85

Development of Adsorbent Hollow Fibres for Environmental Applications

Chin-Chih Tai* and Yun-Hsin Wang Material and Chemical Research Laboratories, Industrial Technology
Research Institute, 195, Section 4, Chung Hsing Road, Chutung, Hsinchu, Taiwan 31040, R.O.C.

(Received 31 October 2012; accepted 15 January 2013)

ABSTRACT: In this paper, a new generic synthesis route for the single-step
production of adsorbent hollow fibres, based on polymer dry/wet spinning
followed by a phase inversion process, is presented. This main advantage of
this preparation technique is that it avoids impregnation of precursors or the
use of chemicals for zeolite deposition, while dramatically reducing
production times and costs. Primary factors (polymer, solvent and
temperature) affecting the structure and adsorption performance of adsorbent
hollow fibres are studied. The adsorptive properties of HiSiv 3000 hollow
fibres and their commercial particulate counterpart have been obtained in a
laboratory-scale flow system using n-butane as the adsorbate. The fibres
prepared from solvents such as N, N-dimethylformamide, N, N-
dimethylacetamide and 1-methyl-2-pyrrolidone (NMP) and from three types
of polymers, namely, polysulfone, polyethersulfone (PESF) and
polyvinylidenefluoride, are compared. The adsorbent hollow fibre prepared
from NMP/PESF gave the sharpest breakthrough curve and the longest
breakthrough time compared with others including commercial adsorbent
pellets. By applying this novel technique, fibres with unique adsorbent
properties and a high surface area per unit volume ratio can be prepared with
a range of adsorbents to target a range of pollutants. The proposed method is
not just limited to HiSiv 3000; in principle, many adsorbents or catalysts may
be used, which means that this method can pave the way for a new generation
of energy-efficient low-pressure-drop adsorbent fibres with low mass transfer
resistance.

1. INTRODUCTION

Certain types of dense polymeric membranes offer good potential for removing selective
volatile organic carbon (VOC) by vapour permeation or pervaporation owing to their high
permeability (He et al. 2002). However, current limitations arise from their low selectivities for
organics over air or water and low fluxes. The addition of an adsorptive filler to the polymeric
membrane has been demonstrated to be an effective way to improve membrane performance by
enhancing membrane sorption capacity for one or more of the compounds to be separated
(Li et al. 1994).
The application of zeolite-filled membranes to remove VOC by vapour permeation has recently
gained attention (Gao et al.1996; Li et al. 2002). In view of the solution-diffusion mechanism for

*Author to whom all correspondence should be addressed. E-mail: CCTAI@itri.org.tw (Chin-Chih Tai)
86 Chin-Chih Tai and Yun-Hsin Wang/Adsorption Science & Technology Vol. 31 No. 1 2013

molecular transport, ideal fillers for preparing VOC-selective polymer membranes should have
hydrophobicity and high sorption capacity for organic compounds and fast diffusion of the organic
molecules within the adsorbent filler. An ideal candidate for this task would be high-silica zeolites
(Lee et al. 2000). During the last few years, the number of papers published on the preparation of
mordenite framework inverted (MFI)-type zeolite membranes has increased (Jia et al. 1992; Tan
et al. 2001). The first reported zeolite (MFI)-filled membranes were polymeric. Zeolites have been
used as adsorptive fillers for improving membrane properties because of their unique crystalline
microporous structure, surface chemistry and mechanical strength. Among the many synthetic
zeolites available, only two zeolites are hydrophobic, silicalite and dealuminized-Y-zeolite, both
of which are pure crystalline silica molecular sieves. Silicalite is a dealuminized form of ZSM-5
zeolite (Li et al.1998a, b). Zeolite particles were embedded in a polymer matrix/membrane to
change the transport properties of the polymeric membrane (Hennepe et al. 1987; Pereira et al.
2003). The performance of the zeolite-filled polymeric membranes was improved compared with
the unfilled membrane. The results suggested that the higher the percentage of silicalite in the
structure the better the performance.
Silicalite-filled poly(dimethylsiloxane) membranes were first applied for the combined
pervaporation and fermentation of alcohol–water mixtures in a membrane bioreactor by
Hennepe et al. (Hennepe et al. 1991). Both selectivity and permeability of silicone rubber
membranes were enhanced by the incorporation of silicalite during pervaporation of
ethanol/water mixtures (Hennepe et al. 1991; Jia et al. 1992). This was due to the lower water
sorption capacity of silicalite. In addition, alcohol could diffuse through both the zeolite and
polymer phases, while water had to follow a more tortuous path due to the hydrophobicity of
silicalite. So far, zeolites have been used extensively in large-scale adsorption and catalytic
processes only in pellet form and the use of adsorbents in the form of hollow fibre is relatively
novel. The hollow fibres with zeolite layers used for VOC control generally have a membrane
area-to-volume ratio of 30–250 m2/m3. Much higher ratios (>3000 m2/m3) and efficient
recovery can be achieved with molecular sieving hollow fibres. Therefore, our research has
concentrated on the development and characterization of adsorbent hollow fibres instead of
hollow fibre membrane. With these composite fibres, highly compact and light-weight low-
pressure-drop devices could be constructed for wastewater treatment, gas separation or
membrane catalysis.
It is necessary that a good porous membrane used in separation processes must have high
permeability, good hydrophobicity and excellent chemical resistance to the feed streams. For
adsorbent hollow fibre development, three polymers, namely, polysulfone (PSF),
polyethersulfone (PESF) and polyvinylidenefluoride (PVDF), were selected for a number of
reasons. Currently, PVDF, PSF and PESF are the most popular and commercially available
hydrophobic membranes. PVDF is a semi-crystalline polymer containing a crystalline phase and
an amorphous phase. The crystalline phase provides thermal stability even at a temperature (Tm)
in excess of 171 °C while the amorphous phase has flexibility towards membranes. In addition,
the hydrophobicity of PVDF has a potential application in the membrane-based gas absorption
and oil/water separation processes (Tirmizi and Raghuraman 1996). PSF and PESF have been the
preferred membrane materials for applications involving kidney dialysis, water and wastewater
purification, desalination and gas separation. PSFs are a class of amorphous high performance
polymers, characterized by excellent thermal properties (PSF, Tg = 190 °C; PESF, Tg = 220 °C),
good resistance to inorganic acids and bases, and outstanding hydrolytic stability against hot water
and steam sterilization.
Development of Adsorbent Hollow Fibres for Environmental Applications 87

One of the major challenges of the project has been to prepare defect-free fibres with good
adsorption capacity and good mechanical strength using the dry/wet spinning technique. The
HiSiv 3000 hollow fibres were formed by the phase inversion process (Luyten et al. 1999; Tai
2007). First, a spinning mixture is prepared from a polymer, a solvent and an adsorbent powder.
Subsequently, the produced mixture is extruded through a spinneret into a bath of non-solvent.
This non-solvent, usually tap water, is also introduced through the bore of the spinning dye at
slightly elevated temperature. The exchange of solvent and non-solvent leads to thermodynamic
instability of the spinning mixture and induces liquid–liquid demixing. Further exchange leads to
solidification of the polymer-rich phase, while simultaneously entrapping the adsorbent particles.
Average pore size and effective surface porosity of the adsorbent hollow fibres were determined
by the gas permeation studies using the Poiseuille flow model (Shih et al. 1990). Primary factors
affecting the structure and performance of the molecular sieving hollow fibres are presented in this
paper. The adsorbent hollow fibre development from a number of polymers and solvent
combinations are compared. The effect of freshly prepared fibres against the regenerated fibres at
200 °C in N2 on the final adsorption performance is presented. To minimize the mass transfer
limitations, the inner and outer wall skin thickness and the porosity of the hollow fibre were
controlled by varying the solvents in the polymer dope, bore liquid composition and the air gap.
The studies mainly concentrated on the development of defect-free hollow fibres with a high
percentage of adsorbent materials in the structure.

2. EXPERIMENTAL SETUP

2.1. Materials

The adsorbent type used for the hollow fibre preparation was 200-mesh HiSiv 3000 powder
purchased from UOP. The polymers, PSF, PESF and PVDF, were purchased from Solvay. The
solvents, N, N-dimethylacetamide (DMAc) (99.9%, HPLC Grade, Merck), 1-methyl-2-
pyrrolidone (NMP) (99 + %, Spectrophotometric Grade; Merck) and N, N-dimethylformamide
(DMF) (99.8%, ACS Reagent, Aldrich), were used to prepare the polymer dopes.
Polyvinylpyrrolidone (PVP) (Sigma; molecular weight = 10,000) and acetone (Aldrich) were used
as additives. Distilled water was used as an internal coagulant. Tap water was used as the external
coagulant.

2.2. Spinning Solution Preparation

Three types of solvents and polymers were used during polymer dope preparation. The required
quantity of organic solvent (NMP, DMAc or DMF) was poured into a 1–l wide-neck bottle and
then the desired quantity of polymer (PESF, PSF or PVDF) was slowly added. The mixture was
stirred on a rotary pump to form the polymer solution. After the formation of a clear polymer
solution, a desired amount of inorganic adsorbent (HiSiv 3000) powder was added and the mixture
was stirred for 2 days to ensure a good dispersion. This is essential in the spinning process, as
aggregates can lead to unstable spinning and blocking of the spinneret. An IKA WERKE stirrer
was used at a speed between 500 and 2000 rpm. PVP or acetone as an additive was introduced
into the solution to modulate the viscosity of the mixture when required. The compositions of the
spinning mixtures used are given in Table 1.
88 Chin-Chih Tai and Yun-Hsin Wang/Adsorption Science & Technology Vol. 31 No. 1 2013

TABLE 1. Composition of the Spinning Dopes

Dope no. Dope solution Viscosity Spinning parameters
compositions (wt. %) (Pa·s)

Sample A DMF/PESF, 80/20 9.2 Coagulation bath temperature (°C) 25

(DMF/PESF) HiSiv 3000/PESF, Injection rate of internal coagulant
75/25 (m/minute) 14
Sample B NMP/PESF, 80/20 10.7 Nitrogen pressure (bar) 2
(NMP/PESF) HiSiv 3000/PESF, Air gap (cm) 3
75/25 Linear extrusion speed (rpm) 40
Sample C DMAc/PESF, 80/20 8.6 Bore liquid water
(DMAc/PESF) HiSiv 3000/PESF, 75/25 External coagulant water
Sample D NMP/PSF, 80/20 9.1
(NMP/PSF) HiSiv 3000/PSF, 75/25
Sample E NMP/PVDF, 80/20 8.8
(NMP/PVDF) HiSiv 3000/PVDF, 75/25

2.3. Adsorbent Hollow Fibre Spinning

The polymer solution was degassed for 2–4 hours at room temperature (25 °C) before starting the
spinning process. This step was carried out to ensure that gas bubbles are completely removed
from the viscous polymer solution. The tank was pressurized to 2–4 bar using nitrogen during the
spinning process. A schematic diagram of the spinning apparatus is shown in Figure 1.

Solution A
Bore liquid

Solution B Solution B

P Pressure
gauge
Triple orifice spinneret

Nitr
oge Special design
Special piston
n P High pressure
Internal delivery vessel
polymer
Nitr
gel dope
oge
n External
polymer Fine control
for spinning
gel dope
dope Motor guide

Air gap
Internal coagulant Gear pump

Washing bath

Coagulation bath Fibre storage tank

Figure 1. Schematic diagram of the hollow fibre spinning system (Tai 2007).
Development of Adsorbent Hollow Fibres for Environmental Applications 89

Details of the spinning conditions and parameters used are shown in Table 1. A tube-in-orifice
spinneret with orifice diameter and inner tube diameter of 2.0/0.72 (mm) was used to produce the
adsorbent hollow fibres. The air gap was kept at 3 cm and water was used as the internal and
external coagulator for all spinning runs. Finally, the green adsorbent hollow fibre was formed
from the spinneret and it was passed through a water bath to aid in the phase inversion process.
The hollow fibre was then washed thoroughly in a second water bath. Care was taken to ensure
continuity of the pressure and internal water support to avoid entrapment of air and separation of
the fibre, which would eventually result in an unsuccessful spinning. The hollow fibres were left
to soak for 3–4 days in fresh water, which is an essential step for thorough removal of residual
solvent. Then these fibres were dried at ambient conditions for 7 days before regeneration and
characterization.

2.4. Characterization

All the fibres were characterized using scanning electron microscopy, gas permeation test to
measure skin porosity and butane breakthrough testing to examine adsorption properties of the
adsorbent hollow fibres.

2.4.1. Scanning electron micrographs

The scanning electron micrographs (SEMs) were used for the characterization of HiSiv 3000
powders and HiSiv 3000 hollow fibres. The surface structure, particle size and HiSiv 3000 particle
distribution in the matrixes were observed using the JEOL JSM6310 model. First, the sample was
frozen in liquid nitrogen for 20–30 seconds and sectioned using a sharp blade. Then, a specimen
plate was coated with a thin layer of gold under 3 mbar pressure for 3–5 minutes using the
Edwards Sputter Coater (S150B). The SEM was operated in the range 10–20 kV and a number of
areas on each sample were micrographed.

2.4.2. Viscosity test

The viscosity values of the spinning dopes were obtained by using a Bohlin CS 50 Rheometer
(Stress Viscometry Model). To spin good quality adsorbent hollow fibres, the viscosity of the
polymer solution should be generally between 7 and 15 Pa⋅s. It is very important that while
applying the polymer dope the correct amount is used, because overfilling or underfilling the
equipment will result in errors in viscosity readings.

2.4.3. Gas permeation test

Dead-end gas permeation experiments were carried out to determine the pore characteristics of
skin of the fibre. They were sealed with Araldite at one end and nitrogen pressure was applied on
the outside of the fibre at the other end. Nitrogen flow was measured at different transmembrane
pressures using a Brooks mass flow indicator.
The average pore size (r) and the effective surface porosity (defined as the ratio of the surface
porosity to the effective pore length, ε/Lp) are two important parameters of a membrane. The
intercept (K0) and slope (P0) were determined by plotting the pressure-normalized permeation flux
90 Chin-Chih Tai and Yun-Hsin Wang/Adsorption Science & Technology Vol. 31 No. 1 2013

against average pressure. The average pore size (r) and the effective surface porosity, ε/Lp, were
calculated from the following equations (1) and (2):

1
r = (16/3)(P0/K0)(8RT/πR) /2 µ (1)

ε/Lp = 8µµRT0/r2 (2)

where R is the gas constant, T is the absolute temperature, M is the molecular weight and µ the
gas viscosity.

2.4.4. Adsorption performance by n-butane breakthrough curve

Dynamic adsorption experiments were carried out in an apparatus similar to that described
previously (Lee et al. 2000). The adsorption columns contained a fixed amount of adsorbent
material (14 g), either in pellet form (HiSiv 3000 fibre cut into 5.0 × 1.4-mm pieces) or as a
fibre module form (sample B, which contained 50 fibres of 250-mm length). Commercial HiSiv
3000 pellets (1.0 × 1.18 mm mesh, purchased from UOP) of similar weight was used for
comparative analysis. The physical properties of the materials used are shown in Table 2.
n-Butane was selected as a model volatile organic compound to compare the dynamic
adsorption performance of novel adsorbent hollow fibres prepared from selected polymer
solvent combinations (given in Table 2) and the commercial HiSiv 3000 pellets. For this study,
HiSiv 3000-to-polymer ratio was kept at 75:25 during the preparation of all the adsorbent
fibres. This is important because commercial pellets generally have a HiSiv 3000-to-binder

TABLE 2. Properties of HiSiv 3000-Filled Polymeric Hollow Fibres Prepared from the 25 wt.% Polymer
Dopes by Using Three Different Solvents
Sample name Solvent/PESF HiSiv Average pore Gas permeability Effective
(weight ratio) 3000/PESF diameter (nm) (mol m–2 Pa–1 s–1) surface
(weight ratio) [N2, 1.01325 × 105 porosity
Pa (1 atm)] (m–1), ε/Lp

Sample A DMF/PESF HiSiv 166 2.97 × 10–5 2340

(DMF/PESF) 4 3000/PESF
3
Sample B NMP/PESF HiSiv 304 3.29 × 10–5 1250
(NMP/PESF) 4 3000/PESF
3
Sample C DMAc/PESF HiSiv 179 1.08 × 10–5 765
(DMAc/PESF) 4 3000/PESF
3
Sample D NMP/PSF HiSiv 146 1.97 × 10–5 1800
(NMP/PSF) 4 3000/PSF
3
Sample E NMP/PVDF HiSiv 1341 5.22 × 10–5 239
(NMP/PVDF) 4 3000/PVDF
3
Development of Adsorbent Hollow Fibres for Environmental Applications 91

ratio of 75:25 wt.%. The total gas flow rate was fixed at 1.5 l·minute−1 and the concentration of
n-butane was fixed at 6000 ppm in nitrogen.
The feed concentration and the progress of the breakthrough curve from the adsorption column
were continuously monitored with a flame ionization detector (model 3000; Signal Instruments).
To examine the effect of regeneration conditions of the fibre/pellets on the adsorption
performance, the adsorbent hollow fibres (pellets/fibre modules) were subjected to regeneration
for 24 hours in N2 either at 50, 100 or 200 °C before performing adsorption experiments. All
adsorption experiments were carried out at 25 °C. The gas flow through the column was upwards
for adsorption and downwards during tPhe regeneration part of the cycle. The experiments were
terminated when the concentration of n-butane in the effluent from the column became equal to
the feed concentration.

3. RESULTS AND DISCUSSION

3.1. Characterization of HiSiv 3000/Polymer Composite Hollow Fibres

Figures 2–6 show the SEMs of cross sections of HiSiv 3000/polymer composite hollow fibres
prepared from 25 wt.% polymer solution using three different solvents and polymers: DMF/PESF
(Figure 2), NMP/PESF (Figure 3), DMAc/PESF (Figure 4), NMP/PSF (Figure 5) and
NMP/PVDF (Figure 6), respectively. The adsorbent fibres are perfectly formed and symmetrical
and the thickness of the wall is approximately 0.3–0.5 mm. The micrographs show that the

(a) (b) (c)

Figure 2. Hollow fibre prepared from DMF/PESF (4/1) and HiSiv 3000/PESF (3/1) (Sample A): (a) cross-section of the
fibre, 40×; (b) cross-section showing finger structure, 200×; (c) cross-section showing macrovoids, 1000×.

(a) (b) (c)

Figure 3. Hollow fibre prepared from NMP/PESF (4/1) and HiSiv 3000/PESF (3/1) (Sample B): (a) cross-section of the
fibre, 40×; (b) cross-section showing large macrovids, 150×; (c) distribution of HiSiv 3000 in the structure, 1000×.
92 Chin-Chih Tai and Yun-Hsin Wang/Adsorption Science & Technology Vol. 31 No. 1 2013

(a) (b) (c)

Figure 4. Hollow fibre prepared from DMAc/PESF (4/1) and HiSiv 3000/PESF (3/1) (Sample C): (a) cross section of the
fibre, 45×; (b) cross-section showing finger-like voids, 200×; (c) distribution of HiSiv 3000 in the structure, 1000×.

(a) (b) (c)

Figure 5. Hollow fibre prepared from NMP/PSF (4/1) and HiSiv 3000/PSF (3/1) (Sample D): (a) cross-section of the
dense fibre, 50×; (b) cross-section showing spongy type of structure, 250×; (c) distribution of HiSiv 3000 in the structure,

(a) (b) (c)

Figure 6. Hollow fibre prepared from NMP/PVDF (4/1) and HiSiv 3000/PVDF (3/1) (Sample E): (a) cross-section of the
dense fibre, 50×; (2) cross-section showing dense structure with irregular voids, 200×; (c) distribution of HiSiv 3000 in
the structure, 1000×.

inorganic adsorbent particles are present in the cavities of the polymer matrix and are not
entrapped in the polymer itself. Most importantly, the micrographs show that the HiSiv 3000
particles are not covered by a polymer coating. It seems that the particles act as nuclei around
which the polymer lean phase can grow. Table 2 presents the results of pore size, effective surface
porosity and nitrogen permeability for the adsorbent hollow fibres developed.
It was found that in order to spin hollow fibres, the viscosity of the polymer solution should
be between 8 and 12 Pa·s. The viscosity of the dope prepared from PESF (10.7 Pa·s) was found
to be higher than the dopes prepared from PSF (9.1 Pa·s) and PVDF (8.8 Pa·s). The wall
thickness of the fibre increased with the increase in the viscosity of the spinning dope. Results
Development of Adsorbent Hollow Fibres for Environmental Applications 93

of the SEM analysis show that the wall thickness has increased in the following order: sample
E (0.30 mm) < sample D (0.31 mm) < sample C (0.34 mm) < sample A (0.35 mm) < sample
B (0.46 mm).
Figures 2–4 show the cross-sectional structure of HiSiv 3000/PESF hollow fibres prepared
from different solvents (DMF, NMP and DMAc). The fibre produced from PESF/DMF has a long
thin finger-like structure extending from the inner layer to the outer layer while fibres prepared
from PESF/DMAc and PESF/NMP produced a sponge-like structure with some large macrovoids
(Figures 3 and 4). The appearance of the fibre structure shown in SEMs can be attributed to the
rapid precipitation that occurred at the inner fibre wall, resulting in the long finger-like structures.
The N2 gas permeability (Table 2) of PESF fibres prepared using NMP as the solvent is higher than
that of the fibres prepared using DMF and DMAc as the solvent. The gas permeation data were
analyzed using Poiseuille flow model and the average skin pore size and the effective porosity are
given in Table 2. High molecular weight of NMP leads to slower exchange of solvent diluents and
may lead to large pore formation during the phase inversion process. In order to understand the
influence of polymer properties on adsorption capacity, the three different polymers were also
compared. The adsorbent hollow fibre prepared from NMP/PVDF gave the highest nitrogen
permeation and the larger average skin pore size compared with the fibres prepared from
NMP/PESF and NMP/PSF.

3.2. Dynamic Adsorption of n-Butane onto HiSiv 3000 Hollow Fibres

A comparison of the breakthrough curves of HiSiv 3000/polymer (PSF, PESF and PVDF)
composite hollow fibres prepared from different solvents (DMF, NMP and DMAc) is shown
in Figure 7. The results of commercial adsorbent pellets (HiSiv 3000, sphere 2 mm × 2 mm)
are also provided. The breakthrough curves reveal that, irrespective of the solvent used,
adsorbent fibres prepared from PESF showed better performance than that of its equivalent

100

90

80

70

60
C/C0 (%)

50

40 DMF/PESF (Sample A)
NMP/PESF (Sample B)
30 DMAc/PESF (Sample C)
NMP/PSF (Sample D)
20
NMP/PVDF (Sample E)
10 Commercial pellets

0
0 10 20 30 40 50 60 70 80 90
Time (minute)

Figure 7. Comparison of breakthrough curves of n-butane onto composite HiSiv 3000 hollow fibres prepared from
different solvents and polymers [HiSiv 3000 (75%): polymer (25%) w/w] with those of commercial pellets.
94 Chin-Chih Tai and Yun-Hsin Wang/Adsorption Science & Technology Vol. 31 No. 1 2013

particulate system. The breakthrough times of the samples A, B, C, D, E and commercial

pellets are 28, 33, 27, 20, 18 and 23 minutes, respectively. These results show that the
breakthrough times increased in following order: sample E (NMP/PVDF) < sample D
(NMP/PSF) < commercial pellets < sample C (DMAc/PESF) < sample A (DMF/PESF) <
sample B (NMP/PESF). The results clearly demonstrate that the solvent type and the various
types of polymer used during the spinning process have a significant influence on the
structure, the porosity of the hollow fibre and kinetic performance of the fibre. The open
finger-like structure in the PESF fibres seems to be providing more accessibility for the
adsorbate molecules to reach the adsorption sites and therefore providing better kinetic
performance. The hollow fibre prepared from the NMP solvent and the PESF polymer gave the
sharpest breakthrough curve and the longest time to breakthrough. The breakthrough curve for
the hollow fibre prepared from DMF is broader than those for the equivalent pellets. In
addition, sample D (NMP/PSF) and sample E (NMP/PVDF) have a shorter breakthrough time
and broad curve as compared with sample B (NMP/PESF) for the same operating conditions.
Certainly, the higher molecular weight solvent NMP with the higher Tg polymer PESF seems
to be a better combination than the DMF or DMAc solvents and PSF or PVDF polymers for
producing superior adsorbent hollow fibres. The breakthrough times and the kinetic
performance of HiSiv 3000 hollow fibres produced are significantly better than the
commercial pellets, indicating the importance of solvent and polymer contribution to its
porosity and effective surface area in creating accessible adsorption sites.

3.3. Effect of Regeneration Temperatures on Adsorption Performance

To examine the effect of regeneration temperature of the adsorbent composite hollow fibres on
adsorption capacity, the fibres were subjected to a number of pre-treatment conditions. Figure 8
shows the experimental breakthrough curves obtained using sample B (HiSiv 3000/PESF) hollow

100

90

80

70

60
C/C0 (%)

50
50 °C
40
100 °C
30 200 °C

20 250 °C
200 °C-module
10

0
0 10 20 30 40 50 60 70 80 90 100
Time (minute)

Figure 8. Comparison of breakthrough curves of n-butane adsorption onto sample B (HiSiv 3000/PESF) composite hollow
fibres after a range of pre-treatment temperatures; (closed squares) 50 °C, (closed circles) 100 °C, (closed triangles)
200 °C, (closed diamonds) 250 °C and (closed stars) hollow fibre module at 200 °C.
Development of Adsorbent Hollow Fibres for Environmental Applications 95

fibre (cut into pellet form) after regenerating at 50, 200, 250 °C and the hollow fibre module
regenerated at 200 °C in N2 for 24 hours. The breakthrough times of HiSiv 3000/PESF hollow
fibre pellets treated at 50, 100, 200, 250 °C and the module at 200 °C are 16, 18, 34, 28 and 37
minutes, respectively. The breakthrough curves revealed that the adsorption breakthrough time
increases with increasing pre-treatment temperatures because the porosity of hollow fibre surface
and adsorption sites of HiSiv 3000 are enhanced. As expected, with PESF/HiSiv 3000, a loss of
adsorption capacity and broadening of the curve was noticed above 250 °C. This confirms that as
the temperature exceeded the PESF Tg (220 °C), the polymers undergo a phase change causing
the HiSiv 3000 adsorption sites to be blocked. To analyze the adsorption performance of packed
bed form with fibre monolith form, a similar weighted PESF/HiSiv 3000 (sample B) fibre module
was compared with the pelleted form, keeping all the other conditions the same. Figure 8 shows
that the adsorption curve of the hollow fibre module is sharper than those of hollow fibre pellets,
which implies that the hollow fibre module gives better adsorption kinetic performance than the
hollow fibre pellets.
When HiSiv 3000/PSF (sample D) was treated with three different heat treatment temperatures
(50, 100 and 200 °C), the breakthrough times increased from 17 (50 °C) to 21 minutes (100 °C)
(Figure 9). However, further increase in the regeneration temperature to 200 °C resulted in a 14%
decrease in breakthrough time (18 minutes) compared with regeneration at 100 °C. This is due to
the result of regeneration temperature beyond the Tg of PSF (190 °C).

100

90

80

70

60
C/C0 (%)

50

40
50 °C
30
100 °C
20
200 °C

10

0
0 10 20 30 40 50 60 70
Time (minute)

Figure 9. Comparison of breakthrough curves of n-butane adsorption onto sample D (HiSiv 3000/PSF) composite hollow
fibres treated at (closed squares) 50 °C, (closed circles) 100 °C, and (closed triangles) 200 °C for 24 hours.

The effect of regenerated temperatures on the n-butane adsorption breakthrough curves for
sample E (HiSiv 3000/PVDF) is shown in Figure 10. The breakthrough times were found to
increase from 16 to 21 minutes as the regeneration temperature increased from 50 to 100 °C. A
total loss of adsorption capacity was noticed when the temperature exceeded beyond 180 °C. The
HiSiv 3000 adsorption sites have been fully blocked and covered by the degrading PVDF, and
therefore, the loss of adsorption capacity when the heating temperature exceeded the Tm (171 °C).
96 Chin-Chih Tai and Yun-Hsin Wang/Adsorption Science & Technology Vol. 31 No. 1 2013

100

90

80

70

60
C/C0 (%)

50

40
50 °C
30
100 °C
20
180 °C

10

0
0 10 20 30 40 50 60 70 80
Time (minute)

Figure 10. Comparison of breakthrough curves of n-butane adsorption onto sample D (HiSiv 3000/PVDF) composite
hollow fibres after the heat treatment at (closed squares) 50, (closed circles) 100 and (closed triangles) 180 °C for 24 hours.

4. CONCLUSIONS

HiSiv 3000 adsorbent hollow fibres were successfully prepared by dry/wet spinning a polymer
solution containing suspended HiSiv 3000 crystals in a hollow fibre precursor. The morphology
and the adsorption properties of the fibre were found to be mainly depending on the organic
solvent used, viscosity of the precursor, the ratio of the adsorbent to the polymer content and the
regeneration temperature. It is possible to prepare adsorbent hollow fibres from all the three
solvents (DMF, NMP and DMAc) successfully. However, the fibres produced from NMP were
superior in quality with larger pore size, better adsorption capacity and improved kinetic
performance than fibres produced from other two solvents. The inner and outer wall skin
thicknesses and the porosity of the hollow fibre were controlled by varying the solvent in the
polymer dope and the bore liquid composition. The macrostructure of the fibre seems to be largely
determined by the composition of the spinning dope. Because the hollow fibres have highly open
porous structures with a small skin thickness, they are expected to have minimal mass transfer
resistances during molecular transport processes.
Regeneration temperature has influenced not only the morphology but also
adsorption/separation performances of the fibre. The adsorption breakthrough time increased
as the regeneration temperature increased. From the results it is possible to conclude that the
appropriate regeneration temperature of HiSiv 3000/PESF fibre is 200 °C for 24 hours. The
breakthrough performances of HiSiv 3000 hollow fibres produced are significantly better than
the commercial pellets, indicating the importance of solvent and polymer contribution to its
porosity and effective surface area in creating accessible adsorption sites. These results are a
clear indication that the polymer has not blocked the adsorption sites of the HiSiv 3000 during
synthesis. It is possible to conclude that the combined effects of suitable polymer/adsorbent
dope composition and reasonable heat treatment can produce adsorbent hollow fibres that have
superior quality than the commercial pellets for environmental pollution control applications.
These results augur well for the adsorbent hollow fibre composite systems.
Development of Adsorbent Hollow Fibres for Environmental Applications 97

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