a super ultrathin window (SUTW) connected to a scanning electron
microscopy (SEM JEOL JSM-5600LV) operating at 15 kV.
3.5.7 Density measurements
Membrane density was measured by a micro balance (ML204, Mettler Toledo)
and a density kit (ML-DNY-43, Zurich) provided by Mettler-Toledo (S.E.A.)
Pte Ltd. The membrane was first measured in air and then in hexane, and the
density was finally calculated by the following equation:

𝑚0
(𝑚0 − 𝑚0′ ) = 𝜌𝑒 (3.3)
𝜌0
where, 𝑚0 and 𝑚0′ represent the masses of the membrane in air and in hexane,
respectively. 𝜌0 and 𝜌𝑒 are the densities of the membrane and hexane,
respectively. At least three samples were tested for each kind of membranes to
obtain the average values.
3.5.8 Contact angle tests
A Rame´- Hart Contact Angle Goniometer (model 100-22) was used to
measure the contact angle at room temperature. Deionized water droplets were
placed onto the membrane surface by a Gilmont microsyringe and the contact
angles were automatically measured. For each membrane, at least 10
measurements were conducted and the average was reported.
50
3.5.9 Solvent uptake analyses
Before conducting the experiments, the membrane strips were first dried in a
vacuum oven overnight to remove any moisture. The pre-weighed dry strips
were subsequently immersed in pure solvents and water separately at 60°C,
the same temperature of pervaporation testing. At different time intervals, the
swollen strips were removed from the solvent, blotted with tissue papers to
remove the excess solvent on their surfaces and their weights were determined
by a digital microbalance in a closed condition. The solvent uptake data at
different time intervals were recorded until there was no further notable
change in their weights which indicates that the swollen membranes have
reached sorption equilibrium. The solvent uptake ratio for each sample was
determined by the weight difference between the swollen strip (𝑀𝑤𝑒𝑡 ) at the
equilibrium condition and the initial strip (𝑀𝑑𝑟𝑦 ) as shown below
𝑀𝑤𝑒𝑡 −𝑀𝑑𝑟𝑦
𝑆𝑜𝑙𝑣𝑒𝑛𝑡 𝑢𝑝𝑡𝑎𝑘𝑒 𝑟𝑎𝑡𝑖𝑜 = (3.4)
𝑀𝑑𝑟𝑦
3.5.10 Positron annihilation lifetime spectroscopy (PALS)
The microstructures of membranes were measured by bulk positron
annihilation lifetime spectroscopy (PALS). A fast-fast coincident PALS
spectrometer in our laboratory with a system channel width of 50.53
picoseconds per channel was used to measure the lifetime and intensity of
22
positron species. Na was selected as the positron source and the counting
rate was around 165 counts s-1. A detailed description of the experimental
procedures can be found elsewhere [1, 2]. To perform the wet sample tests for
51
four polyarylether membranes, the membranes were firstly saturated in an
85/15 ethanol/water feed at 60 °C for 12 hours, the same duration as
pervaporation tests, and then hermetically sealed in a plastic bag with the 22Na
source sandwiched in between these samples. Details can be found elsewhere
[3]. The PATFIT program was employed to analyze the raw data and acquire
the three lifetime components (τ1, τ2 and τ3). The mean free-volume radius R
(Å) was correlated with τ3 and calculated by the following semi-empirical
correlation equation [4-7]:
𝑅 1 2𝜋𝑅
𝜏3−1 = 2[1 − ∆𝑅 + 2𝜋 𝑠𝑖𝑛 ( ∆𝑅 )] (3.5)
where τ3 is the o-Ps lifetime. ΔR represents an empirical constant (1.66 Å). The
relative fractional free volume (FFV) can be obtained by the following
equation [6-8]:
4
𝐹𝐹𝑉 = 0.0018𝐼3 (3 𝜋𝑅33 ) (3.6)
where I3 is the o-Ps intensity (%).
3.6 Pervaporation studies
The pervaporation system was a lab-scale static cell as depicted elsewhere [9].
Aqueous alcohol solutions were used as the feed solutions. The downstream
pressure was maintained at less than 1 mbar by a vacuum pump. The test
temperatures were controlled at 40°C, 60°C and 80°C. The system was
conditioned for 2h before any sample collection. Thereafter, the permeate
mixtures were collected in a cold trap immersed in liquid nitrogen. The
permeate samples were weighted, and their compositions were analyzed by a
52
gas chromatography (HP-INNOWAX column, Hewlett-Packard GC 7890)
with a TCD detector. Throughout the experiment, the feed concentration
could be considered as constant because the quantity of the permeate sample
was much smaller than that of the feed solution and the variation (less than 1
wt%) could be neglected. In order to make sure the good reproducibility, all
the data were repeated at least three times.
The total flux J was determined by the following equation:
𝑄
𝐽= (3.7)
𝐴𝑡
where A, Q and t are the effective membrane area, total mass of the permeate
and operating time, respectively. Separation factor was defined as below:
𝑦 /𝑦
1/2 = 𝑥𝑤,1/𝑥𝑤,2 (3.8)
𝑤,1 𝑤,2
where subscripts 1 and 2 represent water and alcohol, respectively; xw and yw
indicate the components’ weight fractions in the feed and the permeate.
To study the intrinsic properties of the MMMs, the permeability and mole-
based selectivity were calculated by the following equation:
𝑙
𝑃𝑖 = 𝐽𝑖 × (3.9)
𝑥𝑖 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡 −𝑦𝑖 𝑃𝑝
where 𝑃𝑖 is the permeability of component i, l is the membrane thickness,
𝐽𝑖 ,𝑃𝑖𝑠𝑎𝑡 and 𝛾𝑖 are the flux, the saturated vapor pressure of component 𝑖 and the
activity coefficient, respectively. 𝑥𝑖 and 𝑦𝑖 are the mole fractions of
component 𝑖 in the feed and the permeate, respectively. 𝑃𝑝 is the total pressure
at the permeate side, which could be viewed as zero because the pressure in
the permeate side is much smaller than the saturated vapor pressure in the feed
53
side due to the vacuum condition. By using the AspenTech Process Modelling
software, both 𝛾𝑖 and 𝑃𝑖𝑠𝑎𝑡 were calculated by the Wilson and the Antoine
equations, respectively. Mole-based selectivity was calculated by the
following equation:
𝑀 𝑃
𝛽𝑚𝑜𝑙𝑒 = ( 𝑀𝑗 ) (𝑃 𝑖 ) (3.10)
𝑖 𝑗
where 𝑀𝑖 and 𝑀𝑗 are the molecular weights of water and alcohol, respectively.
3.7 References
[1] N.L. Le, Y.P. Tang, T.S. Chung, The development of high-performance
6FDA-NDA/DABA/POSS/Ultem® dual-layer hollow fibers for ethanol
[2] Y.P. Tang, H. Wang, T.S. Chung, Towards high water permeability in
triazine-framework-based microporous membranes for dehydration of ethanol,
ChemSusChem, 8 (2015) 138-147.
[3] Y.P. Tang, D.R. Paul, T.S. Chung, Free-standing graphene oxide thin films
assembled by a pressurized ultrafiltration method for dehydration of ethanol, J.
Membr. Sci. 458 (2014) 199-208.
[4] S.J. Tao, Positronium annihilation in molecular substances, J. Chem. Phys.
56 (1972) 5499.
[5] S.J. Lue, D.T. Lee, J.Y. Chen, C.H. Chiu, C.C. Hu, Y.C. Jean, J.Y. Lai,
Diffusivity enhancement of water vapor in poly(vinyl alcohol)–fumed silica
nano-composite membranes: Correlation with polymer crystallinity and free-
volume properties, J. Membr. Sci. 325 (2008) 831-839.
54
[6] V.P. Shantarovich, I.B. Kevdina, Y.P. Yampolskii, A.Y. Alentiev, Positron
annihilation lifetime study of high and low free volume glassy polymers:
dffects of free volume sizes on the permeability and permselectivity,
Macromolecules, 33 (2000) 7453-7466.
[7] H.M. Chen, W.S. Hung, C.H. Lo, S.H. Huang, M.L. Cheng, G. Liu, K.R.
Lee, J.Y. Lai, Y.M. Sun, C.C. Hu, R. Suzuki, T. Ohdaira , N. Oshima, Y.C.
Jean, Free-volume depth profile of polymeric membranes studied by positron
annihilation spectroscopy: layer structure from interfacial polymerization,
Macromolecules, 40 (2007) 7542-7557.
[8] M.L. Williams, R.F. Landel, J.D. Ferry, The temperature dependence of
relaxation mechanisms in amorphous polymers and other glass-forming
liquids, J. Am. Chem. Soc. 77 (1955) 3701-3707.
[9] Y. Wang, M. Gruender, T.S. Chung, Pervaporation dehydration of
ethylene glycol through polybenzimidazole (PBI)-based membranes. 1.
Membrane fabrication, J. Membr. Sci. 363 (2010) 149-159.
55
CHAPTER 4: POLYARYLERHER MEMBRANES FOR
DEHYDRATION OF ETHANOL AND
METHANOL VIA PERVAPORATION
4.1 Introduction
The idea of sustainability has stimulated global interests toward new
technologies that can conserve energy, minimize waste discharge and reduce
costs. In this regard, membrane technology is emerging as a promising
technology and has been widely used in various industries because it has the
advantages of ‘high selectivity, low energy consumption, moderate cost to
performance ratio and compact modular design’ [1].
Pervaporation, one of membrane-based processes, provides the distinct
advantages of high energy efficiency, environmental friendliness, low cost,
small footprint and ease of operation [2, 3]. In addition, this process is not
limited by the thermodynamic vapor-liquid equilibrium [3]. Therefore,
pervaporation is a promising candidate to compete with conventional
separation techniques such as distillation and absorption processes, especially
in the separation of azeotropic mixtures and thermally sensitive compounds [4,
5]. Among different applications of pervaporation, dehydration of alcohols is
now very popular in the industry [6-8]. In solvent dehydration applications,
hydrophilic polymers such as poly(vinyl alcohol) (PVA), poly(acrylic acid)
(PAA), chitosan, cellulose and alginate have been employed in early
generation pervaporation membranes due to their preferential affinity to water
56
and the enhanced solubility selectivity of water to organic solvents [9-11].
However, these membranes are prone to swell which results in a reduction of
separation efficiency and a loss of mechanical strength. Therefore, these
membranes need further modifications such as crosslinking, blending, grafting,
copolymerization as well as addition of adsorbent materials to improve their
stability and selectivity [6, 12-14]. Meanwhile, glassy polymers with rigid and
stiff chains such as polyimide (PI), polyamide, polybenzoxazole (PBO),
polybenzoxazinone (PBOZ) and polybenzimidazole (PBI) have emerged as
potential membrane materials for this application because their rigid and stiff
structures could not only improve the diffusivity selectivity but also enhance
the anti-swelling property and long-term stability [15-19]. However, the
applications of these polymers in solvent dehydration are frustrated by their
relative hydrophobicity and poor solubility selectivity.
As one of the most attractive membrane materials, polyarylether (PAE)
polymer has been widely used owing to its good mechanical properties,
excellent thermal and hydrolytic stability [20]. To alter their hydrophobic
properties and enhance their performance [20-22], substantial modifications
have been carried out: namely, (1) bulk modification of the PAE material, e.g.
sulfonation of PAE [23] and grafting hydrophilic groups to its chains [24, 25];
(2) surface modifications of PAE membranes via coating [26, 27] and
interfacial polymerization [28, 29]; and (3) blending directly with hydrophilic
polymers such as polyvinylpyrrolidone (PVP) [30], polyethyleneglycol (PEG)
[31]. These modifications not only improve membrane hydrophilicity but also
have positive effects on performance enhancement. For example, Li et al.
57
modified PESU membranes using a copolymer Pluronic F127 as a surface
modifier via surface segregation and applied the membranes to separate
thiophene from n-octane via pervaporation [32]. Both the permeation flux and
enrichment factor were effectively improved.
Different from previous work which just modified the membrane surface or
grafted hydrophilic segments onto the side-chains of the PAE polymers, we
recently synthesized a new hydrophilic PESU-co-Pluronic (H-PESU)
copolymer by directly incorporating a Pluronic copolymer into the main chain
of PESU. To our best knowledge, no exploration has been conducted on this
polymer for pervaporation. Therefore, the first objective of this work is to
investigate the potential of this new H-PESU for dehydration of alcohols via
pervaporation. The second objective of this work aims to study the influence
of main-chain structure on mass transport phenomena and pervaporation
performance. Therefore, another three different PAE polymers have also
been synthesized for comparison. They are polyethersulfone (PESU),
polyphenylsulfone (PPSU), polytrimethylphenylethersulfone (T-PESU). The
structures of these four PAE polymers are depicted in Figure 4.1. To meet our
objectives, flat dense membranes were prepared and fundamental
characteristics of these membranes were investigated. Dehydration of ethanol
and methanol aqueous solutions is our focus because they are smaller
molecules and difficult to be dehydrated compared to isopropanol and butanol
[33]. Besides, solvent uptake and fractional free volume were characterized to
reveal their solubility and diffusivity preferences and to explain their different
swelling phenomena as well as pervaporation performances. Finally, long-
58
term stability tests have also been carried out to give a comprehensive
evaluation about these membranes. This work may provide useful insights to
understand the correlations between polymer microstructure and mass
transport phenomena and to design membrane materials for alcohol
dehydration.
Figure 4.1 Chemical structures of PESU, T-PESU, PPSU and H-PESU
4.2 Experimental
The PAE membranes were prepared by knife casting as introduced in Chapter
3. Thermal stability of the membranes was studied by TGA under nitrogen
atmosphere. Density measurements were carried out as shown in Chapter 3.
D-spacing was obtained by XRD measurements. Hydrophilicity was
determined by contact angle tests. Solvent uptake tests were conducted at 60℃
to study the affinities of alcohol and water with the membranes. PALS tests
59
were carried out for membranes at both dry state and wet state to study the
influence of swelling on free-volume.
4.3 Results and discussion
4.3.1 Characterizations of membranes
A comparison of thermal behaviors of the four membranes is displayed in
Figure 4.2. PESU and PPSU have better thermal stability than T-PESU and H-
PESU. The former two show no obvious weight loss (less than 1 wt%) until
490°C when the polymer backbones start to decompose. In contrast, the T-
PESU membrane starts to degrade from 400°C, while the H-PESU membrane
undergoes an earlier weight loss at a lower temperature range from 200 to 400
°C probably due to the decomposition of the Pluronic moiety, which is in good
agreement with previous studies [34, 35]. After that, the decomposition of the
PESU moiety in H-PESU leads to a more weight loss at a higher temperature
range. Nevertheless, these four membranes have sufficient thermal stability for
pervaporation applications because most operating temperatures of
pervaporation are lower than 100 oC.
60
PESU
100
PPSU
Weight percentage (%) T-PESU
80 H-PESU
60
40
20
0
0 200 400 600 800
Temperature (ºC)
Figure 4.2 TGA curves of PESU, T-PESU, PPSU and H-PESU membranes
Intensity (a.u.)
PPSU
T-PESU
H-PESU
PESU
5 10 15 20 25 30 35 40 45 50
2 theta (º)
Figure 4.3 XRD patterns of PESU, T-PESU, PPSU and H-PESU membranes
61
Figure 4.3 displays the XRD patterns of the four membranes. It is found that
the peak of T-PESU appears at the smallest angle while the other three show
insignificant differences. Based on the Bragg's law, a polymer with a smaller
peak angle should have a larger d-spacing value. Therefore, among these four
kinds of membranes, T-PESU possesses the largest d-spacing value. This is
because the three -CH3 groups in T-PESU can prevent polymer chains from
close packing due to the steric hindrance effect. Table 4.1 shows that the
density of these four membranes follows the trend of T-PESU < PPSU < H-
PESU < PESU. The lowest density of T-PESU agrees well with its highest d-
spacing. This phenomenon was also reported in a previous study [36].
Table 4.1 Densities and water contact angles of PESU, T-PESU, PPSU and H-
PESU membranes
Membrane Density (g/cm3) Water Contact Angle (º)
PESU 1.354±0.021 88.8±1.4
PPSU 1.266±0.005 85.8±0.9
T-PESU 1.213±0.017 85.4±0.9
H-PESU 1.294±0.013 41.8±1.4
Table 4.1 also summarizes the water contact angles of these four membranes.
PESU, PPSU and T-PESU membranes have close and comparable water
contact angles, while the water contact angle of the H-PESU membrane is
much smaller than those of the other three. Therefore, it can be concluded that
among these four membranes, the H-PESU membrane has the largest
hydrophilicity which can be attributed to the existence of hydrophilic Pluronic
moieties in its polymer chains.
62
In order to investigate the affinity of water and ethanol towards the
membranes, the solvent uptake tests were carried out and characterized by the
membrane weight changes due to the sorption of different solvents. Table 4.2
compares the solvent uptake ratios of the membranes in water and ethanol and
methanol. The water uptake ratios follow the trend of PESU < PPSU < T-
PESU<H-PESU while the ethanol and methanol uptake ratios present an
inverse trend. This phenomenon can be explained by the contact angle results.
Since the water contact angles follow the trend of PESU < PPSU < T-PESU <
H-PESU as aforementioned, so the hydrophilicities follow the same trend and
the membranes can absorb more water and less ethanol and methanol
according to this trend. Therefore, the H-PESU membrane provides the
highest water solubility and lowest ethanol and methanol solubilities, followed
by T-PESU, PPSU and PESU. Correspondingly, the solubility selectivity
towards water of these four membranes obeys the trend of PESU < PPSU < T-
PESU < H-PESU.
Table 4.2 Solvent uptake results for PESU, T-PESU, PPSU and H-PESU
membranes
Water Ethanol Methanol Uptake ratio Uptake ratio
Membrane uptake uptake uptake ratio of water to of water to
ratio (%) ratio (%) (%) ethanol methanol
PESU 3.1±0.7 9.9±1.6 5.2±1.1 0.31 0.60
PPSU 3.9±0.8 8.1±1.5 4.8±0.7 0.48 0.81
T-PESU 4.1±0.7 7.5±1.5 4.6±1.1 0.55 0.89
H-PESU 7.9±0.8 5.7±1.5 3.3±0.7 1.39 2.39
63
4.3.3 PALS analyses
To further quantitatively analyze the free volume size of the four membranes,
PALS measurements were carried out. The cavity size of free volume and its
concentration are correlated with two important parameters; namely, o-Ps
lifetime τ3 and its intensity I3, respectively [37, 38]. Table 4.3 shows PALS
raw data, free volume sizes and FFVs of the four membranes at the dry state.
The FFVs follow the trend of PESU<H-PESU<T-PESU< PPSU. To further
investigate the effects of penetrants on membrane swelling and polymer
microstructure, PALS measurements were carried out for the membranes at
the wet state by immersing membrane samples in an 85/15 wt% ethanol/water
solution for 12 hr before tests. Table 4.4 tabulates the results. Comparing the
PALS data at dry and wet states, increases in τ3 and R are observed for all four
membranes, suggesting that swelling results in a larger free volume. This
clearly accounts for the significant flux increment after swelling. On the
contrary, I3 decreases for all the membranes, indicating that adjacent small
cavities at the dry state may coalesce to form large cavities at the wet state or
some cavities are filled with the penetrants at the wet state [39].
Table 4.3 PALS data of dry PESU, T-PESU, PPSU and H-PESU membranes
Membrane τ3 (ns) I3 (%) R (Å) FFV (%)
PESU 1.779±0.009 19.52±0.15 2.644±0.008 2.720±0.046
PPSU 1.922±0.008 23.83±0.14 2.782±0.006 3.871±0.049
T-PESU 1.928±0.009 20.19±0.13 2.788±0.007 3.299±0.048
H-PESU 1.839±0.009 18.91±0.14 2.703±0.008 2.816±0.045
64
Table 4.4 PALS data of wet PESU, T-PESU, PPSU and H-PESU membranes
PESU 1.867±0.010 18.88±0.14 2.731±0.008 2.898±0.047
PPSU 2.044±0.009 22.16±0.12 2.896±0.006 4.057±0.050
T-PESU 1.967±0.010 20.12±0.13 2.824±0.007 3.418±0.049
H-PESU 2.117±0.010 18.07±0.11 2.961±0.007 3.535±0.048
A comparison of FFVs at dry and wet states is shown in Figure 4.4. For PESU,
T-PESU and PPSU, the percentage of FFV increment follows the order of
PESU>PPSU>T-PESU which is consistent with the trend of ethanol uptake
ratio. This is because the FFV increment is caused by swelling and for these
three membranes, swelling is mainly induced by ethanol since their ethanol
uptake prevails over the water uptake as shown in Table 4.2. Therefore, the
FFV incremental trend is in good agreement with the ethanol uptake ratio
trend for these three membranes. On the contrary, swelling of the H-PESU
membrane is mainly caused by water due to its preferential affinity to water as
implied in Table 4.2. Figure 4.4 shows that the FFV increment for the H-
PESU membrane is much more severe than the other three. As a result, FFV of
the H-PESU membrane becomes the second largest after swelling. In addition,
by comparing the structures of H-PESU and PESU, it can be concluded that
the big difference between their percentages of FFV increment is caused by
the incorporation of the Pluronic moiety. This suggests that the swelling of H-
PESU membrane mainly occurs in the hydrophilic Pluronic regions.
65
5 30
4.5
3.8714.057 25
FFV increment percentage (%)

4 3.535
3.5 3.2993.418
20
3 2.72 2.898 2.816
FFV(%)
2.5 15
2
1.5 10
1 5
0.5
0 0
PESU PPSU T-PESU H-PESU
Dry state Wet state FFV increment percentage %
Figure 4.4 Comparison of FFVs at dry and wet states measured by PALS
4.3.4 Ethanol and methanol performance
Table 4.5 summarizes the ethanol dehydration performance of the four
membranes at 60 oC. Normalized flux is used in this study, which is the
product of flux and membrane thickness. This is to eliminate the impact of the
slight inconsistency in membrane thickness.
Table 4.5 Ethanol dehydration performance of PESU, T-PESU, PPSU and H-

PESU membranes
Total Water Ethanol Water
normalized normalized normalized Conc. in Separation
Membrane flux* flux* flux* permeate factor
2 2
（gμm/m h）（gμm/m h）（gμm/m h）（wt%）
2
PESU 661.8±82.6 657.2±82.0 4.6±0.6 99.3±0.4 784.6

T-PESU 815.8±5.0 810.9±4.9 4.9±0.1 99.4±0.2 936.4
PPSU 1333.1±25.4 1314.4±25.0 18.7±0.4 98.6±0.5 389.6
H-PESU 4352.1±124.7 4299.9±123.2 52.2±1.5 98.8±0.2 483.9
o
* Feed composition: 85% ethanol+15% water; Test temperature: 60 C
66
For these four PAE membranes, the water normalized flux is much higher than
the ethanol normalized flux and accounts for most of the total normalized flux,
suggesting that these PAE membranes are highly water selective. In
pervaporation, the commonly cited separation mechanism is the solution-
diffusion model. Based on this model, permeability depends on solubility and
diffusivity. Generally, higher hydrophilicity and water uptake may signify a
higher water solubility while a higher FFV is conducive to the fast diffusion of
the permeate components across the membranes. Thus, membranes with
higher hydrophilicity and higher FFV are favorable to attain a high permeation
flux. In this regard, the PESU membrane shows the smallest water normalized
flux due to its smallest water solubility and diffusivity since it has the lowest
water uptake ratio and the smallest FFV as aforementioned in Table 4.2 and
Table 4.4, respectively. The increases of water normalized flux for T-PESU
and PPSU are because of the increases in both water solubility and diffusivity.
It's worth noting that the H-PESU membrane shows the largest water
normalized flux, which is 2-6 times higher than those of the other three
membranes. This can be explained by the following reasons: (1) the H-PESU
membrane has the largest water solubility as shown in Table 4.2 due to the
hydrophilic nature of the Pluronic moiety and (2) its FFV value is moderate as
shown in Table 4.4, and its hydrophilic Pluronic moiety may form special
water transport channels for fast water diffusion, which lead to a high water
diffusivity. At the same time, the H-PESU membrane also has the highest
ethanol normalized flux among these four PAE membranes which may be due
to the swelling effect.
67
In addition, the PPSU membrane shows the lowest separation factor which is
mainly ascribed to its smallest diffusivity selectivity since it has the largest
FFV. It is interesting to observe that the H-PESU membrane exhibits a
comparable separation factor although its degree of swelling is much higher
than the others. This is due to the constraint of the hydrophobic and rigid
PESU moiety. In other words, the swelling mainly occurs in the Pluronic
regions, which have the highest solubility selectivity and most likely promote
the transport of water molecules rather than ethanol molecules. These Pluronic
channels are preferentially occupied by water molecules and this possibly adds
the resistance for ethanol transport. Therefore, the water molecules have
priority to diffuse through these channels. On the other hand, the rigid PESU
moiety prevents the membrane from uncontrolled swelling and ensures good
separation efficiency. Clearly, the combination of PESU and Pluronic moieties
results in a synergistic microstructure that endows the membrane with a
superior flux and a remarkable separation factor.
Table 4.6 shows a benchmarking comparison with literature data [40-45] . The
four membranes developed in this study not only exhibit comparable water
permeability but also higher mole-based selectivity than most of the rest in the
table. Especially, the H-PESU membrane displays the most promising
performance and may have great potential for industrialization.
68
Table 4.6 A comparison of pervaporation performance for ethanol
dehydration
Water
Membrane Water Mole-
Temp. permeability
Membrane thickness concentration o based Ref.
( C) (mg m-1 h-1
(μm) in feed selectivity
kPa-1)
Crosslinked
20 10% 60 1.136 417 [40]
Chitosan
Crosslinked
29 10% 60 0.823 456 [41]
PVA
P84®
--- 15% 60 0.034 1874 [42]
copolyimide
Pervap® 2201 --- 10% 60 0.022 309 [43]
TR PBO 20-25 10% 25 1.254 186 [44]
Matrimid
45-55 15% 60 0.136 481 [45]
/hPIM-1
This
PESU 21 15% 60 0.049 1111
study
This
T-PESU 20 15% 60 0.061 1326
study
This
PPSU 23 15% 60 0.098 552
study
This
H-PESU 36 15% 60 0.322 685
study
To date, methanol dehydration by polymer membranes via pervaporation has
not been widely studied, which may be attributed to the lack of suitable and
affordable membrane materials with excellent anti-methanol swelling
properties [33]. Inorganic membranes are dominant in methanol dehydration
since they don’t have the solvent-induced swelling problem. However, their
extensive applications are restricted by the fragility and high costs of
fabrication. In contrast, polymeric membranes are easy to fabricate and scale-
up with relatively low costs. However, polymeric membranes for methanol
dehydration usually suffer from poor separation efficiency because of swelling
69
[4, 6, 17]. Therefore, polymeric membranes are still not popular for methanol
dehydration.
In view of the good performance for ethanol dehydration, the four membranes
developed in this study were employed for methanol dehydration. Table 4.7
summarizes the results. PESU, T-PESU and PPSU membranes have
comparable water and methanol normalized fluxes. While similar to ethanol
dehydration, the H-PESU membrane shows both the highest water and
methanol normalized fluxes. On the other hand, all these four PAE membranes
show separation factor higher than 28 and mole-based selectivity more than 82
which is far better than most of the other polymeric membranes listed in
Table 4.8 [33, 46, 47]. Especially, the T-PESU membrane has the highest
separation factor of 39.8 which corresponds to 86.8% water in the permeate.
In addition, compared to other polymeric membranes, the membranes
developed in this work have the more balanced separation performance in
terms of superior separation factors and moderate normalized fluxes.
Table 4.7 Methanol dehydration performance of PESU, T-PESU, PPSU and

H-PESU membranes
Total Water Methanol Water
normalized normalized normalized Conc. in Separation
Membrane flux* flux* flux* permeate factor
2 2
（gμm/m h）（gμm/m h）（gμm/m h）（wt%）
2
PESU 1066.2±32.3 886.0±26.8 180.2±5.5 83.1±1.8 29.7

T-PESU 1072.7±64.9 931.1±56.3 141.6±8.6 86.8±1.5 39.8
PPSU 1133.5±21.6 936.3±17.8 197.2±3.8 82.6±1.3 28.7
H-PESU 2134.7±254.1 1788.9±212.9 345.8±41.2 83.8±1.8 31.3
* Feed composition: 85% methanol+15% water; Test temperature: 60 oC
70
Table 4.8 A comparison of pervaporation performance for methanol
dehydration
Water Mole-
Membrane Water
Temp. permeability based
Membrane thickness concentration Ref.
(oC) (mg m-1 h-1 selectivity
(μm) in feed
kPa-1)
5%-sPPSU 16 15% 60 0.033 33.8 [33]
2.5%-sPPSU 16 15% 60 0.030 32.1 [33]
Agarose 14-20 14% 30 0.925-1.321 8.3 [46]
Polyamide-
30 10% 20 0.268-0.415 9.2-99.9 [47]
sulfonamide
This
PESU 21 15% 60 0.085 85.1
study
This
T-PESU 20 15% 60 0.089 114.0
study
This
PPSU 23 15% 60 0.089 82.0
study
This
H-PESU 36 15% 60 0.171 89.7
study
The H-PESU membrane is chosen for further studies of the effect of feed
concentration on pervaporation performace since its has the best separation
performance with the highest normalized flux and comparable separation
factor. Aqueous ethanol and methanol systems with alcohol concentrations of
85wt%, 90wt% and 95wt% are investigated. Figure 4.5 shows that the water
normalized flux decreases while the ethanol and methanol normalized fluxes
increase with an increase in alcohol concentration in ethanol/water and
methanol/water systems. These phenomena are mainly because a higher
alcohol concentration results in a lower driving force for water transport but a
higher driving force for alcohol transport [44]. As a result, both total
normalized flux and separation factor decrease with an increase in alcohol
concentration as shown in Figure 4.6 and Figure 4.7. Similar trends have been
reported elsewhere [44, 48].
71
a 6000
Water normalized flux

Ethanol/water system
5000 Methanol/water system
(gμm/m2h)
4000
3000
2000
1000
0
80 85 90 95 100
Alcohol Concentration (%)
1000
b Ethanol/water system
900
Alcohol normalized flux
800 Methanol/water system

700
(gμm/m2h)
600
500
400
300
200
100
0
80 85 90 95 100
Alcohol Concentration (%)
Figure 4.5 (a) Water and (b) ethanol/methanol normalized flux of H-PESU
membranes at different feed concentrations at 60 ºC
6000
Total normalized flux
500
Separation factor
5000
400
(gμm/m2h)
4000
3000 300
2000 200
1000 100
0 0
80 85 90 95 100
Ethanol Concentration (%)
Figure 4.6 Ethanol dehydration performance of H-PESU membranes at

different feed concentrations at 60 ºC
72
6000 40

5000 35
Separation factor
30
(gμm/m2h)
4000 25
3000 20
2000 15
10
1000 5
0 0
80 85 90 95 100
Methanol Concentration (%)
Figure 4.7 Methanol dehydration performance of H-PESU membranes at

different feed concentrations at 60 ºC
4.3.5 Long-term stability tests
Long-term operating stability is another important factor to evaluate the
potential of a membrane material. Therefore, the long-term stability tests of
the H-PESU membrane were conducted for ethanol dehydration at 60 oC with
the feed composition of 85wt%/15wt% ethanol/water. The PESU membrane
was selected for comparison. Their fluxes and separation factors were
continuously monitored for 250h. Figure 4.8 shows their results. It can be
found that for H-PESU membrane, the water concentration in the permeate
decreases slightly from 98.7 wt% to 96.5 wt% at the early stage, which is
caused by swelling. Subsequently, it becomes stable at around 96.3%, which is
still acceptable for ethanol dehydration. Overall, the long-term performance of
the H-PESU membrane is quite reliable. This is again due to the combination
of the strengths from both rigid hydrophobic PESU moiety and flexible
hydrophilic Pluronic moiety in the H-PESU polymer. In contrast, the PESU
membrane shows quite stable performance with little fluctuations in both
73
normalized flux and separation factor during the entire testing duration of
250h. This is because the PESU membrane has higher anti-swelling properties
than the H-PESU membrane because the latter contains the hydrophilic
Pluronic moiety.
100.0
14000
Normalized flux (gμm/m2h)
Water concentration in the

98.0
12000 96.0
permeate (wt%)
10000 94.0
92.0
8000 90.0
6000 88.0
4000 86.0
84.0
2000 82.0
0 80.0
100 0 50
150 200 250
Test Duration (h)
PESU H-PESU
Figure 4.8 Long-term stability of the PESU and H-PESU membranes for
ethanol dehydration at 60 ºC with the feed composition of 85wt%/15wt%
ethanol/water
4.4 Conclusions
In this study, pervaporation membranes made from four polyarylether (PAE)
materials: PESU, PPSU, T-PESU and H-PESU have been explored for
pervaporation dehydration of ethanol and methanol. These PAE membranes
showed impressive separation performance for both dehydration cases. Some
interesting correlations between mass transport phenomena and structural
characteristics were also unveiled.
74
PALS measurements reveal that swelling results in a larger free volume radius
and a bigger FFV. In addition, the adjacent small cavities in the membranes at
the dry state may coalesce to form large cavities at the wet state. Among these
four PAE membranes, the H-PESU membrane shows the best ethanol
dehydration performance with the highest water permeability of 0.322 mg m-1
h-1 kPa-1 and a comparable mole-based selectivity of 685 due to its unique
structure consisting of both hydrophilic and hydrophobic moieties. The
hydrophilic Pluronic moiety may form special channels which are
preferentially occupied by water molecules and promote the fast transport of
water molecules. Therefore, the H-PESU membrane has the highest water
solubility and solubility selectivity. On the other hand, its hydrophobic and
rigid PESU moiety can prevent the membrane from uncontrolled swelling and
contribute to good separation efficiency. The long-term operating stabilities of
PESU and HPESU have been demonstrated. In addition, the separation
performance of these PAE membranes are better than most of reported
polymeric membranes for both ethanol and methanol dehydration, implying
their great potential for pervaporation applications.
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82
CHAPTER 5: POLYIMDE AND CROSSLINKED
THERMALLY REARRANGED
POLY(BENZOXAZOLE-CO-IMIDE)
MEMBRANES FOR ISOPROPANOL
DEHYFRATION VIA PERVAPORATION
5.1 Introduction
Isopropanol (IPA) is an important alcohol which is used for a variety of
industrial and consumer applications. For example, it can be used as an
effective cleaner for electronic and optical devices because of its non-toxicity,
fast evaporation and ability to dissolve a wide range of non-polar compounds.
Moreover, it is also a chemical intermediate for the production of isopropyl
acetate, rubbing alcohol, vitamin B12 and a pharmaceutical additive used in
hand sanitizer and disinfecting pads [1, 2]. In addition, it can be considered as
an alternative fuel to alleviate global warming and slow down the depletion of
fossil fuels [3, 4]. Isopropanol is produced either by the chemical reaction
between propene and water or by microorganism’s fermentation [4]. However,
both processes require the separation of water from IPA to produce high purity
IPA. Hence, the successful production and applications of isopropanol
strongly depends on the development of effective dehydration technologies
[5]. Currently, distillation is the dominant separation technology employed for
the dehydration of IPA. However, its high energy consumption and
ineffectiveness in separating azeotropic mixtures pave the way for the
development of other separation technologies [6].
83
Pervaporation, a membrane-based separation technology, may be regarded as
a promising dehydration process [7] because it offers several unique
advantages over distillation. First, pervaporation is not limited by the vapor-
liquid equilibrium, and thus expected to have surpassing separation efficiency,
particularly in separating azeotropic and close boiling point liquid mixtures [8].
Second, it is a clean technology and can avoid cross-contamination because it
does not need third components, which are commonly employed in the so-
called “azeotropic distillations” [9]. Third, pervaporation is an energy-saving
process because only the permeating component consumes the latent heat [10,
11]. Moreover, pervaporation has a mild operation condition by using low
feed pressures and temperatures [8, 12]. Last, the compactness in module
fabrication as well as simplicity in process control are also advantageous
characteristics of pervaporation [13].
In pervaporation processes, membrane is vitally important. Polymeric
membranes are currently widely used in pervaporation because of their
advantages in ease of fabrication and scale-up, low capital costs, and low
footprint [14]. Polybenzoxazole (PBO) is a kind of glassy polymers which has
a unique rigid-rod structure and possesses advantageous characteristics such as
excellent solvent resistance, good thermal stability and high mechanical
strength [15-21]. However, its high solvent resistance reduces its solubility in
common solvents, and this brings about obstructions in membrane preparation
and constrains their applications [15-17]. To solve this problem, researchers
have developed an alternative PBO membrane preparation method via the in-
84
situ thermal conversion of hydroxyl-containing polyimide precursors. In this
method, an aromatic polyimide, which contains hydroxyl groups ortho to the
imide nitrogen, can be converted to a polybenzoxazole through thermal
rearrangement (TR) upon heating between 350 and 500 °C in an inert
atmosphere or under vacuum [15-17]. This method makes the fabrication of
PBO membranes more feasible.
Numerous works have focused on the application of thermally rearranged
polybenzoxazole (TR-PBO) membranes for gas separation. TR-PBO
membranes have shown superior gas separation properties especially in
separating CO2/CH4 mixtures, surpassing the 2008 upper bound [22-25]. The
existence of micropores and high free volume in TR polymers is the reason for
the high permeability, while the rigid-rod benzoxazole structure contributes to
the relatively stable selectivity [22]. Researchers have also investigated the
effects of different polyimide precursor structures [26-28], imidization
methods [29], TR protocols [27, 30-32] and TR-PBO membrane thickness [33]
on the free volume distribution and gas separation performance.
Although TR-PBO membranes have been widely explored for gas separation,
there are limited studies on their applications for pervaporation [34, 35].
Among the limited studies, only one of them was related to alcohol
dehydration where Ong et al. studied the effects of dwell duration and thermal
rearrangement temperature on alcohol dehydration performance [34].
Experimental results indicated that the thermal rearrangement temperature had
more significant impact on pervaporation performance than the dwell time. In
85
addition, the TR-PBO membranes which were treated at 450°C for half an
hour exhibited the highest flux with a reasonable separation factor for ethanol
dehydration.
In this study, a set of crosslinked thermally rearranged polybenzoxazole (C-
TR-PBO) membranes are prepared via in-situ thermal conversion of hydroxy-
containing polyimide precursors and are utilized for isopropanol dehydration
via pervaporation. The polyimide precursors are synthesized from the
polycondensation of 4,4’-(hexafluoroisopropylidene) diphthalic anhydride
(6FDA), 3,3’-dihydroxybenzidine diamine (HAB) and 3,5-diaminobenzoic
acid (DABA). The resultant polyimide precursors are first cast into
membranes, and then converted to C-TR-PBO through the thermal treatment.
The advantages of these three chosen monomers are: (1) 6FDA contains
fluorine groups –CF3, which are expected to prevent polymer chains from
compact packing and increase the free volume of the resultant polymer; (2)
HAB has a hydroxyl group ortho to the amine group, which meets the
essential requirement for the TR process; and (3) DABA possesses a
carboxylic group in the structure, which can undergo thermal crosslinking
during the thermal treatment. The thermally induced crosslinking mechanism
for the carboxylic-group containing polyimide was proposed by Qiu et al. [36]
as shown in Figure 5.1. Under vacuum or an inert condition and at high
temperatures, the carboxylic groups of two neighboring polymer chains react
to form anhydride groups. Subsequently, two phenyl free radicals are
generated from the decarboxylation of the anhydride along with the release of
a CO and CO2 molecule. After that, these adjacent phenyl radicals combine to
86
form linkages that yield biphenyl crosslinking. This would further enhance the
stability and swelling resistance of resultant membranes.
The present research aims to (1) develop new polybenzoxazole membrane
materials with combination of crosslinking and thermal rearrangement for
pervaporation applications (2) study the synergistic effects of crosslinking and
thermal rearrangement on the physicochemical properties of the membranes.
To our best knowledge, this is the first time that this material is synthesized
and studied for pervaporation dehydration.
Figure 5.1 Crosslinking mechanism of the polyimide containing carboxylic

groups under thermal treatment
5.2 Experimental
6FDA-HAB/DABA polyimides were synthesized as the method shown in
Chapter 3. Crosslinked polybenzoxazole membranes were obtained by
thermal rearrangement of polyimide precursors. The chemical structures of the
synthesized polyimide and poly(benzoxazole-co-imide) were analyzed by
FTIR. Membranes’ thermal stability was examined by TGA. In order to
investigate the reactions during the thermal treatment, TGA-IR was carried
out. PALS measurements and solvent uptake analyses were also conducted to
know the diffusivity and solubility information.
87
5.3.1 Characterizations of PI and C-TR membranes
In order to verify the success in synthesizing the 6FDA-HAB/DABA
polyimide, ATR-FTIR analyses are carried out and the results are shown in
Figure 5.2. The synthesized polymers possess the characteristic peaks at 1774
and 1716 cm-1 which are mainly attributed to typical double bands stretching
of the C=O group in the imide ring [37-40]. In addition, the C–N stretching at
1365 cm-1, the transverse stretching of C–N–C groups at 1084 cm-1, and the
out-of-plane bending of C–N–C groups at 717 cm-1 also characterize the
presence of imide groups [34, 37, 38]. This confirms the successful fabrication
of the polyimide membrane.
Figure 5.2 FTIR spectra of synthesized polyimides
In contrast, for the C-TR-PBO membranes, it should be noted that the ATR-
FTIR spectra show weak peak intensities due to the dark brown colour of the
88
membranes. Therefore, a transmission mode of FTIR is used for the C-TR-
PBO membranes. According to Figure 5.3, three new peaks for C-TR-PBO
membranes can be observed at around 1477, 1554 and 1620 cm−1, which
characterize the vibration of benzoxazole rings [32, 41, 42]. Peaks at 1477 and
1554 cm−1 are the absorbing bands of benzoxazoles whereas the characteristic
peak at 1620 cm−1 is due to C=N stretching [32, 42]. These results validate the
successful formation of the polybenzoxazole structure.
Figure 5.3 FTIR spectra of poly(benzoxazole-co-imide)
Figure 5.4 shows the thermal behavior of the synthesized polyimides. The
polyimides undergo a three-stage weight loss as the temperature increases
from 100 to 700 oC. The initial weight loss (less than 1%) between 100oC to
250oC is ascribed to the elimination of residual solvents or moisture. The
second stage weight loss at 250-500oC is due to the release of gas molecules
89
produced from crosslinking and thermal rearrangement reactions. From 500 ºC
onwards, polymer chains start to decompose which results in the last stage
weight loss.
100
PI-5-5
90 PI-7-3
Weight percentage (%)
PI-9-1
80 PI-10-0
70
60
50
40
100 150 200 250 300 350 400 450 500 550 600 650 700
Temperature (ºC)
Figure 5.4 TGA curves of polyimide precursors
Figure 5.5 and Figure 5.6 show the TGA curve and the simultaneous IR
spectra of gases released from polyimide membranes PI-10-0 and PI-9-1
during pyrolysis, respectively. In TGA-IR spectra, yellow represents the
lowest intensity of a peak, red signifies the medium intensity, and turquoise
denotes the highest intensity. After about 48 min of heating corresponding to a
temperature of about 420oC, the CO2 characteristic IR peak (2250-2400 cm−1)
and the -C=O characteristic peak (1750 to 1850 cm−1) show up in the TGA-IR
spectra. The detected CO2 comes from the thermal rearrangement process.
When the temperature increases to about 520 oC, additional IR peaks including
H2O (3600-3750 cm−1), CFx (1150-1200 cm−1) and -C-O (1000-1050 cm−1)
groups are evolved. This suggests that the polymer backbone starts to
decompose at this high temperature.
90
Compared with the IR spectrum of PI-10-0, Figure 5.6 reveals that PI-9-1
experiences an earlier appearance of H2O peak, -C=O peak, -C-O peak and
CO2 peak at a lower temperature and illustrates the distinct peak of CO
molecules.
Figure 5.5 (a) Top-view 3D TGA-FTIR analyses of the polyimide precursor

PI-10-0 and (b) Heating time of TGA and weight percentage vs. temperature
correlation
Figure 5.6 (a) Top-view 3D TGA-FTIR analyses of the polyimide precursor

PI-9-1 and (b) Heating time of TGA and weight percentage vs. temperature
correlation
91
According to Figure 5.1, water, CO2 and CO molecules are released during the
crosslinking reaction. Therefore, this phenomenon implies that the thermally
induced crosslinking reaction occurs at lower temperatures than thermal
rearrangement. As temperature further increases, thermal rearrangement starts
to occur, while the crosslinking process is continuing. When temperature
reaches about 500 oC, decomposition of polymer chains starts, similar to the
case of PI-10-0.
In order to understand the affinity between the permeate molecules and the
membrane, solvent uptake analyses were carried out at 60 oC. This temperature
is kept the same as the pervaporation test in order to have a fair comparison.
Figure 5.7 shows a comparison of solvent uptakes for the three polyimide
precursors and their respective C-TR membranes in isopropanol and water.
Both the polyimide precursors and C-TR membranes have higher affinity
towards isopropanol than water, which implies that the membranes remain
relatively hydrophobic. However, as the amount of carboxylic group increases,
the water uptake increases while isopropanol uptake decreases for both
polyimide precursors and C-TR membranes, indicating an improvement in
solubility selectivity towards water. This phenomenon is attributed to the
hydrophilic nature of carboxylic groups, which can play as absorption sites of
water. Comparing the polyimide and its respective C-TR membrane, it can be
observed that the latter absorbs less water and more isopropanol, which
implies C-TR membranes have lower solubility selectivity towards water than
92
polyimide membranes. This phenomenon corresponds well with the
observation reported by Ong et al. and Wang et al. [34, 43].
HAB-DABA
Figure 5.7 Solvent uptake analyses for PI and C-TR membranes
5.3.3 Positron annihilation lifetime spectroscopy analyses
Positron annihilation lifetime spectroscopy (PALS) was applied to
quantitatively analyze the free volume size and distribution for the polyimide
and C-TR membrane samples. In PALS measurements, the o-Ps lifetime τ3
and its intensity I3 are correlated to the size and concentration of the free
volume, respectively [44-46]. Figure 5.8 presents the PALS results. It can be
observed that the polyimide membranes have τ3 data in the range of 2.19 to
2.32 ns that corresponds to a mean cavity radius of 3.02 to 3.13Å. After
thermal rearrangement, τ3 increases to 2.47-2.69 ns, indicating an increase in
cavity sizes to 3.28-3.41Å. This increase is attributed to the formation of
93
cavities during the thermal rearrangement and thermal crosslinking reactions.
At the same time, compared with polyimide precursors, the intensities I3 of C-
TR membranes also increase, signifying that more pores are created after the
thermal treatment.
6 8
5.5 C-TR
5
PI
6
4.5
τ3(ns)
I3 (%)
4 4
3.5
3 C-TR 2
2.5
PI
2 0
10-0 9-1 7-3 5-5
HAB-DABA
Figure 5.8 PALS data of PI membranes and C-TR membranes
On the other hand, Figure 5.8 also reveals the effect of DABA content on
membrane free volume. For the PI membranes, τ3 and I3 do not show
significant change (4.59-4.72%) as the DABA to HAB ratio increases. This is
probably because the carboxylic side chain in DABA is too small to affect
polymer free volume. In contrast, the intensity I3 of C-TR membranes
decreases from C-TR-10-0 to C-TR-9-1 and subsequently increases from C-
TR-9-1 to C-TR-5-5. This decrease-and-increase trend of intensity for C-TR
membranes may be due to the combined effects of cavity formation during
thermal treatment and crosslinking’s inhibitory influence on TR [23, 24]. A
similar trend was reported by Calle et al. [24].
94
Figure 5.9 indicates the calculated fractional free volume as a function of
DABA to HAB ratio. Given that the lifetime τ3 for PI and C-TR membranes
remains relatively constant, it can be concluded that their fractional free
volumes are mainly affected by the change of intensity. The fractional free
volumes of PI membranes do not change significantly (0.96 to 1.09%) while
those of C-TR membranes exhibit a V-shape in the range from 1.44 to 2.20 %.
2.5
Fractional free volume (%)
2 C-TR
1.5
1 PI
0.5
0
10-0 9-1 7-3 5-5
HAB-DABA
Figure 5.9 Fractional free volumes of PI and C-TR membranes
5.3.4 Pervaporation performance of PI and C-TR membranes
Figure 5.10 summarizes the pervaporation performance of PI membranes and
C-TR membranes for dehydration of 85 wt% isopropanol aqueous solutions.
In order to eliminate the influence of membrane thickness, normalized flux is
used in this study for comparison.
95
4000 100.0
C-TR
Water concentration in permeate (wt%)

99.5
Total normalized flux (gμm/m h)
3500
2
PI 99.0
3000 98.5
98.0
2500
C-TR 97.5
2000
97.0
PI
1500 96.5
96.0
1000
95.5
500 95.0
10-0 9-1 7-3 5-5
HAB-DABA
Figure 5.10 Isopropanol dehydration performance of PI and C-TR membranes

at 60 ºC
As illustrated in Figure 5.10, as the DABA to HAB ratio increases, the
normalized flux of PI membranes also increases. However, their separation
factor initially increases from PI-10-0 to PI-7-3 but subsequently decreases for
PI-5-5. The increase in normalized flux is attributed to two factors. First, the
high DABA to HAB ratio increases the hydrophilicity of the membranes, as
discussed in section 3.2, which allows more water to be absorbed onto the
membranes. This, in turn, results in the loosening of polymeric chains (in the
wet state) and the increase in flux. Second, the membranes with a higher
DABA to HAB ratio have higher fraction free volumes (PI-7-3 and PI-5-5) as
indicated in Figure 5.9, which may lead to a higher flux in the wet state. On
the other hand, when the DABA to HAB ratio increases from 10:0 to 7:3, the
96
increase in separation factor is mainly due to the enhanced solubility
selectivity as discussed in section 3.2. For the membrane PI-5-5, the slight
decrease in separation factor may be attributed to the water-induced swelling.
Nonetheless, the water concentrations in permeate of all studied PI membranes
remain higher than 99.0%, indicating good separation performance.
Although the separation factors of PI membranes are high, their normalized
fluxes are relatively low. In order to further enhance the pervaporation
performance, the PI membranes are thermally treated to enable thermal
rearrangement and crosslinking. Figure 5.10 shows that the normalized fluxes
of C-TR membranes are higher than those of PI membranes for all DABA to
HAB ratios. The increase in flux of C-TR membranes is attributed to their
larger free volume sizes and higher fractional free volumes. However, when
compared with the PI membranes, the C-TR-10-0, C-TR-9-1 and C-TR-7-3
membranes have slightly lower separation factors. This is due to the decreased
diffusivity selectivity when their free volume sizes are larger and decreased
solubility selectivity as discussed in section 3.2. When the DABA to HAB
ratio increases to 5:5; however, the separation factor of C-TR-5-5 membranes
increases while that of PI membranes decreases, leading to the result that the
former is higher than the latter. This interesting result is attributed to anti-
swelling capacity of C-TR-5-5 membranes produced by the thermal
crosslinking reaction among carboxylic groups. Among C-TR membranes, C-
TR-5-5 displays the best separation performance with a normalized flux of
2138 gμm/m2h and a water concentration in permeate of approximate 99.8
wt%, as shown in Figure 5.10.
97
5.3.5 Performance benchmarking and stability of C-TR membranes
Table 5.1 compares the pervaporation performance in terms of permeability
and selectivity for the membranes in this study with various pervaporation
membranes available in literatures [34, 47-52]. Both the PI-5-5 and C-TR-5-5
membranes show comparable water permeability with other membranes. In
terms of selectivity, C-TR-5-5 exhibits outstanding water selectivity, which is
much higher than others. This superior performance opens up the opportunity
of using the newly designed polybenzoxazole-based membranes for biofuel
dehydration via pervaporation.
Besides having satisfactory performance, their long-term stability also needs
to be addressed. Therefore, in order to evaluate the long-term stability of the
C-TR membrane, the pervaporation performance is monitored continuously
for 200 h at 60 ºC. Figure 5.11 shows that the C-TR membrane displays quite
stable separation performance and no obvious reduction of flux and separation
factor can be observed during the entire testing duration of 200 h. The stable
long-term performance has verified the benefits of crosslinking and signifies
the feasibility of the C-TR membranes for pervaporation processes.
98
Table 5.1 A comparison of pervaporation performance of dense membranes
for isopropanol dehydration
Water Mole-
Water permeability
Temp. based
Membrane concentration -1 -1 Ref.
(ºC) (mg m h selectivity
in feed -1
kPa )
Matrimid 18% 100 0.490 50 [47]
Torlon 15% 60 0.011 3302 [48]
Ultem 15% 60 0.012 683 [48]
BPADA-ODA-
20% 60 0.145 9530 [49]
DABA polyimide
Crosslinked
10% 60 0.835 609 [50]
Chitosan
Matrimid/MgO
18% 100 0.067 1513 [47]
MMMs
PBI/ZIF-8 MMMs 15% 60 0.358 1969 [51]
P84/ZIF-90 MMMs 15% 60 0.166 449 [52]
TR PBO 10% 80 0.299 670 [34]
C-TR-5-5 15% 60 0.150 4019 This study
PI-5-5 15% 60 0.129 882 This study
200 100 Water concentration in permeate

90
180
80
160 70
Total flux (g/m2h)
140 60
(%)
50
120 40
100 30
20
80
10
60 0
0 50 100 150 200
Operating time (h)
Figure 5.11 Long-term stability of the C-TR-5-5 membrane for isopropanol

dehydration at 60 ºC
99
5.4 Conclusions
In this study, 6FDA-HAB/DABA copolyimides with four different HAB to
DABA molar ratios were synthesized and subsequently thermally treated to
form C-TR membranes. The science of both PI and C-TR membranes has
been studied and their isopropanol dehydration performance of isopropanol
has been evaluated. The following conclusions can be drawn:
(1) Thermal treatment of the 6FDA-HAB/DABA polyimides at 450 C for
half an hour induces thermal rearrangement and crosslinking reaction though
decarboxylation. A higher fractional free volume is achieved during thermal
rearrangement and crosslinking processes.
(2) As the DABA to HAB ratio increases, both PI and C-TR membranes
absorb more water and less isopropanol, which suggests an increase in
solubility selectivity towards water. On the other hand, the C-TR membrane
shows a higher affinity towards isopropanol than PI precursors, which
indicates that C-TR membranes have lower solubility selectivity towards
water than PI membranes.
(3) C-TR membranes show a higher normalized flux than their PI precursor
membranes. As the DABA to HAB ratio increases, both normalized flux and
separation factor of C-TR membranes increase simultaneously. C-TR-5-5
exhibits the best pervaporation performance.
(4) The C-TR-5-5 membrane displays stable isopropanol dehydration
performance at 60 C throughout the continuous duration of 200 h, indicating
great potential of the C-TR material for pervaporation application.
100
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107
CHAPTER 6: UiO-66/POLYIMIDE MIXED MATRIX
MEMBRANES FOR ETHANOL,
ISOPROPANOL AND N-BUTANOL
DEHYDRATION VIA PERVAPORATION
6.1 Introduction
The global warming resulting from the heavy utilization of fossil fuels has
raised the urgency to explore renewable and sustainable energy so that
mankind can alleviate the reliance on fossil fuels. Biofuels, produced from
biomass by biological processes, have been viewed as a promising candidate
to substitute fossil fuels [1]. In the production of biofuels, the separation of
biofuels from fermentation broth is the most expensive process, which can
account for 60 to 80% of the total cost [1]. Therefore, the development of an
economic and effective separation technology is essential to produce cost-
effective biofuels. Pervaporation has been considered as a promising
candidate to replace conventional separation technologies such as distillation
and adsorption in chemical and energy industries as it has advantages of low
energy consumption, environmental friendliness, small footprint and mild
operation conditions [2-5]. What’s more, pervaporation is powerful to
separate azeotropic mixtures because it is not restricted by the vapor-liquid
equilibrium [6].
108
Based on membrane materials, pervaporation membranes can be classified
into inorganic membranes and polymeric membranes. Inorganic membranes
have superior thermal, chemical and mechanical stabilities. They are not
subjected to any solvent-induced swelling problem. Therefore, inorganic
membranes have superior separation performance especially in harsh
environments with strong solvents, low pH or high temperatures [7]. However,
their fragility and high costs of fabrication limit their wide applications.
Compared with inorganic membranes, polymeric membranes are more widely
utilized for pervaporation due to the advantages such as ease of fabrication and
scale-up, lower capital costs, better utilization of space and reasonable
separation performance [6, 8-10]. However, these membranes usually
encounter the trade-off relationship between permeability and selectivity.
They also suffer from the problem of long-term stability due to the solvent-
induced swelling effect.
In order to combine the strengths of inorganic and polymeric membranes,
mixed matrix membranes (MMMs) consisting of inorganic fillers dispersed in
organic polymers were first developed by Kulprathipanja et al. in 1988 [11].
The incorporation of inherently high permeability and selectivity inorganic
particles into polymeric matrices may result in MMMs that not only have
better separation performance than the original polymeric membranes but also
minimize the fragility issue in inorganic membranes [12, 13]. Numerous
inorganic fillers including zeolites, carbon molecular sieves, silica, metal
oxides, carbon nanotubes, silicate, metal organic frameworks (MOFs),
graphene oxide (GO), porous organic cages, covalent organic frameworks
109
have been investigated and employed in mixed matrix membranes [8, 14-16].
Among them, metal organic frameworks (MOFs), have been demonstrated as
promising materials for MMMs due to their unique characteristics such as
large surface areas, controllable porosity, high adsorption capacity for certain
gases and good affinity with polymer chains, as well as the tuneable chemical
properties [14-16].
Among various MOFs, UiO-66, synthesized by ZrCl4 and 1,4-benzene-
dicarboxylate (BDC), possessing 12-coordinated zirconium-oxo clusters, has
received significant attention since the pioneering work by Cavka et al. in
2008 [17]. UiO-66 based membranes have shown excellent gas separation
performance especially in CO2/CH4 separation with high selectivity and good
adsorption capacity [18-23]. Nik et al. reported CO2 permeability of the UiO-
66 based MMMs increased significantly compared to the neat polymer
membrane without compromising the selectivity [18]. Besides, UiO-66 based
membranes also show great potential in water reuse and desalination [24, 25].
The pure-phase UiO-66 polycrystalline membranes fabricated on alumina
hollow fibres exhibited excellent multivalent ion rejections with good
permeability and outstanding water stability up to 170h tests in a wide range
of saline solutions [24, 25]. The excellent chemical stability was attributed to
the strong coordination covalent bonds between the hard-acid−hard-base
interactions of the Zr atoms and carboxylate oxygens. Yin et al. combined
amino-functionalized UiO-66 (UiO-66-NH2) with ceramic membranes for
adsorptive removal of Pb (II) from wastewater [25]. The resultant membrane
110
was able to effectively remove most of Pb (II) (61.4%) and exhibited
remarkably high adsorption capacity (1795.3 mg·g-1).
Although UiO-66 based MMMs have a wide range of applications as
aforementioned, to our best knowledge, there is no study of UiO-66 based
MMMs for pervaporation. Since UiO-66 possesses many important
characteristics suitable for pervaporation such as high porosity, excellent
chemical and thermal stability and tunable chemical properties [26-29], this
work aims to explore the feasibility of applying UiO-66 based MMMs for
pervaporation and investigate the fundamental science behind the performance
enhancement. To meet the objectives, uniform UiO-66 nanoparticles with a
relatively small particle size would be firstly synthesized and subsequently
employed to prepare UiO-66/6FDA-HAB/DABA polyimide (PI) MMMs with
different particle loadings for dehydration of ethanol, isopropanol and n-
butanol via pervaporation. In addition, basic research on water and alcohol
uptakes and free volume size would be characterized in order to reveal the
actual mechanisms for the performance enhancement. This study may provide
useful insights to develop high performance UiO-66 based MMMs for alcohol
6.2 Experimental
The 6FDA-HAB/DABA polyimide was synthesized by polycondensation of
three monomers 6FDA, HAB and DABA with HAB to DABA of 9:1. UiO-66
was synthesized and MMMs were prepared as the methods in Chapter 3. The
111
crystallographic structure of the UiO-66 nanoparticles was explored by XRD
and cross-sectional morphologies of MMMs were observed by FESEM. EDX
was used to study the distribution of zirconium element. Thermal stability and
UiO-66 loading of MMMs were investigated by TGA. TGA-IR was
conducted to investigate the reactions during the heat treatment. PALS
measurements and solvent uptake tests were carried out to reveal the
mechanism of performance enhancement.
6.3.1 Characterizations of UiO-66 and mixed matrix membranes
The crystallographic structure of the synthesized UiO-66 was measured by
XRD. Figure 6.1 compares the tested XRD result with the simulated one. All
characteristic diffraction peaks match very well with the simulated UiO-66
pattern in the database [30], showing the existence of a highly crystalline
structure of UiO-66 without other impurities. The peaks of the original MMM
are in accordance with the peaks of UiO-66 nanoparticle, indicating the
successful incorporation of UiO-66. In order to investigate the water stability
of UiO-66 based MMMs, a MMM with 20wt% loading was soaked in pure
water at 60°C for one week followed by XRD testing. Remarkably, the peaks
of the MMM after soaking in pure water at 60°C for one week are the same as
the original MMM without any treatment, which means that UiO-66 can
maintain its structure in pure water at 60°C for one week. This finding
confirms the good water stability of UiO-66 based MMMs reported by
previous works [24, 25]. Figure 6.2 shows the FESEM images of UiO-66
112
particles after removing the solvent by drying them in a vacuum oven. The
particles are quite uniform with a particle size of around 100nm.

Intensity (AU)
MMM, in water, 60 ºC, 1 week
MMM
UiO-66 Simulated result
UiO-66 Experimental result
5 15 25 35 45
2 Theta (º)
Figure 6.1 A comparison of XRD patterns of UiO-66 and MMMs
Figure 6.2 FESEM images of (a) UiO-66 nanoparticles and cross-sectional

morphologies of (b) the pristine PI membrane and MMMs containing (c) 10wt%
UiO-66, (d) 20wt% UiO-66, (e) 30wt% UiO-66
Figure 6.2 also displays the cross-sectional morphologies of MMMs consisting
of different UiO-66 loadings. The UiO-66 nanoparticles are dispersed evenly
113
in the polyimide matrix. There is no apparent particle agglomeration even at
the highest Uio-66 loading (30 wt%). These observations demonstrate good
compatibility between UiO-66 nanoparticles and the 6FDA-HAB/DABA
polyimide matrix. Since Zr element only exists in UiO-66 nanoparticles, EDX
mappings of Zr element can be utilized to investigate the dispersion of UiO-66
nanoparticles across the membrane. The result shown in Figure 6.3 further
confirms the even distribution of UiO-66 nanoparticles across the MMM.
MMMs containing 30wt% UiO-66
TGA-IR was conducted to investigate the thermal stability of the UiO-66
nanoparticles and MMMs as well as the reactions during heat treatment.
Figure 6.4 and Figure 6.5 display the TGA curves and the simultaneous IR
spectra of gases released from UiO-66 nanoparticles and the MMM containing
20% UiO-66 during pyrolysis, respectively. For UiO-66, characteristic peaks
of CO2 (2250-2400 cm−1) and H2O (3600-3750 cm−1) are evolved when the
temperature increases to 530°C, which indicates the onset of decomposition of
the UiO-66 framework. These results confirm the superior thermal stability of
UiO-66 nanoparticles.
114
Figure 6.4 (a) Top-view of 3D TGA-FTIR analyses of UiO-66 and (b) its
temperature vs. weight percentage and heating time
Figure 6.5 (a) Top-view of 3D TGA-FTIR analyses of the MMM containing

20wt% UiO-66 and (b) its temperature vs. weight percentage and heating time
For MMMs, the situation is more complicated compared with pure UiO-66
nanoparticles because the 6FDA-HAB/DABA polyimide itself can go through
decarboxylation, thermal rearrangement and decomposition processes during
the heat treatment as explained in our previous study [31]. Figure 6.5(b) shows
that the MMM undergoes two stages of weight loss during the heat treatment.
The first stage of weight loss starts from 300°C to 520°C due to the
decarboxylation reaction in the DABA moieties and the thermal
rearrangement of the pristine polyimide. Figure 6.5(a) reveals that -C=O peak
(1750 to 1850 cm−1) and -C-O peak (1100 to 1200 cm−1) firstly show up at
115
around 300°C, which suggests the beginning of the decarboxylation reaction
[31, 32]. The evolved CO2 peak (2250-2400 cm−1) between 300°C and 520°C
comes from the decarboxylation reaction and the thermal rearrangement. As
temperature further increases to about 520oC, decompositions of UiO-66 and
polyimide chains begin, which results in the second stage of weight loss.
Along with these decomposition processes, -C-O, CFx, CO, CO2 and H2O are
released and their characteristic peaks are detected.
Besides the thermal stability, TGA curves can be used to determine the actual
loadings of UiO-66 nanoparticles in MMMs. As illustrated in Figure 6.6, the
residual ash at 800°C is ZrO2 because of the complete oxidation of UiO-66
under air atmosphere. Based on the remaining weight of ZrO2, the actual
loadings of UiO-66 nanoparticles in the UiO-66/PI MMM-10wt%, UiO-66/PI
MMM-20wt% UiO-66/PI MMM-30wt% are calculated to be 13.15wt%,
18.17wt% and 28.23wt%, respectively.
100
PI (0%)
90 MMM (10%)
80 MMM (20%)
70 MMM (30%)
60
50
40
30
20
10
0
0 100 200 300 400 500 600 700 800
Temperature (ºC)
Figure 6.6 TGA curves of the pristine PI membrane and MMMs
116
The solvent uptake ratio gives the information about the affinity of water and
organic species towards the membranes. The solvent uptake tests were
conducted at 60 oC and characterized by the percentages of weight gain caused
by the sorption of tested solvents. Table 6.1 presents the solvent uptake ratios
of the membranes in water, ethanol, isopropanol and n-butanol. As the UiO-66
particle loading increases, the water uptake ratio increases from 3.0% to
14.0%. This suggests that the addition of UiO-66 nanoparticles into MMMs
would provide a higher water solubility. On the other hand, all ethanol,
isopropanol and n-butanol uptake ratios decrease, implying that the
membrane’s solubility selectivity towards water increases with an increase in
UiO-66 nanoparticle loading. This phenomenon may be because the ligand of
UiO-66, terephthalic acid, contains the hydrophilic functional groups that may
favour the sorption of water rather than alcohols. As a result, the water uptake
ratio increases while the organic species uptake ratio decreases with an
increase in UiO-66 nanoparticle loading.
Table 6.1 Solvent uptake analyses for the pristine PI membrane and MMMs
UiO-66 Water Ethanol Isopropanol n-Butanol
Membrane loading uptake uptake uptake uptake
wt% ratio% ratio% ratio% ratio%
PI 0 3.0±0.8 11.9±0.2 20.0±1.2 14.6±0.3
MMM 10 4.9±0.5 9.5±0.4 15.1±1.0 14.2±0.5
MMM 20 8.4±1.2 8.7±0.4 11.3±0.2 14.0±0.5
MMM 30 14.0±1.5 7.5±0.5 8.5±0.7 13.2±0.1
Test temperature: 60 ºC
117
Positron annihilation lifetime spectroscopy (PALS) measurements were
carried out to investigate the free volume size and its distribution for the
membranes. In PALS, the o-Ps lifetime τ3 and its intensity I3 are related to the
size and concentration of the free volume, respectively [33-35]. Based on the
results of τ3 and I3, fractional free volume (FFV) of the MMMs can be
calculated from equations 2 and 3. Table 6.2 shows that τ3, I3, R and FFV all
increase with an increase in UiO-66 nanoparticle loading. Clearly, the
incorporation of the highly porous UiO-66 nanoparticles into the polyimide
matrix can create more and larger free volume, thus leads to an increase in
FFV. Remarkably, the FFV value is almost doubled when embedding 30wt%
UiO-66 nanoparticles into the polyimide matrix. Since permeability is a
product of diffusivity and solubility, and a larger FFV is beneficial for higher
diffusivity in alcohol dehydration, the addition of UiO-66 nanoparticles into
the polyimide would likely increase the overall permeability for alcohol
dehydration.
Table 6.2 PALS data for the pristine PI membrane and MMMs
UiO-
66
loading
wt%
PI 0 1.928±0.029 4.416±0.084 2.788±0.023 0.722±0.032
MMM 10 2.015±0.027 5.041±0.080 2.870±0.020 0.898±0.033
MMM 20 2.164±0.025 5.767±0.074 3.001±0.017 1.175±0.035
MMM 30 2.304±0.023 6.298±0.069 3.119±0.015 1.441±0.037
118
6.3.4 Pervaporation performance
• The effect of UiO-66 loading on dehydration performance of
ethanol, isopropanol and n-butanol
Figure 6.7, Figure 6.8 and Figure 6.9 present the ethanol, isopropanol and n-
butanol dehydration performance of the pristine polyimide membrane and
MMMs as a function of UiO-66 loading at 60 ºC, respectively. In order to
exclude the influence of membrane thickness, the normalized flux (i.e., the
product of flux and membrane thickness) is used in this study.
10000 100.0
Total normalized flux (gμm/m2h)
9000 90.0

8000 80.0
7000 70.0
permeate (wt%)
6000 60.0
5000 50.0
4000 40.0
3000 30.0
2000 Normalized Flux 20.0
1000 10.0
Water Concentration in Permeate
0 0.0
0 10 20 30
UiO-66 loading (%)
Figure 6.7 Ethanol dehydration performance of the pristine PI membrane
and MMMs at 60 ºC using ethanol/water (85/15wt%) as the feed
In terms of normalized flux, ethanol/water, isopropanol/water and n-
butanol/water systems have similar trends with an increase in UiO-66 loading.
The normalized flux increases rapidly with the increase of UiO-66 content in
119
MMMs. For example, the highest normalized flux for isopropanol dehydration
is 4724.5 gμm/m2h when the MMM contains 30wt% UiO-66. This value is
more than two times higher than that of the pristine polyimide membrane. The
improvements of normalized flux are attributed to two factors: higher
solubility and diffusivity. As shown in solvent uptake analyses in Section 3.2,
membranes with higher UiO-66 loadings display higher water uptake ratios
and higher water solubilities, which can allow more water molecules to be
absorbed by the membranes. The higher diffusivity can be proved by the
PALS analyses. Table 6.2 demonstrates that membranes with higher UiO-66
loadings exhibit higher FFV values, which can help penetrants to diffuse faster
across the membranes. As a consequence, the resultant MMMs exhibit a
higher normalized flux.
5000 100.0
4500 99.0 Water concentration in the

4000 98.0
3500 97.0
permeate (wt%)
3000 96.0
2500 95.0
2000 94.0
1500 93.0
500 Water Concentration in Permeate 91.0
0 90.0
0 10 20 30
UiO-66 loading (%)
Figure 6.8 Isopropanol dehydration performance of the pristine PI membrane

and MMMs at 60 ºC using isopropanol/water (85/15wt%) as the feed
120
5000 100.0
4500 99.0

4000 98.0
3500 97.0
permeate (wt%)
3000 96.0
2500 95.0
2000 94.0
1500 93.0
500 Water Concentration in Permeate 91.0
0 90.0
0 10 20 30
UiO-66 loading (%)
Figure 6.9 n-Butanol dehydration performance of the pristine PI membrane

and MMMs at 60 ºC using n-butanol/water (85/15wt%) as the feed
In terms of separation efficiency, the increase of UiO-66 loading may induce
two opposite effects. On one hand, an increase in UiO-66 loading would
enlarge the free volume size and the FFV value of the membranes, as shown
by the PALS data, resulting in the decrease of diffusivity selectivity which is
not favorable for alcohol and water separation. On the other hand, a higher
UiO-66 loading may result in MMMs that possess higher solubility selectivity,
as evidenced by the solvent uptake data, which is beneficial for higher
separation efficiency. These two effects compete with each other and may lead
to different results for different pairs of alcohol/water systems. For ethanol
dehydration, an increase in UiO-66 loading results in a lower water
concentration in permeate, as illustrated in Figure 6.7. However, for
isopropanol dehydration (Figure 6.8), the water concentration in the permeate
is kept at 99.9% if the MMMs contain UiO-66 less than 20wt%, but drops
slightly to 99.7% if the particle loading increases to 30wt%. For n-butanol
121
dehydration (Figure 6.9), the water concentration in the permeate stays
impressively high at 99.9% for all MMMs studied. The fundamental reasons
behind different separation behaviors for these three alcohol/water systems
will be further discussed in the following section.
• Comparison of dehydration performance for ethanol, isopropanol
and n-butanol
Figure 6.10 plots and compares the normalized fluxes and water
concentrations in permeate of the 6FDA-HAB/DABA polyimide and the
newly designed MMMs as a function of carbon number in alcohols. The
normalized flux follows the trend of ethanol/water system > isopropanol/water
system > n-butanol/water system. This trend is consistent with the reverse
order of alcohols’ molecular sizes because the alcohol with a smaller
molecular size can diffuse through the membrane easier and faster. Therefore,
the ethanol/water system shows the highest normalized flux, while the n-
butanol/water system has the lowest normalized flux. Meanwhile, the
separation efficiency in terms of water concentration in the permeate follows
the trend of n-butanol/water system≥ isopropanol/water system> ethanol/water
system. This trend obeys the order of alcohols’ molecular sizes because the
alcohol with a larger molecular size is easier to be separated. In addition, the
swelling effect induced by the ethanol/water system may lead to the loosening
of polymer chains and thus deteriorate the membrane’s ability to dehydrate
ethanol [36]. Furthermore, ethanol can form clusters with water and then pass
through the membranes together [6, 36]. This coupling effect also reduces the
122
separation efficiency of MMMs for ethanol dehydration. In summary, except
for the ethanol/water system, the newly developed MMMs are very effective
for isopropanol and n-butanol dehydration because their water concentrations
in the permeate are more than 99.7% for all MMMs studied.
a 10000
PI (0%)
9000
MMM (10%)
8000
MMM (20%)
7000 MMM (30%)
(gμm/m2h)
6000
5000
4000
3000
2000
1000
0
1 2 3 4 5
Carbon number of alcohols
b 100
98
96
94
permeate (wt%)
92
90
88
86 PI (0%)
84 MMM (10%)
MMM (20%)
82
MMM (30%)
80
1 2 3 4 5
Figure 6.10 Dehydration performance of the pristine PI membrane and

MMMs for C2–C4 alcohols at 60 ºC using alcohol/water (85/15wt%) as the
feed: (a) Total normalized flux and (b) Water concentration in the permeate vs.
carbon number
123
• The effect of feed temperature and feed composition on
dehydration performance of isopropanol
A MMM containing 20% UiO-66 and an isopropanol/water system were
chosen to study the temperature effect. Pervaporation performance at
temperatures of 40, 60 and 80°C are shown in Figure 6.11. The normalized
flux increases with an increase in operating temperature from 40 to 80°C. The
flux enhancement is due to a significant increase in fugacity at the feed side
for the isopropanol/water system as shown in Table 6.3. This finding is
consistent with previous studies [36, 37]. On the other hand, the water
concentration in permeate keeps high and stable throughout the entire
temperature testing range.
5000 100.0
Water concentration in permeate
4500 95.0
4000 90.0
3500 85.0
3000 80.0
(wt%)
2500 75.0
2000 70.0
1500 65.0
Normalized Flux
1000 60.0
Water Concentration in
500 55.0
Permeate
0 50.0
20 40 60 80 100
Feed Temperature (ºC)
Figure 6.11 Isopropanol dehydration performance of the MMM containing 20

wt% UiO-66 using isopropanol /water (85/15wt%) as the feed
124
Table 6.3 Thermodynamic properties of feed mixtures as a function of
operating temperature
Saturated Saturated
vapor vapor Fugacity Fugacity
Feed Activity Activity
pressure pressure of of
Feed temp. coefficient coefficient
of of solvent water
(℃) of solvent of water
solvent water (kPa) (kPa)
(kPa) (kPa)
Isopropanol
/Water 40 1.164 1.901 14.047 7.387 13.898 2.106
60 1.161 1.942 38.949 19.940 38.437 5.809

80 1.158 1.969 93.316 47.368 91.851 13.990
To study the effect of feed concentration, pervaporation performance of a
MMM with 20wt% UiO-66 loading was tested under three different feed
concentrations: 75/25 wt%, 85/15 wt% and 95/5 wt% IPA/water. Figure 6.12
shows the results. As the feed IPA concentration increases, the normalized
flux shows a decreasing trend. The reduction of the normalized flux is mainly
due to the decrease of driving force as the feed IPA concentration increases.
Since the vacuum condition at the permeate side is maintained, the fugacity at
the permeate side can be neglected. Therefore, the normalized flux mainly
depends on the fugacity at the feed side which is determined by concentration,
saturated vapour pressure and activity coefficient of species in the feed side.
As shown in Table 6.4, the fugacities of IPA and water at the permeate side
decrease as the IPA concentration increases. Therefore, the normalized flux
decreases. In terms of separation efficiency, water concentration in the
permeate can keep more than 99% when the feed concentration is lower than
85% but decrease to around 96% when the feed concentration increases to
95%. The drop of separation efficiency may be due to the swelling of the
MMM at this high feed concentration.
125
6000 100.0

Total ormalized flux (gμm/m2h)
95.0
5000
90.0
85.0
4000
80.0
(wt%)
3000 75.0
70.0
2000
65.0
Normalized Flux
60.0
1000
Water Concentration in Permeate 55.0
0 50.0
70 75 80 85 90 95 100
Feed Concentration(%)
Figure 6.12 Isopropanol dehydration of the MMM containing 20 wt% UiO-66

at 60 ºC
Table 6.4 Thermodynamic properties of feed mixtures as a function of

isopropanol concentration
Fugacity
Solvent Activity Activity Fugacity of
of
Feed concentration coefficient coefficient solvent
water
wt% of solvent of water (kPa)
(kPa)
Isopropanol/Water 75 1.385 1.566 40.458 7.807
85 1.161 1.942 38.437 5.809
95 1.023 2.773 37.853 2.765
6.3.5 Pervaporation benchmarking
A benchmarking of the 30/70 (wt/wt) UiO-66/6FDA-HAB/DABA polyimide
MMM with other pervaporation membranes for isopropanol and n-butanol,
ethanol dehydration is presented in Table 6.5, Table 6.6 and Table 6.7 [31, 36-
49]. The newly developed MMM containing 30wt% UiO-66 not only displays
a comparable mole-based selectivity of 2209 for isopropanol dehydration but
also possesses a much higher water permeability of 0.329 mg m-1 h-1 kPa-1
126
than most of others. For n-butanol dehydration, the 30/70 UiO-66/6FDA-
HAB/DABA polyimide MMM exhibits a high water permeability of 0.292 mg
m-1 h-1 kPa-1 and an extremely high mole-based selectivity of 14214. For
ethanol dehydration, the 30/70 UiO-66/6FDA-HAB/DABA polyimide MMM
shows a comparable water permeability but a low mole-based selectivity.
Since permeance is the ratio of permeability to the active layer thickness [56],
Table 6.5 and Table 6.6 also indicate the newly developed membranes have
comparable or superior dehydration performance of isopropanol and n-butanol
to other membranes. Therefore, the newly developed UiO-66/6FDA-
HAB/DABA MMMs have great potential for isopropanol and n-butanol

isopropanol dehydration
Water
Membrane Water
Temp. permeability Mole-based
Membrane thickness concentration in Ref.
(ºC) (mg m-1 h-1 selectivity
(μm) feed
kPa-1)
®
Matrimid 30-60 18% 100 0.490 50 [38]
®
Torlon 23 15% 60 0.011 3302 [39]
®
Ultem 24 15% 60 0.012 683 [39]
BPADA-ODA-
DABA 15-20 20% 60 0.145 9530 [40]
polyimide
Crosslinked
20 10% 60 0.835 609 [41]
Chitosan
®
Matrimid /MgO 30-60 18% 100 0.067 1513 [38]
MMM
P84/ZIF-90
19-22 15% 60 0.166 449 [37]
MMM
TR PBO 20-25 10% 80 0.299 670 [36]
C-TR-5-5 27 15% 60 0.150 4019 [31]
Polyimide/UiO- This
30 15% 60 0.329 2209
66 MMM study
127
Table 6.6 A comparison of pervaporation performance of membranes for n-
butanol dehydration
Water
Membrane Water
(μm) in feed
kPa-1)
Crosslinked
10 10% 30 0.916 87 [42]
PVA
SYMPLEX 2 10% 25 3.881 153 [43]
®
Pervap 2510 0.5-2 15% 60 0.08 17 [44]
TR PBO 20-25 10% 80 0.122 390 [36]

PBI 35-65 15% 60 0.029 2766 [45]
PBI/ZIF-8
35-65 15% 60 0.276 690 [45]
MMM
Polyimide/UiO- This
25 15% 60 0.292 14214
66 MMM study

ethanol dehydration
Water
Membrane Water
(μm) in feed
kPa-1)
Crosslinked
20 10% 60 1.136 417 [41]
Chitosan
Crosslinked
29 10% 60 0.823 456 [46]
PVA
®
P84 --- 15% 60 0.034 1874 [47]
copolyimide
®
Pervap 2201 --- 10% 60 0.022 309 [48]
TR PBO 20-25 10% 25 1.254 186 [36]
Polyimide/UiO- This
30 15% 60 0.572 34.5
66 MMM study
128
6.4 Conclusions
In this study, novel MMMs consisting of UiO-66 nanoparticles and 6FDA-
HAB/DABA polyimide have been designed for dehydration of ethanol,
isopropanol and n-butanol via pervaporation. The MMMs show superior
separation performance, signifying great potential for isopropanol and n-
butanol dehydration. The following conclusions can be also drawn:
(1) Uniform UiO-66 nanoparticles of around 100nm have been
successfully synthesized and confirmed with XRD. They disperse
evenly in the 6FDA-HAB/DABA polyimide matrix without any visible
agglomeration even at the highest 30wt% loading.
(2) An increase in UiO-66 loading results in an increase in water uptake
ratio but a decrease in alcohol uptake ratio. Thus, the MMMs’ solubility
selectivity towards water increases with the increase of UiO-66 loading
in MMMs.
(3) PALS data have confirmed that both free-volume radius R and
fractional free volume (FFV) increase with an increase in UiO-66
loading due to the high porosity nature of the UiO-66 nanoparticles.
(4) The incorporation of UiO-66 nanoparticles significantly improves
MMMs’ normalized flux and permeability because of enhanced
diffusivity and solubility. The water concentration in the permeate
decreases with the increase of UiO-66 loading for ethanol dehydration.
However, water concentration in the permeate for isopropanol
dehydration stays high at 99.9% for MMMs containing UiO-66
loadings less than 20wt%. For n-butanol dehydration, water
129
concentration in the permeate remains always high at 99.9% for all
MMMs.
(5) The normalized flux follows the trend of ethanol/water system >
isopropanol/water system > n-butanol/water system. However, the
separation efficiency in terms of water concentration in the permeate
obeys the opposite trend.
6.5 References
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130
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[7] T.C. Bowen, R.D. Noble, J.L. Falconer, Fundamentals and applications of
pervaporation through zeolite membranes, J. Membr. Sci. 245 (2004) 1-33.
[8] Y.K. Ong, G.M. Shi, N.L. Le, Y.P. Tang, J. Zuo, S.P. Nunes, T.-S. Chung,
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[12] T.S. Chung, L.Y. Jiang, Y. Li, S. Kulprathipanja, Mixed matrix
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[13] R. Mahajan, W.J. Koros, Factors Controlling Successful Formation of
Mixed-Matrix Gas Separation Materials, Ind. Eng. Chem. Res. 39 (2000)
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zeolites?, Curr. Opin. Chem. Eng. 1 (2011) 77-83.
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136
CHAPTER 7: FUNCTIONALIZED UiO-66-TYPE MOFS
FOR 6FDA-POLYIMIDE BASED MIXED
MATRIX MEMBRANES FOR
DEHYDRATION OF C1-C3 ALCOHOLS VIA
PERVAPORATION
7.1 Introduction
The development of renewable and sustainable energy has received worldwide
attention due to the highly fluctuated oil price and global warming.
Bioalcohols are one of promising renewable and sustainable energy sources to
substitute fossil fuels [1]. For bioalcohol dehydration, pervaporation is a
promising technology due to its advantages of high energy efficiency,
environmental benignity, mild operation conditions and small footprint [2-5].
More importantly, pervaporation can be used to separate azeotropic mixtures
because it is not restricted by the thermodynamic vapor-liquid equilibrium [6].
Membrane is the heart of pervaporation processes. Substantial works have
been done to develop pervaporation membranes [7-10]. Polymeric
membranes are widely used for pervaporation because they have reasonable
separation performance. In addition, they can be fabricated easily and scaled
up cost-effectively [6, 11-13]. However, there is a trade-off relationship
between permeability and selectivity for polymeric membranes. They are also
vulnerable to the solvent-induced swelling issue that may deteriorate their
137
separation performance. Compared with polymeric membranes, inorganic
membranes don’t suffer from the swelling problem because of their superior
chemical, thermal and mechanical stability [14]. Nonetheless, their wide
applications are limited by the fragility and high fabrication cost. In order to
integrate the advantages of both polymeric and inorganic membranes, mixed
matrix membranes (MMMs) consisting of inorganic fillers and polymeric
matrices were invented by Kulprathipanja et al. in 1988 [15]. The inorganic
particles with an inherently high permeability and selectivity can help increase
the separation performance, while the polymeric matrices can minimize the
fragility issue and reduce the overall fabrication cost for MMMs [16,17].
Among numerous inorganic fillers [11, 18-20], metal organic frameworks
(MOFs) have been regarded as a promising material due to their unique
characteristics of ultrahigh porosities, tuneable chemical functionalities,
controllable structures, good affinity with polymers and high adsorption
capacity [18-20]. Among them, UiO-66 MOFs have been extensively studied
due to their noticeably high thermal, chemical and mechanical stability [21].
By altering ligands with various functional groups, one can easily manipulate
the pore size and chemical properties of UiO-66-Type MOFs [22,23]. UiO-66
functionalized with amine groups, UiO-66-NH2 MOFs, have been widely
applied in a variety of applications [24-28]. For example, Anjum et al.
reported that both selectivity and permeability were significantly improved by
incorporating UiO-66-NH2 into Matrimid because the amine groups inside
MOF pores facilitated the CO2 transport [24]. Nik et al. found that the
presence of amine-functional groups in UiO-66-NH2 MOFs increased both the
138
ideal selectivity and CO2 permeability for CO2/CH4 separation [25]. The study
of Peterson et al. suggested that UiO-66-NH2 MOFs could effectively remove
nitrogen dioxide from air with the aid of amine groups [26]. In addition, UiO-
66-NH2 based membranes also show great potential for water treatment and
dye removal [27-29].
Although UiO-66-NH2 based membranes have a wide range of applications as
aforementioned, there are limited studies for pervaporation [30, 31]. However,
none of them is related to alcohol dehydration. Therefore, the first objective of
this work is to explore the feasibility of applying UiO-66-NH2 based MMMs
for pervaporation. 6FDA-HAB/DABA polyimide is chosen as the polymer in
the MMMs because the original polyimide membrane has high separation
factor [32]. The incorporation of UiO-66-NH2 nanoparticles aims to improve
the overall flux due to the high porosity and the positive influence of
hydrophilic amino-functional groups on water transport. The other objectives
of this work are to (1) explore the effect of functional groups of UiO-66-Type
MOF on alcohol dehydration and (2) investigate and compare their separation
performances in three alcohol dehydration systems including isopropanol
/water, ethanol/water and methanol /water as a function of MOF particle
loading.
To meet the objectives, uniform UiO-66-NH2 nanoparticles would be firstly
synthesized for the fabrication of MMMs. To explain the effects of functional
groups on dehydration performance, fluorine functionalized UiO-66-Type
MOFs, UiO-66-F4 nanoparticles would be synthesized and incorporated into
139
MMMs for comparison. In addition, solvent uptake and positron annihilation
lifetime spectroscopy (PALS) analyses would be carried out to reveal the
fundamental science and mechanisms for the performance enhancement. 200-
h stability tests would be carried out to study their long-term performance.
This study suggests UiO-66-NH2 based MMMs are very promising for
dehydration of alcohols.
7.2 Experimental
The 6FDA-HAB/DABA polyimide, UiO-66-NH2 and UiO-66-F4 were
synthesized as the methods described in Chapter 3. The crystallographic
structure of the MOFs particles was explored by XRD. Cross-sectional
morphologies of MMMs were observed by FESEM. EDX was conducted to
study the distribution of particles by zirconium element. Thermal stabilities of
the MOFs particles and MMMs were examined by TGA. Solvent uptake and
positron PALS analyses as well as 200-hour stability tests were carried out to
reveal the fundamental science and underline mechanisms for the performance
enhancement.
7.3.1 Characterizations of particles and mixed matrix membranes
XRD characterizations were carried to study the crystalline structure of the
synthesized particles. Figure 7.1 shows the XRD spectra of UiO-66-NH2 and
140
UiO-66-F4. All the characteristic diffraction peaks agree quite well with the
simulated result in the database [33], indicating that both UiO-66-NH2 and
UiO-66-F4 have a highly crystalline structure and an isostructural framework
similar to UiO-66.
40000
UiO-66-Simulated
35000 UiO-66-NH2
30000 UiO-66-F4
Intensity (a.u.)
25000
20000
15000
10000
5000
0
5 15 25 35 45
2 theta (º)
Figure 7.1 XRD spectra of UiO-66-NH2 and UiO-66-F4
Figure 7.2 shows the morphology of the synthesized UiO-66-NH2 and UiO-66-
F4 observed by FESEM. The synthesized UiO-66-NH2 particles are quite
uniform with a particle size of 80-90nm while the size of UiO-66-F4 particles
is around 90-130nm. Figure 7.3 shows the cross-sectional morphologies of the
pristine polyimide membrane and MMMs with various UiO-66-NH2 and UiO-
66-F4 loadings. The images reveal that UiO-66-NH2 and UiO-66-F4
nanoparticles can be dispersed homogenously in the polyimide matrix. The
nanoparticles don’t show any obvious agglomeration even at the highest
loading (30 wt%). These observations indicate good compatibility between
polyimide matrix and the synthesized nanoparticles. Figure 7.4 and Figure 7.5
141
show the EDX mapping of Zr across the MMMs and further confirms the
uniform distributions of UiO-66-NH2 and UiO-66-F4 in the MMMs since Zr
element only exists in the nanoparticles.
Figure 7.2 FESEM images of (a) UiO-66-NH2 and (b) UiO-66-F4

nanoparticles
Figure 7.3 FESEM images cross-sectional morphologies of (a) the pristine PI

membrane (b) MMM containing 10wt% UiO-66-F4 and MMMs containing (c)
10wt%, (d) 20wt%, (e) 30wt% UiO-66-NH2
142
MMMs containing 30wt% UiO-66-NH2
MMMs containing 10wt% UiO-66-F4
TGA was carried out to study the thermal stability of the UiO-66-NH2
nanoparticles, pristine PI membrane and MMMs. Figure 7.6 and Figure 7.7
depict the TGA curves of the UiO-66-NH2, UiO-66-F4 nanoparticles, pristine
PI membrane and MMMs under air atmosphere. The TGA curves of UiO-66-
NH2 and UiO-66-F4 agree well with literatures [22, 34]. The weight loss from
200 °C is attributed to the removal of the residual DMF solvent in the particles.
After that, the nanoparticles start to decompose. The detailed explanation of
the thermal behaviour of the pristine polyimide can be found in our previous
study [32]. The weight loss at 250–500 °C is because of decarboxylation
crosslinking and thermal rearrangement reactions. The weight loss after
500 °C is owing to the decomposition of polyimide chains. For MMMs, the
143
weight loss is mainly because of (1) the decomposition of UiO-66-type
nanoparticles, (2) decarboxylation crosslinking of the pristine polyimide, (3)
thermal rearrangement of the pristine polyimide and (4) degradation of the
pristine polyimide.
100
UiO-66-NH2
90 PI
MMM-10%
80
MMM-20%
70 MMM-30%
60
50
40
30
20
10
0
0 200 400 600 800
Temperature (℃)
Figure 7.6 TGA curves of UiO-66-NH2, pristine PI membrane and UiO-66-

NH2 based MMMs under air atmosphere
In addition, the TGA results can be applied to calculate the actual MOFs
loadings in MMMs. Assuming all nanoparticles have been completely
oxidized at 800°C under air atmosphere and the final ash is ZrO2. the actual
MOFs loading in MMMs can be determined based on the amount of ZrO2.
Therefore, the actual loadings of UiO-66-NH2 nanoparticles in MMM-NH2-
10wt%, MMM-NH2-20wt% and MMM-NH2-30wt% are calculated to be
8.8wt%, 19.7wt% and 27.5wt%, respectively while the actual loading of UiO-
66- F4 nanoparticles in MMM-F4-10wt% is 12.2wt%.
144
100
UiO-66-F4
90
PI
80
70 MMM-F4-10%
60
50
40
30
20
10
0
0 200 400 600 800
Temperature (℃)
Figure 7.7 TGA curves of UiO-66-F4, pristine PI membrane and UiO-66-F4

based MMMs under air atmosphere.
To understand the interaction and affinity of water and different organic
solvents towards the membranes, solvent uptake tests were carried out at 60oC,
the same temperature used in the pervaporation tests. Table 7.1 shows the
effects of UiO-66-NH2 loading on solvent uptake ratios of its MMMs in water,
methanol, ethanol and isopropanol, while Table 7.2 tabulates the solvent
uptake ratios of MMMs containing different type MOFs. With an increase in
UiO-66-NH2 loading, the water uptake ratio increases but the uptake ratios of
methanol, ethanol and isopropanol decrease. This means that the adding of
UiO-66-NH2 nanoparticles into MMMs results in a higher water solubility but
a lower alcohol solubility. As a result, the solubility selectivity of UiO-66-NH2
based MMMs towards water increases as the UiO-66-NH2 loading increases.
145
Clearly, the hydrophilic amine groups in UiO-66-NH2 nanoparticles provide
more water sorption sites and work as water selective fillers.
Table 7.1 Solvent uptake ratios of the pristine PI membrane and UiO-66-NH2
based MMMs
UiO-66- Water Methanol Ethanol
Isopropanol
NH2 uptake uptake uptake
Membrane uptake ratio
loading ratio ratio ratio
%
wt % % % %
PI 0 3.3±0.3 9.2±0.3 11.5±0.7 18.4±0.6
MMM 10 5.6±0.5 8.0±0.6 8.3±0.3 10.4±0.6
MMM 20 9.4±0.5 6.1±0.9 7.1±0.3 9.8±0.8
MMM 30 16.9±0.7 5.0±0.2 6.5±0.6 8.2±0.8
Table 7.2 Comparison of solvent uptake ratio among different UiO-66 MOF
based MMMs
Particle Water Ethanol
Membrane loading uptake ratio uptake ratio
wt % % %
MMM-UiO-66-NH2 10 5.6±0.5 8.3±0.3
MMM-UiO-66-F4 10 4.4±0.2 12.1±1.0
The effect of hydrophilic amine groups in UiO-66-NH2 nanoparticles on water
uptake ratio can be further confirmed by comparing the solvent uptake ratios
of MMMs containing MOFs with different functional groups at the same 10
wt% loading. As shown in Table 7.2, the water uptake ratio follows the order
of UiO-66-NH2 > UiO-66-F4, which is mainly due to the different
hydrophilicities of the UiO-66-type particles resulted from the hydrophilic
amine and hydrophobic fluorine functional groups. While the ethanol uptake
ratio follows the opposite order. These orders indicate that UiO-66-NH2 based
MMMs should have greater water solubility and higher solubility selectivity
towards water.
146
Positron annihilation lifetime spectroscopy (PALS) was employed to
investigate the free volume of the MMMs. The free volume size and its
concentration were characterized by the o-Ps lifetime τ3 and its intensity I3,
respectively [35-37]. Based on τ3 and I3, fractional free volume (FFV) can also
calculated. Table 7.3 summarizes the PALS data for the pristine polyimide
membrane and UiO-66-NH2 based MMMs. τ3, I3, R and FFV all increase with
an increase in UiO-66-NH2 loading because of the highly porous structure of
UiO-66-NH2 nanoparticles.
Table 7.3 PALS data of the pristine PI membrane and UiO-66-NH2 based
MMMs
UiO-
66-NH2
loading
wt%
PI 0 1.650±0.038 3.020±0.100 2.510±0.036 0.360±0.028
MMM 10 1.769±0.034 3.449±0.089 2.633±0.030 0.475±0.028
MMM 20 1.773±0.029 4.187±0.092 2.637±0.025 0.579±0.029
MMM 30 1.913±0.029 4.439±0.084 2.774±0.023 0.715±0.032
For comparison, the PALS data of UiO-66-F4 based MMMs at 10wt% particle
loading were also measured. Table 7.4 shows that at the same particle loading,
UiO-66-HN2 based MMMs have a larger free volume size (R) and a higher
FFV than UiO-66-F4 based MMMs because UiO-66-HN2 has a larger pore
volume (0.763cm3g−1) than that of UiO-66-F4 (0.616cm3g−1) [22].
147
Table 7.4 Comparison of PALS data between UiO-66-NH2 and UiO-66-F4
based MMMs
Particle
Membrane loading τ3 (ns) I3 (%) R (Å) FFV (%)
wt%
MMM-
UiO-66- 10 1.769±0.034 3.449±0.089 2.633±0.030 0.475±0.028
NH2
MMM-
10 1.660±0.030 3.639±0.105 2.520±0.029 0.420±0.028
UiO-66-F4
7.3.4 Pervaporation performance
• The effect of functional groups of MOFs particles on ethanol
dehydration
Table 7.5 compares the ethanol dehydration performance of UiO-66-NH2 and
UiO-66-F4 based MMMs using an ethanol/water mixture of 85/15 wt% as the
feed. All MMMs have a particle loading of 10wt%. To exclude the influence
of variation in membrane thickness, normalized flux is employed in this work,
which is defined as the product of membrane thickness and flux. It is found
that at the same particle loading, UiO-66-NH2 based MMMs have both higher
normalized flux and higher separation factor than that of UiO-66-F4 based
MMMs. Clearly, the functional groups of MOF particles play a determining
role on the dehydration performance of these MMMs. Not only the high FFV
of the UiO-66-NH2 MMMs facilitates the water transport, but also the
hydrophilic amino-functional groups on the MOF surface or inside the MOF
pores provide high water solubility and help water diffuse across the
membranes. Since the UiO-66-NH2 based MMMs have both the higher
148
normalized flux and separation factor, the UiO-66-NH2 based MMMs are the
focus of the following studies.
Table 7.5 Ethanol dehydration performance of UiO-66-NH2 and UiO-66-F4

based MMMs
Particle Normalized Water
Separation
Membrane loading flux Concentration in
factor
wt% (gμm/m2h） permeate （wt%）
MMM-UiO-
10 3560.4 96.2 142
66-NH2
MMM-UiO-
10 3057.1 93.7 84
66-F4
• The effect of UiO-66-NH2 loading on dehydration performance of
alcohols
Because UiO-66-NH2 based MMMs have better separation performance, their
methanol, ethanol and isopropanol dehydration performance as a function of
UiO-66-NH2 loading at 60 ºC were studied and shown in Figure 7.8, Figure
7.9 and Figure 7.10.
In terms of normalized flux, all methanol/water, ethanol/water and
isopropanol/water systems have similar trends. The normalized flux increases
as the UiO-66-NH2 loading increases. The flux enhancement can be attributed
to two factors: (1) higher water solubility due to the presence of hydrophilic
hydrophilic amino-functional groups and (2) higher diffusivity due to the
existence of higher FFV values. As a result, the MMMs with a 30wt% UiO-
66-NH2 loading have the highest normalized flux of 8878 gμm/m2h for ethanol
149
dehydration which is more than three times of the normalized flux of the
pristine polyimide membrane.
12000 100

90
10000
80
70
8000
60
(wt%)
6000 50
40
4000
30
Normalized Flux 20
2000
10
0 0
0 10 20 30
UiO-66-NH2 loading (%)
Figure 7.8 Methanol dehydration performance of the pristine PI membrane

and MMMs at 60 ºC with feed composition of methanol/water (85/15wt%)
10000 100
9000 90
8000 80
7000 70
6000 60
(wt%)
5000 50
4000 40
3000 30
2000 Normalized Flux 20
1000 Water Concentration in Permeate 10
0 0
0 10 20 30

MMMs at 60 ºC with feed composition of ethanol/water (85/15wt%)
150
4500 100

4000 90
3500 80
70
3000
60
(wt%)
2500
50
2000
40
1500
30
1000 Normalized Flux 20
500 10
0 0
0 10 20 30
Figure 7.10 Isopropanol dehydration performance of the pristine PI membrane

and MMMs at 60 ºC with feed composition of isopropanol/water (85/15wt%)
In terms of separation efficiency, the water concentration in permeate firstly
increases when the UiO-66-NH2 loading is increased from 0 to 10wt% for
methanol/water and ethanol/water systems, but it decreases if the MOF
loading is further increased to 30wt%. As shown by solvent uptake and PALS
analyses, with an increase in UiO-66-NH2 loading, solubility selectivity
increases while diffusivity selectivity decreases. These two contradictory
effects lead to different results at various particle loadings. At a lower particle
loading range of 0–10 wt%, the FFV increment degree is relatively small and
the decrease of diffusivity selectivity is not severe. Therefore, the
enhancement of solubility selectivity is the main reason for the increase of
water concentration in permeate. However, when the particle loading is further
increased, the FFV value becomes much higher especially at the highest
particle loading of 30 wt% thus the decrease of diffusivity selectivity becomes
the dominant factor for the decrease of water concentration in permeate at
151
higher particle loadings. In addition, the up-and-down convex trend between
water concentration and UiO-66-NH2 loading is much severer for the
methanol/water system than the ethanol/water system because methanol has a
much small kinetic diameter than ethanol (i.e., 0.38 vs. 0.43 nm).
Nevertheless, the water concentrations in permeate of MMMs-10% and
MMMs-20wt% are higher than that of the pristine polyimide membrane for
methanol/water and ethanol/water systems.
The isopropanol/water system shows the best separation performance and the
water concentration in permeate can keep impressively high at 99.9% for all
the membranes studied. In addition, there is no an up-and-down convex trend
between water concentration and UiO-66-NH2 loading because IPA has a large
kinetic diameter and molecular size.
• Comparison of dehydration performance for methanol, ethanol
and isopropanol
Figure 7.11 replots the normalized flux and water concentration in permeate as
a function of carbon number in alcohols. The normalized flux follows the
trend of methanol/water system > ethanol/water system > isopropanol/water
system. This order is consistent with the reverse order of alcohol molecular
sizes because a small alcohol size tends to diffuse faster across the membrane.
While the water concentration in permeate follows the order of alcohol
molecular sizes: isopropanol/water system > ethanol/water system >
methanol/water system. This is because (1) an alcohol with a larger molecular
152
size can be easily intercepted and separated by the membrane and (2) an
alcohol with a higher linearity can pass through the membrane network more
easily [38, 39]. Since isopropanol has the largest molecular size and lowest
linearity among these three alcohols, the isopropanol/water system shows the
highest separation factor.
a
12000
PI (0%)
MMM (10%)
10000
MMM (20%)
8000 MMM (30%)
(gμm/m2h)
6000
4000
2000
0
0 1 2 3 4
b
100
Water concentration in
80
permeate (wt%)
60
40 PI (0%)
MMM (10%)
20 MMM (20%)
MMM (30%)
0
0 1 2 3 4
Figure 7.11 Dehydration performance of the pristine PI membrane and UiO-

66-NH2 based MMMs for C1–C3 alcohols at 60 ºC with feed composition of
alcohol /water (85/15wt%): (a) Normalized flux and (b) Water concentration
in the permeate vs. carbon number
153
7.3.5 Long stability of UiO-66-NH2 based MMMs
Besides separation performance, long-term stability is another significant
factor to evaluate a membrane. Therefore, a 200-h test was carried out for IPA
dehydration at 60oC using MMMs consisting of 10wt% UiO-66-NH2. Figure
7.12 presents the results. The MMMs display very stable performance without
obvious changes of flux and separation factor in the entire testing duration.
The good stability of UiO-66-NH2 based MMMs is mainly because the amine
groups in UiO-66-NH2 can improve the compatibility between the MOF
particles and the 6FDA-HAB/DABA polyimide through intermolecular
bonding with imide groups, thus effectively reduce membrane swelling [24].
5000
Water concentration in the permeate

4500 100
4000
3500 80
3000
(wt%)
60
2500
2000
40
1500
1000 20
500
0 0
0 50 100 150 200
Test Duration (h)
Figure 7.12 Long-term stability performance of 10wt% UiO-66-NH2 MMMs

for isopropanol dehydration at 60 ºC with feed composition of
isopropanol/water (85/15wt%)
154
7.3.6 Performance benchmarking
Table 7.6, Table 7.7 and Table 7.8 compare the dehydration performance of
methanol, ethanol and isopropanol of the newly developed UiO-66-NH2 based
MMMs with different pervaporation membranes in literatures [39-51]. Up to
now, methanol dehydration via pervaporation has not been widely used due to
the lack of suitable materials with both affordable price and good anti-swelling
properties [39]. However, compared with other polymeric membranes, Table
7.6 shows that the MMM comprising 10 wt% UiO-66-NH2 has better
methanol dehydration performance than most of other membranes with the
most balanced performance of normalized flux and separation factor. For
ethanol dehydration, the MMMs have comparable performance with the
literature data. For isopropanol dehydration, the MMMs with 30wt% UiO-66-
NH2 not only show a comparable water permeability of 0.295 mg m-1 h-1 kPa-1
but also have an outstanding mole-based selectivity of 66250, which is much
higher than most of others. Overall, the newly developed UiO-66-NH2 based
MMMs possess great potential for alcohol dehydration via pervaporation.
155
Table 7.6 A comparison of pervaporation performance for methanol
dehydration
Water Mole-
Membrane Water
Temp. permeability based
Membrane thickness concentration in Ref.
(μm) feed
kPa-1)
5%-sPPSU 16 15% 60 0.033 33.8 [39]

2.5%-sPPSU 16 15% 60 0.030 32.1 [39]
Agarose 14-20 14% 30 0.925-1.321 8.3 [47]
Polyamidesulfon-
30 10% 20 0.268-0.415 9.2-99.9 [48]
amide
Polyimide/UiO-66- This
NH MMM-10% 34 15% 60 0.413 43.0
2 study
NH MMM-20% 40 15% 60 0.455 28.8
2 study
NH MMM-30% 22 15% 60 0.599 19.8
2 study

ethanol dehydration
Water
Temp. permeability
Membrane thickness concentration based Ref.
(ºC) (mg m-1 h-1
kPa-1)
Crosslinked
20 10% 60 1.136 417 [44]
Chitosan
Crosslinked PVA 29 10% 60 0.823 456 [49]
®
P84 copolyimide --- 15% 60 0.034 1874 [50]
®
Pervap 2201 --- 10% 60 0.022 309 [51]
TR PBO 20-25 10% 25 1.254 186 [41]

NH2 MMM-10% 33 15% 60 0.256 202.5
study
NH2 MMM-20% 44 15% 60 0.345 124.5
study
NH2 MMM-30% 21 15% 60 0.602 80.3
study
156
isopropanol dehydration
Water
Temp. permeability
Membrane thickness concentration based Ref.
(ºC) (mg m-1 h-1
kPa-1)
®
Matrimid 30-60 18% 100 0.490 50 [40]
®
Torlon 23 15% 60 0.011 3302 [42]
®
Ultem 24 15% 60 0.012 683 [42]
BPADA-ODA-
15-20 20% 60 0.145 9530 [43]
DABA polyimide
Crosslinked
20 10% 60 0.835 609 [44]
Chitosan
P84/ZIF-90 MMM 19-22 15% 60 0.166 449 [46]
TR PBO 20-25 10% 80 0.299 670 [41]
C-TR-5-5 27 15% 60 0.150 4019 [32]
NH2 MMM-10% 34 15% 60 0.205 66250
study
NH2 MMM-10% 47 15% 60 0.265 66250
study
NH2 MMM-10% 19 15% 60 0.295 66250
study
7.4 Conclusions
In this study, making mixed matrix membrane (MMMs) containing porous
UiO-66-NH2 particles and 6FDA-HAB/DABA polyimide was demonstrated
as an effective method of improving membrane’s normalized flux and
separation factor simultaneously. The UiO-66-NH2 based MMMs have
excellent separation performance, showing great potential for alcohol
dehydration. The following conclusions can be drawn:
(1) UiO-66-NH2 nanoparticles with particle size of 80-90nm and UiO-66-
F4 nanoparticles with particle size of 90-130nm have been successfully
synthesized. The nanoparticles can disperse uniformly in the polyimide
157
matrix without visible agglomerations even for the highest loading of
30wt%.
(2) The hydrophilic amine groups in UiO-66-NH2 nanoparticles can
provide more water sorption sites and work as water selective fillers. A
higher UiO-66-NH2 loading results in higher water solubility, lower
alcohol solubility, thus higher solubility selectivity towards water. At
the same particle loading, UiO-66-NH2 based MMMs have higher
water solubility, lower ethanol solubility and higher solubility
selectivity towards water than UiO-66-F4 based MMMs.
(3) FFV increases with an increase in UiO-66-NH2 loading increases due
to the highly porous structure of UiO-66-NH2. At the same particle
loading of 10wt%, UiO-66-HN2 based MMMs have larger free volume
size (R) and higher FFV than that of UiO-66-F4 based MMMs.
(4) UiO-66-NH2 based MMMs have better separation performance than
UiO-66-F4 based MMMs. Incorporation of UiO-66-NH2 nanoparticles
can greatly improve both the normalized flux and separation factor of
MMMs simultaneously if the particle loading is within the range of 0–
20 wt%.
(5) The normalized flux shows the trend of methanol/water system >
ethanol/water system > isopropanol/water system and water
concentration in permeate follows the reverse trend.
(6) The UiO-66-NH2 based MMMs have stable isopropanol dehydration
performance throughout the uninterrupted 200-h testing due to the good
compatibility of UiO-66-NH2 particle and the polyimide.
158
7.5 References
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(MHT) Approach for the Facile Synthesis of UiO-66-Type MOFs, Inorg.
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tagged UiO-66 Zr-MOFs, Chem. Mater. 22 (2010) 6632-6640.
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Vankelecom, Modulated UiO-66-based mixed-matrix membranes for CO2
separation, ACS Appl. Mater. Inter. 7 (2015) 25193-25201.
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Extraordinary NO2 Removal by the Metal-Organic Framework UiO-66-NH2,
Angew. Chem. Int. Ed. 55 (2016) 6235–6238.
[27] N. Yin, K. Wang, L. Wang, Z. Li, Amino-functionalized MOFs
combining ceramic membrane ultrafiltration for Pb (II) removal, Chem. Eng. J.
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[28] B.J. Yao, W.L. Jiang, Y. Dong, Z.X. Liu, Y.B. Dong, Post‐Synthetic
polymerization of UiO-66-NH2 nanoparticles and polyurethane oligomer
toward stand-alone membranes for dye removal and separation, Chem. Eur.J.
22 (2016) 10565-10571.
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dehydration of acetic acid using NH2-UiO-66/PEI mixed matrix membranes,
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Walton, Stability and degradation mechanisms of metal–organic frameworks
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415-416 (2012) 686-695.
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with 4,4 ′ -(hexafluoroisopropylidene) diphthalic anhydride (6FDA)-based
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functional UiO-66-type MOFs embedded in 6FDA-HAB/DABA Polyimide for
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Press.
165
CHAPTER 8: CONCLUSIONS AND ECOMMENDATIONS
8.1 Conclusions
Understanding the limitations and challenges of current pervaporation
technology, design and development of novel polymeric and mixed matrix
membranes with high separation performance and good stability have been
conducted in this PhD study. Polyarylether (PESU, PPSU, T-PESU and H-
PESU), polyimide and crosslinked thermally rearranged poly(benzoxazole-co-
imide) were explored as membrane materials. Three UiO-66-type MOFs
(UiO-66, UiO-66-NH2 and UiO-66-F4) were synthesized as fillers of mixed
matrix membranes. Different alcohol/water systems including methanol/water,
ethanol/water, isopropanol/water, and n-butanol/water were investigated.
Fundamental chemical and thermal properties, mass transport behaviour,
dehydration performance and long-term stability were systematically studied.
The following conclusions can be drawn from the aforementioned study.
8.1.1 Polyarylether membranes for dehydration of ethanol and methanol
via pervaporation
In this work, pervaporation membranes made from four kinds of polyarylether
(PAE) polymers including polyethersulfone (PESU), polyphenylsulfone
(PPSU), polytrimethylphenylethersulfone (T-PESU) and hydrophilic PESU-
co-Pluronic (H-PESU) were developed for dehydration of ethanol and
methanol. These PAE membranes exhibited excellent separation performance
166
for both alcohol dehydration cases. Fundamental characteristics of pore
structure, free volume, d-spacing, water contact angle, water and ethanol
uptakes were investigated and correlated with their dehydration performance.
PALS measurements show that swelling gives rise to a larger free volume
radius and a bigger FFV. Moreover, the adjacent small cavities in the
membranes at the dry state may coalesce to form large cavities at the wet state.
The H-PESU membrane shows the best ethanol dehydration performance due
to its synergetic combination of the strengths from both rigid hydrophobic
PESU and flexible hydrophilic Pluronic moieties. It has the highest water
permeability of 0.322 mg m-1 h-1 kPa-1 which is 2-6 times higher than other
three membranes because the hydrophilic Pluronic moiety may form special
water transport channels. It also has a comparable mole-based selectivity of
685 due to the rigid hydrophobic PESU moiety that prevents the membrane
from uncontrolled swelling. Long-term tests evidence the operating stability of
both H-PESU and PESU membranes. In addition, the methanol dehydration
performance of these membranes is superior to the other reported polymeric
membranes. The water in the permeate can be concentrated to 86.8%. These
promising preliminary results suggest that these polyarylether (PAE)
membranes have great potential for ethanol and methanol dehydration.
167
8.1.2 Polyimide and Crosslinked Thermally Rearranged Poly(benzoxazole-
co-imide) Membranes for Isopropanol Dehydration via
Pervaporation
In this study, successful synthesis of PI precursors by the polycondensation of
three monomers; namely, 4,4’-(hexafluoroisopropylidene) diphthalic
anhydride (6FDA), 3,3’-dihydroxybenzidine diamine (HAB) and 3,5-
diaminobenzoic acid (DABA) was demonstrated. Novel crosslinked thermally
rearranged polybenzoxazole (C-TR-PBO) membranes, which show impressive
results for isopropanol dehydration, have been obtained via in-situ thermal
conversion of hydroxyl-containing polyimide precursors. Due to the
incorporation of the carboxylic-group containing diamine DABA into an
ortho-hydroxypolyimide precursor, the thermal induced crosslinking reaction
can be achieved together with the thermal rearrangement process.
Consequently, a synergistic effect of high permeability and high selectivity
can be realized in one step. The resultant C-TR-PBO membrane exhibits an
unambiguous enhancement in permeation flux compared to their PI precursors
due to the higher fractional free volume of C-TR-PBO membrane achieved in
thermal rearrangement and crosslinking processes. As the DABA to HAB
ratio increases, both normalized flux and separation factor of C-TR
membranes increase simultaneously. C-TR-5-5 exhibits the best pervaporation
performance with a comparable water permeability of 0.15 mgm-1h-1kPa-1 and
an impressively high mole-based selectivity of 4019. Moreover, the newly
developed C-TR-PBO membrane displays stable isopropanol dehydration
performance at 60 C throughout the continuous 200 hours. The promising
168
preliminary results achieved in this study may offer useful insights for the
selection of membrane materials for pervaporation and new methods to
molecularly design next-generation pervaporation membranes.
8.1.3 UiO-66/Polyimide Mixed Matrix Membranes for Ethanol,
Isopropanol and n-Butanol Dehydration via Pervaporation
In this study, novel MMMs consisting of UiO-66 nanoparticles and 6FDA-
HAB/DABA polyimide have been developed for dehydration of ethanol,
isopropanol and n-butanol via pervaporation. Uniform UiO-66 nanoparticles
with a particle size of around 100nm were successfully synthesized and they
can be evenly dispersed in the 6FDA-HAB/DABA polyimide matrix without
visible agglomeration even at the highest 30wt% loading. Adding UiO-66 into
the 6FDA-HAB/DABA polyimide not only significantly enhances both free-
volume radius and fractional free volume but also water solubility and
solubility selectivity towards water of the MMMs. Therefore, the
incorporation of UiO-66 remarkably improves the normalized flux of MMMs
for the dehydration of ethanol/water, isopropanol/water and n-butanol/water
systems. The MMMs show excellent separation performance for the
dehydration of isopropanol and n-butanol. At the highest UiO-66 loading of
30wt%, the MMMs have the water permeability of 0.329 and 0.292 mg m-1 h-1
kPa-1 and mole-based selectivity of 2209 and 14214 respectively for
isopropanol/water and n-butanol/water systems, outperforming most literature
data. These experimental results strongly suggest the newly developed UiO-
169
66/polyimide MMMs have great potential for isopropanol and n-butanol
Moreover, dehydration performances for different alcohol/water systems were
compared. Normalized flux of the MMMs for different alcohol/water systems
follows the trend of ethanol/water system > isopropanol/water system > n-
butanol/water system. However, the separation efficiency in terms of water
concentration in the permeate obeys the opposite trend. In addition, the study
of feed temperature effects shows that with the increase of feed temperature,
normalized flux increases and water concentration in permeate keeps high and
stable at 99.9%. The study of feed composition effects reveals that with the
increase of feed concentration, both normalized flux and separation factor
show decreasing trends.
8.1.4 Functionalized UiO-66-Type MOFs for 6FDA-Polyimide based
Mixed Matrix Membranes for Dehydration of C1-C3 Alcohols via
Pervaporation
This work further developed mixed matrix membranes consisting of two
different functionalized UiO-66-type MOFs (UiO-66-NH2 and UiO-66-F4) and
6FDA-HAB/DABA polyimide for alcohol dehydration via pervaporation.
UiO-66-NH2 with particle size of 80-90nm and UiO-66-F4 with particle size
of 90-130nm were successfully synthesized. The nanoparticles can disperse
uniformly in the polyimide matrix without visible agglomerations even for the
highest loading of 30wt%. Three different alcohols: methanol, ethanol,
170
isopropanol dehydration performances were studied and compared.
Normalized flux shows the trend of methanol/water system > ethanol/water
system > isopropanol/water system and water concentration in permeate
follows the reverse trend. The effects of functional groups of the MOFs
particles and the effects of particle loading on the alcohol separation
performance were systematically investigated. Results show the UiO-66-NH2
based MMMs have better separation performance than UiO-66-F4 based
MMMs due to the positive influence of hydrophilic amino-functional groups
on water transport. Incorporation of UiO-66-NH2 nanoparticles can greatly
improve normalized flux of the MMMs due to the enhanced water solubility
and diffusivity, and at the same time enhance separation factor within the
particle loading range of 0-20wt% due to the higher selectivity towards water.
The UiO-66-NH2 based MMMs have stable isopropanol dehydration
performance throughout the uninterrupted 200-hour testing due to the good
compatibility of UiO-66-NH2 particle and polyimide resulting from the
intermolecular bonding among their amine and imide groups. The UiO-66-
NH2 based MMMs show excellent alcohol dehydration performance. The
encouraging results suggest a promising future of the UiO-66-NH2 based
MMMs for alcohol dehydration via pervaporation.
8.2 Recommendations
In this thesis, various membranes including polymeric and mixed matrix
membranes have been developed. The performances for ethanol dehydration
of these membranes developed are summarized and compared in Table 8.1.
171
Table 8.1 A comparison of pervaporation performance of dense membranes
for ethanol dehydration
Water
Membrane Water Water Mole-based
Temp. permeability
Membrane thickness concentration concentration selectivity
(℃) (mg m-1 h-1
(μm) in feed in permeate (water/ethanol)
kPa-1)
PESU 21 15% 60 0.049 99.3% 1111

T-PESU 20 15% 60 0.061 99.4% 1326
PPSU 23 15% 60 0.098 98.6% 552
H-PESU 36 15% 60 0.322 98.8% 685
PI-9-1 19 15% 60 0.161 94.0% 123.9
Polyimide/UiO-
66-NH2 MMM- 33 15% 60 0.256 96.2% 202.5
10%
Polyimide/UiO-
66-NH2 MMM- 44 15% 60 0.345 94.0% 124.5
20%
Polyimide/UiO-
66-NH2 MMM- 21 15% 60 0.602 91.0% 80.3
30%
Based on this table, it can be concluded that:
H-PESU membrane is the most promising candidates for commercialization
with the most balanced separation performance with highest water
permeability and good selectivity. For commercialization, asymmetric
membranes are usually preferred to get a higher flux. But in the asymmetric
membrane fabrication, because of the hydrophilic nature, H-PESU may have
difficulty in forming the defect-free selective layer due to its slow non-solvent
induced phase inversion process. Adjusting dope formula such as blending
with other hydrophobic polymers e.g. PESU and adding non-solvent in dope
may be helpful for fast phase inversion and formation of defect-free selective
layer.
172
The other three PAE membranes i.e. PESU, PPSU and T-PESU are high
barrier materials and show high selectivity but low permeability. Therefore,
there is an urgent need to improve the permeability of these membranes.
Hydrophilic surface modification would be a worthwhile method to enhance
the performance. Based on solution-diffusion model, permeability depends on
solubility and diffusivity. One method to improve solubility of the membranes
is to increase the hydrophilicity of the membrane surface. One can incorporate
hydrophilic polymer chains like poly(4-vinylbenzoic acid) on the top of the
highly water selective membrane as shown in Figure 8.1. The membrane is
first treated with ozone for a certain time then surface initiated radical
polymerization will happen after adding 4-vinylbenzoic acid. Finally, a
hydrophilic layer will be formed on the top layer. The hydrophilic polymer
chains will increase the sorption of the water on the membrane surface and the
PAE layer can provide high selectivity so as to increase its water permeability
without sacrificing membrane selectivity. Besides hydrophilic surface
modification method, coating PAE as an ultrathin selective layer on top of
porous support to make composite membrane is also an effective way to
improve membrane flux. The porous support and the ultrathin selective layer
can greatly reduce the transport resistance and contribute to high flux while
the highly water-selective PAE layer would make sure the good separation
factor.
Figure 8.1 Hydrophilic surface modification
173
PI membrane shows moderate permeability and selectivity. On one hand, to
improve its permeability, the same hydrophilic surface modification method
presented in Figure 8.1 is also applicable for PI membrane. Besides this way,
hydrophilic surface modification of PI membranes can also be achieved by
directly reacting with some chemicals with both hydrophilic functional groups
and amine groups like β-alanine and ethanolamine. Structures of these
chemicals are shown in Figure 8.2. Polyimide can react with –NH2 in these
chemicals to form more hydrophilic polyamide layer. And the hydrophilic
functional groups in these chemicals can help further increase the water
solubility on the membrane surface, thus improve the permeability. On the
other hand, to enhance the selectivity of PI membrane, crosslinking is still
needed.
Figure 8.2 Structures of four hydrophilic chemicals
UiO-66-NH2 based MMMs also show a great potential for further
development with high permeability and moderate selectivity. However, at
the condition of very high particle loading, particles may agglomerate and
voids may form at the particle-polymer interface. The MMMs become brittle
and difficult for handling and testing. Adding modulator with amine groups
e.g. 4-aminobenzoic acid, may be a good approach to solve this problem. The
174
presence of amine groups on the modulators may create a chemical reaction
between the MOF outer surface and the imide group of the polymer, thus
increase the compatibility between MOF particle and polyimide and result in a
stable membrane.
Last, all the developed membranes in this these are used for dehydration of
alcohols via pervaporation. In the future, one can also extend the application
of the developed membranes to dehydration of other solvent or other
separation systems. And also, besides pervaporation, these membranes may
also be applied for vapor permeation because vapor permeation is very similar
to pervaporation but it has higher the operation temperature than pervaporation
and the feed is in vapor phase. A higher temperature is beneficial for a higher
flux. Therefore, vapor permeation may reduce the required membrane size for
a certain separation. Membranes with good thermal-stability may be suitable
for vapor permeation.
175
BIBLIOGRAPHY
PUBLICATIONS
325.
[2] Y.M. Xu, T.S. Chung, High-Performance UiO-66/Polyimide Mixed
Matrix Membranes for Ethanol, Isopropanol and n-Butanol Dehydration via
Pervaporation, J. Membr. Sci. 531 (2017) 16-26.
[3] Y.M. Xu, Y.P. Tang, T.S. Chung, M. Weber, C. Maletzkoc, Polyarylether
membranes for dehydration of ethanol and methanol via pervaporation, Sep.
Purif. Technol. 193 (2018) 165-174.
[4] Y.M. Xu, S. Japip, T.S. Chung, Mixed Matrix Membranes with nano-sized
functional UiO-66-type MOFs embedded in 6FDA-HAB/DABA Polyimide
for Dehydration of C1-C3 Alcohols via Pervaporation, J. Membr. Sci. (2018)
In Press.
CONFERENCE PROCEEDINGS
isopropanol dehydration via pervaporation, 26th NAMS Annual Meeting,
Bellevue, WA USA, May 21-25, 2016.
176

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DESIGN AND DEVELOPMENT OF PERVAPORATION

MEMBRANES FOR DEHYDRATION OF ALCOHOLS

me in its entirety. I have duly acknowledged all the sources of information

which have been used in the thesis.

to my supervisor, Prof. Chung Tai-Shung who provided me a great

opportunity and inspired me to work in the field of membrane science and

technology. His passion towards research gave me enthusiastic encouragement

and consistent support throughout the journey of my research tenure. His

trustful guidance and valuable suggestions provided me inspirations and

confidence to overcome the difficulties during my Doctoral study. I have

working attitude, which will definitely lead me to a bright future in coming

guidance patiently. Special thanks are given to the other members of

knowledge and help in pervaporation. I also extend my sincere thanks to all

my 4-year stay at NUS memorable, colorful and stunning.

suggestions during my oral qualification exam.

research scholarship for the whole duration of my PhD study. My heartiest

thanks go to all lab technologists and staffs in Department of Chemical and

Biomolecular Engineering, who helped me a lot in characterization techniques,

laboratory services and administrative related matters.

standing by my side with complete understanding and unwavering support.

worries about other matters.

LIST OF TABLES ............................................................................................ xi

LIST OF FIGURES .........................................................................................xii

LIST OF SYMBOLS ...................................................................................... xvi

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

1.1 Membrane pervaporation .................................................................... 1

1.2 Current applications of membrane pervaporation ............................... 2

1.2.1 Dehydration of organic solvents .................................................. 2

1.2.2 Removal of organics from aqueous solutions .............................. 4

1.2.3 Separation of organics mixtures................................................... 5

1.3 Main challenges of pervaporation ....................................................... 6

1.4 Comparison with other separation technologies ................................. 8

1.5 Research objectives and thesis organization ..................................... 10

1.6 References ......................................................................................... 14

CHAPTER 2: LITERATURE REVIEW ........................................................ 18

2.1 Mass transport mechanism ................................................................ 18

2.1.1 Solution-diffusion model ........................................................... 18

2.1.2 Pore flow model ......................................................................... 20

2.2 Evaluation of pervaporation membrane performance ....................... 21

2.3 Pervaporation membranes for alcohol dehydration .......................... 23

2.3.1 Membrane materials................................................................... 24

2.3.2 Membrane morphology and configuration ................................ 32

2.4 References ......................................................................................... 34

3.1 Materials ............................................................................................ 42

3.1.1 Polymers .................................................................................... 42

3.1.2 Chemicals for polyimide syntheses ........................................... 42

3.1.3 Chemicals for UiO-66-Type MOFs syntheses ........................... 42

3.1.4 Organic solvents......................................................................... 43

3.2 Polyimide syntheses .......................................................................... 43

3.3 UiO-66-Type MOFs syntheses ......................................................... 44

3.4 Membrane fabrication ....................................................................... 45

3.4.1 Fabrication of polyarylether membranes by knife casting ......... 45

3.4.2 Fabrication of polyimide dense membranes by ring casting ..... 46

3.4.3 Fabrication of crosslinked polybenzoxazole membranes by

thermal treatment ..................................................................................... 46

3.4.4 Fabrication of mixed matrix membranes by ring casting .......... 47

3.5 Characterizations ............................................................................... 47

3.5.1 Fourier transform infrared spectrometer (FTIR)........................ 47

3.5.2 Wide angle X-ray diffraction (XRD) ......................................... 48

3.5.3 Themogravimetric analyses (TGA) ........................................... 48

3.5.4 Themogravimetric analyses-Fourier transform infrared

spectrometer (TGA-FTIR) ....................................................................... 49

3.5.5 Scanning electron microscope (SEM) ....................................... 49