polymers

Article
The Viable Fabrication of Gas Separation Membrane
Used by Reclaimed Rubber from Waste Tires
Yu-Ting Lin 1 , Guo-Liang Zhuang 1 , Ming-Yen Wey 1, * and Hui-Hsin Tseng 2,3, *
1 Department of Environmental Engineering, National Chung Hsing University, Taichung 402, Taiwan;
a0938866458@gmail.com (Y.-T.L.); d102063002@smail.nchu.edu.tw (G.-L.Z.)
2 Department of Occupational Safety and Health, Chung Shan Medical University, Taichung 402, Taiwan
3 Department of Occupational Medicine, Chung Shan Medical University Hospital, Taichung 402, Taiwan
* Correspondence: mywey@dragon.nchu.edu.tw (M.-Y.W.); hhtseng@csmu.edu.tw (H.-H.T.);
Tel.: +886-4-22840441 (ext. 533) (M.-Y.W.); +886-4-24730022 (ext. 12115) (H.-H.T.)




Received: 14 September 2020; Accepted: 28 October 2020; Published: 30 October 2020


Abstract: Improper disposal and storage of waste tires poses a serious threat to the environment
and human health. In light of the drawbacks of the current disposal methods for waste tires,
the transformation of waste material into valuable membranes has received significant attention
from industries and the academic field. This study proposes an efficient and sustainable method
to utilize reclaimed rubber from waste tires after devulcanization, as a precursor for thermally
rearranged (TR) membranes. The reclaimed rubber collected from local markets was characterized
by thermogravimetric analyzer (TGA) and Fourier transfer infrared spectroscopy (FT-IR) analysis.
The results revealed that the useable rubber in the as-received sample amounted to 57% and was
classified as styrene–butadiene rubber, a type of synthetic rubber. Moreover, the gas separation
measurements showed that the C7-P2.8-T250 membrane with the highest H2 /CO2 selectivity of 4.0
and sufficient hydrogen permeance of 1124.61 GPU exhibited the Knudsen diffusion mechanism and
crossed the Robeson trade-off limit. These findings demonstrate that reclaimed rubber is an appealing,
cost effective, and sustainable alternative, as a precursor for TR membranes, for application in gas
separation. The present approach is useful in the selection of a suitable reclaimed rubber precursor
and related membrane preparation parameters, leading to the advancement in the recycling value of
waste tires.

Keywords: gas separation; thermally rearranged membrane; waste material; sustainable development;
circular economy

1. Introduction
Rapid population growth and industrialization are responsible for the significant increase in
production and accumulation of solid waste. Advances in the automobile industry and increased use
of vehicular modes of transport have led to an increase in the number of waste tires [1]. Currently,
the global annual consumption of tires is up to 1 billion units [2,3]. Furthermore, the consumption
rate of tires is expected to grow exponentially with their demand growing in developing countries.
In Taiwan, the annual recovery market for waste tires is approximately 100 thousand tonnes, reaching
approximately 140 thousand tonnes in 2017 according to the statistics of Environmental Protection
Administration Executive Yuan, Republic of China (R.O.C.) (Taiwan) [4]. The most prevalent disposal
methods for waste tires include landfilling and using them as auxiliary fuel for energy recovery [5,6].
However, landfilling is not the preferred option due to the large volumes of tires. Furthermore,
the doughnut shape of tires retains stagnant water, which becomes a breeding habitat for mosquitoes,
thereby resulting in the spread of vector-borne diseases [7], especially in humid environments found in

Polymers 2020, 12, 2540; doi:10.3390/polym12112540 www.mdpi.com/journal/polymers

Polymers 2020, 12, 2540 2 of 15

countries like Taiwan. The incineration of waste tires emits pollutants including carbon monoxide
(CO), carbon dioxide (CO2 ), sulfur oxides (SOx), toxic dioxins, polycyclic aromatic hydrocarbons,
and particulate matter [8]. Therefore, the improper disposal and storage of waste tires can have
adverse effects on the environment and human health. This necessitates the development of sustainable
and efficient recovery and recycling methods for waste tire management. One of the best alternative
solutions for dealing with waste tires is to transform them from waste material into valuable substances
such as membranes. Considering the number of tires being discarded globally, rubber consumption is
facilitating the exhaustion of limited petrochemical resources. Hence, in view of the circular economy
and the drawbacks of current disposal methods for discarded tires, investigating technologies that can
utilize waste materials are an inevitable tendency worldwide. For countries whose energy is imported,
such as Taiwan, the reutilization of waste materials could boost their economic development because
of the reduction in trade deficit. For example, the Taiwanese government is pressing ahead with the
policy for a circular economy to provide financial support for companies and academic scientists to
encourage and promote reutilization technology.
Recently, thermally rearranged (TR) membranes have been widely applied in the field of gas
separation, such as hydrogen recovery, carbon dioxide capture, and natural gas purification, due to
their unique microstructure and superior chemical/thermal stability in harsh environments [9,10].
TR membranes can be fabricated through a simple thermal rearrangement process after the heat
treatment of a polymeric membrane, which facilitates the transformation of interconnected microcavities
with a narrow cavity [11]. The thermal rearrangement process begins when the polymer aromatic chains
undergoes a heating process by reaction of ortho-substituted atoms, creating a new ring. The buckling
of the ring creates free volume elements in the membrane and enhances gas diffusion. Consequently,
the microporous structure of TR membranes is obtained, which exhibits high gas permeance and great
separation property. The frequently used polymer precursors for TR membranes mainly consist of
polyimide, polybenzoxazoles, and polypyrrolone [10–12]. All the above-mentioned precursors are
thermosetting polymers that are priced exorbitantly. The main constituent (approximately 47%) of the
tires is rubber [13,14], usually synthetic, such as styrene–butadiene rubber and butadiene rubber [15].
All rubber materials are thermosetting polymers, except for thermoplastic elastomers. Thus, the rubber
material in waste tires is viewed as a valuable resource, given its potential as a membrane precursor [16].
To date, no research has investigated tire-derived TR membranes for application in gas separation,
which is likely restricted by their three-dimensional cross-linked structure, thereby resulting in inferior
processability. Recently, methods for reclaiming rubber by physical, chemical, biotechnological,
and de-link processes have been developed. The reclaimed rubber, with enhanced process flexibility,
is converted from a three-dimensional cross-linked structure into a one-dimensional thermosetting
polymer by destroying the rubber/sulfur bond [17]. This study was conducted using reclaimed rubber
as the precursor for TR membranes. The effects of precursor concentration, incorporation of additives,
and thermal treatment temperature on as-prepared TR membranes derived from reclaimed rubber
were investigated.

Research Significance
A huge amount of waste tires are produced worldwide due to the expansion of the automobile
industry, and their disposal is an issue faced by all countries. The most common method to handle
waste tires is landfilling or using them as auxiliary fuel for energy recovery. However, the published
studies showed that scrapped rubber tires could not be decomposed under environmental conditions
and pose a serious threat to the environment and human health. Moreover, the incineration of waste
tires is accompanied with emissions of dioxins, volatile organic compounds and particulate matter.
Consequently, recycling waste tire rubber by transforming it into a valuable material (e.g., membranes)
has become the preferred solution to dispose of waste tires. From the circular economy perspective,
reclaimed rubber-derived membrane is a reutilization alternative that contributed to waste reduction.
Therefore, the goals of the present study were to provide a viable and green precursor (reclaimed
Polymers 2020, 12, 2540 3 of 15

Polymers 2020, 12, x FOR PEER REVIEW 3 of 16

rubber) with which to fabricate a TR membrane applied in the field of gas separation, thus boosting the
circular economy via prolonging the life cycle of rubber tires. In order to further extend understanding
were conducted to understand its characteristics and performance in related membranes. The
of the reused rubber from waste tire, a series of characterizations were conducted to understand
membrane fabrication parameters, including precursor concentration, heating temperature, and the
its characteristics and performance in related membranes. The membrane fabrication parameters,
incorporation of a polyphenylene oxide (PPO) modifier, as well as the corresponding gas transport
including precursor concentration, heating temperature, and the incorporation of a polyphenylene
measurements, were also studied to produce an experimental evaluation of this new precursor for a
oxide (PPO) modifier, as well as the corresponding gas transport measurements, were also studied to
gas separation membrane. To the best of our knowledge, there are no other existing studies on rubber-
produce an experimental evaluation of this new precursor for a gas separation membrane. To the best
derived TR membranes applied in gas separation.
of our knowledge, there are no other existing studies on rubber-derived TR membranes applied in
gas separation.
2. Experiment
2. Experiment
2.1. Materials
2.1. Materials
The crumb rubber sample and the reclaimed rubber sample selected as polymer precursors in
this work wererubber
The crumb supplied by and
sample International Quality
the reclaimed rubberMaterials Nano Tech.
sample selected Co., Ltd.
as polymer (TaipeiinCity,
precursors this
Taiwan), as shown in Figure 1. Toluene (extra pure grade—99% purity, Union Chemical
work were supplied by International Quality Materials Nano Tech. Co., Ltd. (Taipei City, Taiwan), Works Ltd.,
Hsinchu
as shown City, Taiwan)
in Figure was (extra
1. Toluene sourced asgrade—99%
pure a solvent for the preparation
purity, Union Chemical of the casting
Works Ltd.,solution. The
Hsinchu City,
polyphenylene oxide (PPO, Cas. No. 25134-01-4) purchased from Sigma-Aldrich (Saint
Taiwan) was sourced as a solvent for the preparation of the casting solution. The polyphenylene oxide Louis, MO,
USA) was
(PPO, Cas.used
No. as an additivepurchased
25134-01-4) to modifyfrom
the microstructure
Sigma-Aldrich of(Saint
the TRLouis,
membrane. Commercial
MO, USA) was used ceramic
as an
embryos,
additive towith an average
modify pore size of
the microstructure of74 TRthickness
theÅ, membrane. of 1.4 mm, and ceramic
Commercial diameterembryos,
of 23 mm were
with an
obtained from Ganya Fine Ceramics Co. (New Taipei City, Taiwan). They were
average pore size of 74 Å, thickness of 1.4 mm, and diameter of 23 mm were obtained from Ganya calcined at 1400 °C
with a heatingCo.
Fine Ceramics rate(New
of 2 °C/min for 2Taiwan).
Taipei City, h holding
Theytime
werein our laboratory
calcined at 1400to◦ Cenhance their physical
with a heating rate of
strength. They
2 ◦ C/min for 2 hwere usedtime
holding as ainbare
oursubstrate.
laboratoryThe tested gases
to enhance their(99.999%
physical pure)—H 2, CO2were
strength. They , O2, N 2, and
used as
CH 4—were obtained from Toyo Gas Co. (Taichung City, Taiwan). All chemical reagents
a bare substrate. The tested gases (99.999% pure)—H2 , CO2 , O2 , N2 , and CH4 —were obtained from were used
directly
Toyo Gaswithout purification.
Co. (Taichung City, Taiwan). All chemical reagents were used directly without purification.

Figure
Figure 1.
1. Optical
Optical image
image of
of as-received
as-received rubber sample provided from local market.

2.2. Synthesis of Rubber-Derived TR Membrane

2.2. Synthesis of Rubber-Derived TR Membrane
Initially, the different concentrations at 4, 5, 6, and 7 wt % of casting solutions were obtained by
Initially, the different concentrations at 4, 5, 6, and 7 wt % of casting solutions were obtained by
dissolving the desired amounts of collected reclaimed rubber in toluene solvents at a fixed temperature
dissolving the desired amounts of collected reclaimed rubber in toluene solvents at a fixed
of 160 ◦ C for 24 h. Similarly, casting solutions with various additive contents within the range of 0.7–2.8%
temperature of 160 °C for 24 h. Similarly, casting solutions with various additive contents within the
were prepared. Afterwards, the as-prepared casting solution was applied onto an alumina substrate
range of 0.7–2.8% were prepared. Afterwards, the as-prepared casting solution was applied onto an
via the spin coating technique at a speed of 2000 rpm for 16 s to obtain the uniform rubber polymeric
alumina substrate via the spin coating technique at a speed of 2000 rpm for 16 s to obtain the uniform
membrane. The fabricated rubber membranes were left overnight in an open environment at room
rubber polymeric membrane. The fabricated rubber membranes were left overnight in an open
temperature to allow the rest of the solvent in the membrane to evaporate. Subsequently, the two-stage
environment at room temperature to allow the rest of the solvent in the membrane to evaporate.
thermal rearrangement procedure was performed in a tubular furnace (Chang-Hua Electric Heating
Subsequently, the two-stage thermal rearrangement procedure was performed in a tubular furnace
Co., Ltd., Changhua city, Taiwan) in terms of a dried polymeric membrane. The polymeric membrane
(Chang-Hua Electric Heating Co., Ltd., Changhua city, Taiwan) in terms of a dried polymeric
membrane. The polymeric membrane was placed in the central zone of a quartz tube equipped with
a tubular furnace, and the heating environment was under a vacuum at less than 10−6 atm. The curing
step was conducted at 200 °C with a ramping rate of 5 °C/min and then maintained for 6 h to stabilize
Polymers 2020, 12, 2540 4 of 15

was placed in the central zone of a quartz tube equipped with a tubular furnace, and the heating
environment was under a vacuum at less than 10−6 atm. The curing step was conducted at 200 ◦ C with
a ramping rate of 5 ◦ C/min and then maintained for 6 h to stabilize the polymer chains. Next, the target
temperatures (250 and 350 ◦ C) were reached at the same heating rate (5 ◦ C/min) and were maintained
for 2 h. Finally, the TR membrane was naturally cooled to room temperature. To prevent aging, the pure
gas permeation value of the resultant TR membrane was measured within 24 h after the conduction of
the thermal rearrangement procedure. The TR membranes fabricated by different parameters were
denoted as Cx-Py-Tz, where x is the precursor concentration, y is the content of PPO additive, and z is
the heating temperature. For example, a C7-P0.7-T250 TR membrane means the polymeric membrane,
with 7 wt % rubber precursor and 0.7 wt % PPO, was heated at 250 ◦ C. Moreover, a C4-P0-T350 TR
membrane refers to a polymeric membrane prepared with a 4 wt % rubber precursor, without the
incorporation of PPO filler and heated at 350 ◦ C.

2.3. Characterization of Collected Rubber Samples and Fabricated TR Membranes

The thermal behavior of the collected rubber samples from the recycling company was studied
using a thermogravimetric analyzer (TGA, Perkin Elmer, simultaneous thermal analyzer 6000, Waltham,
MA, USA). Prior to the analysis, the as-received rubber sample was placed in the oven at 60 ◦ C for 24 h
to remove any trapped moisture. The TGA testing of the rubber sample was conducted following the
guidelines by Perkin Elmer [18]. To evaluate the polymer content in the sample, 6–8 mg of the dried
sample was first heated in a nitrogen atmosphere, with temperatures increasing from 50–700 ◦ C at
the rate of 20 ◦ C/min. Subsequently, the sample underwent second heating at 700–900 ◦ C, at a fixed
heating rate of 20 ◦ C/min, in the air atmosphere to measure the carbon black content. The residue that
remains undecomposed after heating until 900 ◦ C was considered the other filler.
Fourier transfer infrared spectroscopy (FT-IR, FT/IR-4100 spectrophotometer, Jasco Corporation,
Tokyo city, Japan) in the wavenumber range of 4000 to 400 cm−1 was performed to identify the
functional group and to confirm the composition of the collected rubber sample.
The cross-linking density (Ve , mol/cm3 ) of the rubber sample, presented in Equation (1),
was obtained by combining the American Society for Testing and Materials (ASTM) D6814 standard
and the Flory–Rehner equation [19,20].

−[ln(1 − Vr ) + Vr + X1 Vr2
ve =   1   (1)
V1 Vr3 − Vr /2

where Vr refers to the volume fraction of the swollen sample in the equilibrium with the pure solvent
(toluene), X1 refers to the polymer–solvent interaction parameter (0.446) [20], and V1 refers to the molar
volume of the toluene (106.35 cm3 /mol).
The degree of devulcanization (%) of the as-received reclaimed rubber sample was evaluated
using Equation (2):
Vr,reclaimed rubber
Devulcanization(%) = × 100% (2)
Vr,crumb rubber
where Vr,crumb rubber and Vr,reclaimed rubber refer to the cross-linking densities of the rubber sample before
and after the devulcanization process, respectively.
Scanning electron microscopy (SEM) micrographs of the rubber-derived TR membrane were
obtained by a JEOL JSM-6700F scanning electron microscope (JEOL Ltd., Tokyo city, Japan) at an
accelerating voltage of 3 kV to observe the membrane morphology. Prior to morphological analysis,
the outer surface of each sample was sputtered with gold to improve its conductivity.
Atomic force microscopy (AFM, BRUKER Dimension Icon, Billerica, MA, USA) was conducted
to evaluate the topography and surface roughness of the as-obtained TR membrane. Roughness
measurements in this work were performed by surface analysis on a fixed area (5 × 5 µm2 ) taken from
each sample.
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Polymers 2020, 12, x FOR PEER REVIEW 5 of 16

2.4. Permeation Test
2.4.The
Permeation
pure gasTestpermeation value of each as-fabricated TR membrane was measured by using
lab-scale permeation measurement equipment, with an effective membrane area of 0.785 cm2 and an
The pure gas permeation value of each as-fabricated TR membrane was measured by using lab-
operation temperature of 28 ± 2 ◦ C, by the constant volume/variable pressure approach (Figure 2).
scale permeation measurement equipment, with an effective membrane area of 0.785 cm2 and an
Before the permeation test, a vacuum pump was used to maintain the system in a vacuum state to avoid
operation temperature of 28  ±  2  °C, by the constant volume/variable pressure approach (Figure 2).
atmospheric gas interference. Afterwards, the membrane was mounted on a stainless-steel housing
Before the permeation test, a vacuum pump was used to maintain the system in a vacuum state to
(Millipore Corp., Cat.gas
avoid atmospheric No. XX4404700,Afterwards,
interference. Burlington,the MA, USA) with
membrane wasa silicone
mounted O-ring. Two pressure
on a stainless-steel
transducers a range of −1
housing (Millipore Corp., Cat. No. XX4404700, Burlington, MA, USA) with a silicone City,
with to 9 bar (JPT-131S, Jetec Electronics Co., Ltd., Taichung Taiwan)
O-ring. Two
were used to measure the feed and permeate pressures. A gas with a pressure of about
pressure transducers with a range of −1 to 9 bar (JPT-131S, Jetec Electronics Co., Ltd., Taichung City, 1.96 bar was
fed into the
Taiwan) upstream
were used to of the membrane
measure the feed andandpermeate
the downstream
pressures. pressure,
A gas withwhich increased
a pressure with time
of about 1.96
(dp/dt), was recorded with a computer. Then, the gas separation performance
bar was fed into the upstream of the membrane and the downstream pressure, which increased withof the membrane was
obtained. To minimize
time (dp/dt), the investigational
was recorded with a computer. error,
Then,each
themembrane sample
gas separation was measured
performance of the three times
membrane
was obtained. To minimize the investigational error, each membrane sample was measured three
and the average value was reported. The detailed permeation process has been described in our
times and the average value was reported. The detailed permeation process has been described in
previous work [21,22]. The tested gases in the present study contained hydrogen (2.89 Å), carbon
our previous
dioxide work
(3.24 Å), [21,22].
oxygen (3.46The
Å),tested gases
nitrogen in the
(3.64 Å),present study contained
and methane hydrogen
(3.80 Å)—the values(2.89 Å), carbon
in parentheses
dioxide (3.24 Å), oxygen (3.46 Å), nitrogen (3.64 Å), and methane (3.80 Å)—the values in parentheses
correspond to the kinetic diameter. The study inferred the gas separation mechanism of the TR
correspond to the kinetic diameter. The study inferred the gas separation mechanism of the TR
membrane based on the measured permeation results and related characterizations. Additionally,
membrane
pure based onwas
gas permeance thedefined
measured andpermeation
calculated by results and related
Equation (3) andcharacterizations.
expressed according Additionally,
to the gas
cm3 (STP)
pure gas permeance
permeation unit (GPUwas =1× defined
10 −6 and
2
calculated
). by Equation (3) and expressed according to the gas
cm ·s·cmHg
3
𝑐𝑐𝑐𝑐 (𝑆𝑆𝑆𝑆𝑆𝑆)
permeation unit (GPU = 1 × 10−6 ). "
𝑐𝑐𝑐𝑐 2 ∙𝑠𝑠∙𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
#
dp V·T0
P = 𝑑𝑑𝑑𝑑 𝑉𝑉 ∙ 𝑇𝑇 (3)
0
P = [ dt ] A·∆p·P0 (3)
𝑑𝑑𝑑𝑑 𝐴𝐴 ∙ Δ𝑝𝑝 ∙ 𝑃𝑃0
where P represents the gas permeation value (GPU), dp/dt represents the increased rate of the
where P represents
downstream pressure the
at a gas permeation
steady state (cm value V refersdp/dt
Hg/s), (GPU), to therepresents the volume
downstream increased
(cm rate
3 ), Tofis the
the
downstream pressure at a steady state (cm Hg/s), V refers to the downstream volume
permeation temperature (K), A is the effective area of the membrane (cm ), ∆p represents the pressure
2 (cm 3), T is the

permeation temperature sideAand

the feed(K), is the effective area ofofthe
themembrane
membrane(cm(cm),Hg), represents
Δ𝑝𝑝 P the
2
difference between the permeation side 0 is 76 cm Hg,
pressure
and difference
T0 is 273 K. between the feed side and the permeation side of the membrane (cm Hg), 𝑃𝑃0 is
76 cm Hg, and 𝑇𝑇 is 273 K.
The equation0for selectivity calculation is as follows:
The equation for selectivity calculation is as follows:
P
αi/ j = 𝑃𝑃i𝑖𝑖 (4)
𝛼𝛼𝑖𝑖/𝑗𝑗 =P j (4)
𝑃𝑃𝑗𝑗
where αi/ j represents the ideal selectivity of pure gas i over j. Pi and P j are the permeance value of gas
where 𝛼𝛼𝑖𝑖/𝑗𝑗 represents the ideal selectivity of pure gas i over j. 𝑃𝑃𝑖𝑖 and 𝑃𝑃𝑗𝑗 are the permeance value of
i and gas j, individually.
gas i and gas j, individually.

Figure2.2.Schematic
Figure Schematicof
of gas
gas permeation
permeation apparatus.
Polymers 2020, 12, 2540 6 of 15

3. Results and Discussion

3.1. Analysis of As-Received Rubber Sample

The TGA analysis of commercial styrene–butadiene rubber (SBR) and reclaimed rubber were
investigated by the TGA and their proximate compositions are shown in Figure 3. As expected, prior to
heating to a temperature of 700 ◦ C, commercial SBR suffered the greatest weight loss and finally
decomposed completely at approximately 500 ◦ C, which suggests that its whole composition consisted
of polymer, that is, rubber. As presented in Figure 3a, for reclaimed rubber, the initial decomposition
temperature (Td) was 343 ◦ C and the weight-loss curve displayed a two-stage degradation process.
The primary weight-loss was observed at approximately 350 ◦ C, while the secondary weight loss
was at approximately 750 ◦ C, which implied at least two different compositions existing in the
reclaimed rubber sample (i.e., polymer and carbon black). When the temperature reached 900 ◦ C,
approximately 11% of the sample weight remained, which was indicative of the presence of another
filler. In addition, the initial decomposition temperature for reclaimed rubber is lower than that of
commercial SBR, which suggests the presence of an impurity such as carbon black or another filler.
As a result, based on the weight loss percentages corresponding to the degradation temperature,
the approximate composition of reclaimed rubber was determined (Figure 3b). As anticipated, polymer
accounted for 57% of the reclaimed rubber sample. Thus, using reclaimed rubber as a membrane
precursor was feasible because of the abundant rubber polymer in the overall sample. Carbon black,
which accounted for 32% of the reclaimed rubber, was the minor ingredient. A tire generally consists
of 40–48% rubber polymer [13,14], and our findings show that the rubber polymer content is increased
in reclaimed rubber. Additionally, a change in the functional group of the as-received rubber samples
before and after devulcanization was detected using the FTIR technique to gain insight into the rubber
sample properties (Figure 4). For the infrared spectroscopy of crumb rubber, the characteristic peaks at
3100–2800, 1540, 1500–1380, 990–910, 780–660, and 700–590 cm−1 were associated with the stretching
vibration of C–H bonds, the stretching vibration of C=C bonds, C–H vibration, =C–H bands, aromatic
C–H bonds, and C–S bonds, respectively [23]. The spectra for reclaimed rubber revealed that the
characteristic peaks of C–H bonds and C=C bonds were increasingly apparent, and the intensity of
C–S bonds was negligible, which mirrored the validity of the devulcanization procedure and validated
the increase in the rubber polymer content of reclaimed rubber. In addition, the rubber type of the
collected specimen from the local market was shown to be styrene–butadiene rubber because the
detected functional groups of the rubber sample were similar to those of styrene–butadiene rubber
from previous studies [24,25]. Due to the existence of carbon black and other fillers in the adopted
precursor (reclaimed rubber), the light scattering degree would be affected by the black substance.
Therefore, the typical peak of sulfur bridges is not easy to detect by the FTIR technique. As a result,
the effect of devulcanization on reclaimed rubber was evaluated by the change in cross-linking density
between rubber and reclaimed rubber. The cross-linking densities of both rubber samples, as reported
in Table 1, were tested by the combination of the swelling method in the ASTM D6814 standard and
the Flory–Rehner equation [19,20]. The devulcanization degree for reclaimed rubber, calculated by
Equation (2), was 45.5%.
 Polymers2020,
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2020,12, x FOR PEER REVIEW 77 of
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16

Polymers
120
2020, 12, x FOR PEER REVIEW 7 of 16
(a) styrene-butadiene rubber
120 (b)
(a)
reclaimed rubber (a2)
100 styrene-butadiene rubber
(b)
reclaimed rubber (a2)
100
Residual weight (%)

80 Td:343.68 °C
Residual weight (%)

80 Td:343.68 °C
60
carbon black
60
40 carbon black

40
20
polymer
20
0 polymer
0 100 200 300 400 500 600 700 800 900
0
0 100 200
Temperature
300 400
(°C)
500 600 700 800 900

Temperature
Figure 3. (a) TGA curve (°C)
of commercial styrene–butadiene rubber and reclaimed rubber and (b)
approximate
Figure
Figure 3. 3. weight
(a)(a)
TGATGA composition
curve
curve of of of reclaimed
commercial
commercial rubber sample.rubber
styrene–butadiene
styrene–butadiene rubber and
and reclaimed
reclaimed rubber
rubber andand
(b)(b)
approximate
approximate weight
weight composition
composition of reclaimed
of reclaimed rubber
rubber sample.
sample.

Figure4.4. FTIR
Figure FTIR spectra
spectra of
of rubber
rubbersamples
samplesbefore
beforeand
andafter
afterdevulcanization.
devulcanization.
Figure1.4.Property
Table FTIR spectra of rubber
of rubber samples
samples beforebefore and devulcanization.
and after after devulcanization.
Table 1. Property of rubber samples before and after devulcanization.
SampleTable 1. Property
Cross-Linking Density −7 mol/cm3 )
(10before Devulcanization (%)
Sample of rubber samples and after devulcanization.
Cross-Linking Density (10−7 mol/cm3) Devulcanization (%)
Crumb Rubber 2.233 -
Crumb Rubber
Sample 2.233
Cross-Linking1.217
Density (10−7 mol/cm3) -
Devulcanization (%)
Reclaimed Rubber 45.50
Reclaimed
Crumb Rubber
Rubber 1.217
2.233 45.50-
Reclaimed
3.2. Effect Rubber
of Reclaimed Rubber Precursor Concentrations1.217on Gas Separation Performance 45.50
3.2. Effect of Reclaimed Rubber Precursor Concentrations on Gas Separation Performance
3.2.
AsEffect
As shown of Reclaimed
shown Rubber
in Figure
in Figure
5, the
5, thePrecursor Concentrations
gas permeance
gas permeance
of allonTR
of all TRGasmembranes
Separation Performance
membranes
with different precursor
with different precursor
concentrations decreased in the following order: H2 (2.89 Å) > CH4 (3.80 Å) > N2 (3.64 Å) >
As shown in Figure 5, the gas permeance of all TR membranes >with
concentrations decreased in the following order: H 2 (2.89 Å) > CH 4 (3.80 Å) N2 (3.64 Å) > O
different 2 (3.46
precursor
O2 (3.46 Å) > CO2 (3.2 Å), where the values in parentheses represent the kinetic diameter. Evidently,
> CO2 (3.2 Å),decreased
Å)concentrations where theinvalues in parentheses
the following order: Hrepresent
2 (2.89 Å) the
> CH kinetic
4 (3.80 diameter. Evidently,
Å) > N2 (3.64 Å) > O2the(3.46
the change in gas permeance for all rubber-derived TR membranes was uncorrelated with the kinetic
change in gas permeance for all rubber-derived TR membranes was uncorrelated
Å) > CO2 (3.2 Å), where the values in parentheses represent the kinetic diameter. Evidently, with the kineticthe
diameter of tested gas. Moreover, all TR membranes exhibited higher selectivity over H2 /CO2 ,
diameter
change of intested gas. Moreover,
gas permeance for allallrubber-derived
TR membranesTR exhibited higher
membranes selectivity
was over Hwith
uncorrelated 2/COthe
2, Hkinetic
2/N2,
H2 /N2 , and H2 /CH4 separations than CO2 /N2 and CO2 /CH4 separation. The dominant gas separation
and H 2 /CH 4 separations than CO 2 /N 2 and CO 2 /CH 4 separation. The dominant
diameter of tested gas. Moreover, all TR membranes exhibited higher selectivity over H2/CO2, H2/N2, gas separation
mechanism for the membrane depends on the magnitude of the membrane pore. The Knudsen
mechanism
and H2/CH for the membrane
4 separations than depends
CO2/N2onand theCOmagnitude of the membrane
2/CH4 separation. pore. The
The dominant gas Knudsen
separation
diffusion
mechanism model, forasthe
a kind of gas transport
membrane dependsmechanism, governsof
on the magnitude thethe
gasmembrane
separation pore.
process when
The the
Knudsen
diffusion model, as a kind of gas transport mechanism, governs the gas separation process when the
Polymers 2020,12,
Polymers2020, 12,x2540
FOR PEER REVIEW 8 8ofof16
15
Polymers 2020, 12, x FOR PEER REVIEW 8 of 16
effective pore size of the membrane is smaller than the mean free path of penetrates, thus resulting
effective
diffusion
in the linearpore
model, sizeasofa the
relationship kind membrane gasispermeance
of gas transport
between smaller thanandthe
mechanism, mean
thegoverns
square free
the path
root gas of penetrates,
separation
of the reciprocal thusmolecular
process
gas resulting
when the
in the linear
effective
weight pore relationship
[26,27]. size of the
To further between
membrane gas permeance
investigate is the gasand
smaller than the squaremechanism
the mean
separation freeroot of the reciprocal
path of penetrates, gas molecular
thus
of rubber-derived resulting
TR
weight [26,27].
in the
membranes,linear To furthertheinvestigate
relationship
we compared between gas
gas permeance the gas
permeance and
to theseparation
the square
square root mechanism
root of the of rubber-derived
reciprocal
of the reciprocal gas TR
molecular
gas molecular
membranes,
weight (Figure
weight [26,27]. we Tocompared
6). further
As thecorrelations
gas permeance
investigate
expected, the gaswere to
separation the square
observed mechanism root of
between ofrubber-derived
the the permeance
gas reciprocal TR gas
value molecular
membranes,
and the
weight
we compared
square (Figure
root 6). gas
of the
the As expected,
permeance
reciprocal correlations
gas to the square
molecular were root
weightsobserved
of for
the all between
reciprocal the
TR membranesgasgas permeance
molecular
fabricated value
weight and the
at (Figure
different6).
square
precursor root
As expected, of the reciprocal
correlations
concentrations werewt
(4–7 gas %). molecular
observed Theirbetween weights
coefficientsthe gasfordetermination,
of all TR membranes
permeance value andfabricated
labeled the square
R2, were atroot
in different
the of the
range
precursor
reciprocal
of 0.98–0.99. concentrations
gas As a result,(4–7
molecular the wt
weights %). Their coefficients
for all
predominant TR membranes
gas separation of determination,
fabricatedmechanismlabeled
at differentfor all Rrubber-derived
precursor
2 , were in the range
concentrationsTR
2 , were in the range of 0.98–0.99. As a result,
of
(4–70.98–0.99.
wt %). As
Their a result,
coefficients theofpredominant
determination, gas separation
labeled R
membranes was confirmed as Knudsen diffusion. The permeation of hydrogen of all rubber-derivedmechanism for all rubber-derived TR
membranes was
the predominant
membranes was confirmed
gas separation
higher than as Knudsen
mechanism
that of carbondiffusion.
for all The permeation
indicatingofthat
rubber-derived
dioxide, TR hydrogen
membranes of all rubber-derived
the rubber was confirmed
polymer was as
membranes into
Knudsen
transformed was the
diffusion. higher
The
unique than
permeation that of carbon
microporousof hydrogen
structuredioxide,
of of TR indicating
all membrane that
rubber-derived after the
membranes rubber
thermal was polymer
higher
treatment duewas
than that
to
transformed
of
the carbon
presence of into
dioxide, the unique
indicating
aromatic chains microporous
that the rubber
in as-received structure
polymer
reclaimed of TR
was membrane
transformed
rubber after thermal
into
(SBR confirmed the uniquetreatment
in previous due to
microporous
section),
the
ratherpresence
structurethan of membrane
of dense
TR aromatic
rubberchains in as-received
after thermal
polymeric treatment
membrane. reclaimed
due toregard
With rubber
the to(SBR
presencethe ofconfirmed
aromatic
lower in previous
chains
experimental section),
in as-received
selectivity
rather
reclaimed
than thanrubber
theoreticaldense rubber
(SBR
values, thispolymeric
confirmed may in membrane.
beprevious to With
ascribedsection), regard
rather
the presence toofthe
than dense lower
surface rubberexperimental
polymeric
diffusion because selectivity
membrane.
of the
than theoretical
With regard
permeation to thevalues, this
temperaturelower (28  ± may
experimental be ascribed
2  °C). selectivity
The presence to theofpresence
than a surfaceof
theoretical surface effect
values,
diffusion diffusion
this may be
weakensbecause the of
ascribed to the
the
other
◦ C). The presence of a
permeation(Knudsen
presence
mechanism of temperature
surface (28  ±  2  °C). The presence of a surface diffusion effect weakens the other
diffusion
diffusion). because of the permeation temperature (28 ± 2
mechanism
surface diffusion(Knudsen effectdiffusion).
weakens the other mechanism (Knudsen diffusion).
5000 5.0
(a) C4-P0-T350 (b)
5000 5.0 C4-P0-T350
4.5
(a) C5-P0-T350 (b) C5-P0-T350
C4-P0-T350 C4-P0-T350
4000 C6-P0-T350 4.5
4.0 C6-P0-T350
C5-P0-T350
(GPU)

C5-P0-T350
C7-P0-T350 C7-P0-T350
4000 C6-P0-T350 4.0
3.5 C6-P0-T350
(GPU)

(a) (a)

C7-P0-T350 C7-P0-T350
Permeance

3.5
Selectivity

3000 3.0
Permeance

Selectivity

3000 3.0
2.5

2000 2.5
2.0
GasGas

2000 2.0
1.5

1000 1.5
1.0

1000 1.0
0.5

0 0.5
0.0
H2 CO2 O2 N2 CH4 H2/CO2 H2/N2 H2/CH4 O2/N2 CO2/N2 CO2/CH4
0 0.0
H2 CO2 O2 N2 CH4 H2/CO2 H2/N2 H2/CH4 O2/N2 CO2/N2 CO2/CH4
Figure 5. Gas separation performances obtained from resultant thermally rearranged (TR)
Figure 5. Gas
membranes with separation
different performances
precursor obtained from
concentrations. resultant
(a: single thermally rearranged
gas permeance; (TR)
Figure 5. Gas separation performances obtained from resultant thermally rearrangedb:(TR)selectivity
membranesof
membranes
different gas with different precursor concentrations. (a: single gas permeance; b: selectivity of
pairs).
with different precursor concentrations. (a: single gas permeance; b: selectivity of different gas pairs).
different gas pairs).
CO2 O2 N2 CH4 H2
5000
CO2 O2 N2 CH4 H2
5000 C4-P0-T350 R² = 0.9883
C4-P0-T350 R² == 0.9987
R² 0.9883
(GPU)

4000 C5-P0-T350
R²==0.99
0.9987
permeance(GPU)

4000 C5-P0-T350
C6-P0-T350 R²
C6-P0-T350
C7-P0-T350 R² = 0.99
R² = 0.9892
3000 R² = 0.9892
C7-P0-T350
3000
permeance

2000
2000
Gas

1000
Gas

1000
0
00.0 0.2 0.4 0.6 0.8
0.0Square root of
0.2the inverse of
0.4gas molecular
0.6weight, 0.8
Square root of the inverse of gas molecular weight,
Figure
Figure 6. Single gas
6. Single gaspermeance
permeance of of different
different gases
gases obtained
obtained from from resultant
resultant TR membranes
TR membranes with
with different
Figure 6.precursor
different
precursor Single gas permeance
concentrations
concentrations of
as adifferent
as a function of squaregases
function ofroot obtained
square
of root offrom
inverse gasresultant
ofinverse TR membranes
of gas molecular
molecular weights. with
weights.
different precursor concentrations as a function of square root of inverse of gas molecular weights.
Polymers 2020, 12,
Polymers 2020, 12, x2540
FOR PEER REVIEW 9 9of
of 16
15

3.3. Effect of Heating Temperature on Gas Separation Performance

3.3. Effect of Heating Temperature on Gas Separation Performance
The results of pure gas permeation obtained at different heating temperatures showed no
apparent difference
The results of pure when compared to
gas permeation that obtained
obtained at differentfrom a different
heating precursor
temperatures showed concentration,
no apparent
because
differencethewhengas compared
permeation to order was thefrom
that obtained same (Figure 7).
a different Consequently,
precursor the gasbecause
concentration, transport
the
mechanism
gas permeation of TRorder
membraneswas thewas still(Figure
same Knudsen 7).diffusion when the
Consequently, theheating temperature
gas transport shiftedof
mechanism from
TR
350 to 250 °C.
membranes wasWe stillalso observed
Knudsen that the
diffusion when gasthepermeance of resultantshifted
heating temperature membranes from 350 at atoheating
250 ◦ C.
temperature
We also observedof 350that
°C, regardless of precursor
the gas permeance concentration,
of resultant membranes were higher compared
at a heating with membranes
temperature of 350 ◦ C,
at a heating
regardless oftemperature of 250 °C. Inwere
precursor concentration, the higher
heatingcompared
process at with350membranes
°C, the bulking rings create
at a heating more
temperature
space
of 250to◦ C.
provide
In the gases
heating diffusion
processbecause
at 350 ◦of C, the
the higher
bulkingthermal conversion;
rings create therefore,
more space the effect
to provide of
gases
heating
diffusiontemperature
because of the on higher
the as-prepared membranetherefore,
thermal conversion; is a crucial thefactor. In heating
effect of addition, the selectivity
temperature of
on the
the H2/CO2 gas
as-prepared pair obtained
membrane for all
is a crucial TR membranes
factor. In addition, the as aselectivity
function of precursor
of the H2 /CO2concentration
gas pair obtained and
heating
for all TRtemperature
membranesisasplotted in Figure
a function 8. As shown
of precursor in Figureand
concentration 8, the selectivity
heating temperatureof all membranes,
is plotted in
regardless
Figure 8. As of shown
heatingintemperature,
Figure 8, thewas in the range
selectivity of all of 2.4–3.5, which
membranes, indicates
regardless that thetemperature,
of heating influence of
altering
was in the the precursor
range of 2.4–3.5, concentration
which indicates or heating
that the temperature on membrane
influence of altering the precursor permselectivity
concentration is
insignificant. This inferson
or heating temperature that the pore permselectivity
membrane size distinguishing between bigger
is insignificant. Thisgases
infers(CO that2) the
andpore
smaller
size
gases (H2) would
distinguishing not bebigger
between substantially
gases (CO shrunk
2 ) andor enlarged
smaller gases with
(H2 )the changes
would not beinsubstantially
both parameters. shrunkThe or
lower
enlargedselectivity
with theof the TRin
changes membrane was observed
both parameters. The lowerwhen the precursor
selectivity concentration
of the TR membrane was was observed
too high
(6 andthe
when 7 wt %); this concentration
precursor could be correlated was too with
high the(6 derived
and 7 wtmembrane
%); this could thickness. Basedwith
be correlated on the thework
derivedby
D. Grosso [28],
membrane the degree
thickness. Basedofon heat
the for
work thebymembrane
D. Grosso surface
[28], theanddegreethe of
membrane
heat for the interior
membrane was uneven
surface
in
andthethecarbonization
membrane interiorprocesswas and non-selectivity
uneven pores wereprocess
in the carbonization produced and as a result. Consequently,
non-selectivity pores were
while
producedthe membrane
as a result. was fabricated while
Consequently, with higher concentration
the membrane and higher
was fabricated withheating
highertemperature,
concentration a
suppression in H2/CO
and higher heating 2 selectivityawas
temperature, observed.in H2 /CO2 selectivity was observed.
suppression

Figure 7. Single
Figure 7. Singlegas
gaspermeance
permeance of different
of different gasesgases obtained
obtained from resultant
from resultant TR membranes
TR membranes with
with different
different heating temperatures.
heating temperatures. (a: 4 wt % b:
(a: 4 wt % precursor; precursor; b: 5 wt %c:precursor;
5 wt % precursor; c: 6 wt d:
6 wt % precursor; % precursor; d: 7 wt
7 wt % precursor).
% precursor).
Polymers 2020, 12, 2540 10 of 15
Polymers 2020, 12, x FOR PEER REVIEW 10 of 16

4
T=250
T=350

H2/CO2 selectivity (α)

2

0
3 4 5 6 7 8
Polymer conc. (wt. %)

Figure 8.
Figure 8. Selectivity
Selectivity over
over H /CO22 gas
H22/CO gaspair
pairof
ofresultant
resultantTR
TRmembranes
membranes fabricated
fabricated with
with different
different heating
heating
◦ C; the icon in red represents the
temperatures. (The icon in black represents the temperature at 250 °C; the icon in red represents the
temperatures. (The icon in black represents the temperature at 250
◦ C).
temperature at
temperature at 350
350 °C).
3.4. Effect of PPO Additive Content on Gas Separation Performance
3.4. Effect of PPO Additive Content on Gas Separation Performance
Figure 9 shows the influence of incorporating PPO additive into the rubber precursor on the
Figure 9 shows the influence of incorporating PPO additive into the rubber precursor on the
morphological structure of the derived TR membrane. No observable cracks were observed on the
morphological structure of the derived TR membrane. No observable cracks were observed on the
membrane surface of C7-P2.8-T250 compared with other TR membranes. Furthermore, the reduction
membrane surface of C7-P2.8-T250 compared with other TR membranes. Furthermore, the reduction
of membrane surface roughness from 147 nm to 49.8 nm indicated a significant densification of the
of membrane surface roughness from 147 nm to 49.8 nm indicated a significant densification of the
membrane surface after incorporating the PPO additive at 2.8 wt %. As expected, by adding the
membrane surface after incorporating the PPO additive at 2.8 wt %. As expected, by adding the PPO
PPO modifier into membrane matrix, the membrane surface became smoother. The AFM results
modifier into membrane matrix, the membrane surface became smoother. The AFM results
corroborated this finding, indicating that the membrane was successfully modified by the presence
corroborated this finding, indicating that the membrane was successfully modified by the presence
of PPO.2020, 12, x FOR PEER REVIEW
Polymers 11 of 16
of PPO.
As shown in Figure 10, the C7-P2.8-T250 TR membrane exhibited the highest selectivity for all
gas pairs. Specifically, H2/CO2 selectivity differed nearly by a factor of two and was observed to be 4
and 2.68 for C7-P2.8-T250 and C7-P0-T250, respectively. These findings indicate that the
incorporation of PPO additive enhanced the permselectivity of the derived TR membrane for H2/CO2.
These results can be attributed to the dense membrane structure obtained by blending a thermally
stable polymer, in this case PPO, and are in accordance with previous studies [29,30]. According to
the work of Ozaki [31], the pore structure of a carbon membrane is strongly influenced by polymeric
precursors, and their thermal properties are vital in determining the derived carbon membrane
performance. During thermal treatment, a thermally liable polymer precursor tends to decompose
into volatile gas. This provides a diffusion path for gas, leading to an increase in permeance and a
decrease in selectivity. The opposite trend in terms of gas permeance and selectivity was observed
for the thermally stable polymer in this study. Hence, the addition of a thermally stable polymer (PPO,
in this study) improved the resultant TR membrane’s selectivity because of the thermal stable
property of the PPO during the heating procedure.

Figure
Figure 9.
9. SEM
SEMimages
images(1) (1) of
of rubber-derived
rubber-derived TR
TR membranes
membranes as as aa function
function of
of polyphenylene
polyphenylene oxide
oxide
(PPO)
(PPO) additive
additive content
content and
and corresponding
corresponding atomic
atomic force
force microscopy
microscopy (AFM)
(AFM) images
images (2).
(2). (a:
(a:C7-P0-T250;
C7-P0-T250;
b:
b: C7-P0.7-T250;
C7-P0.7-T250; c:c: C7-P2.8-T250).
C7-P2.8-T250).
Polymers 2020, 12, x FOR PEER REVIEW 11 of 16

Polymers 2020, 12, 2540 11 of 15

As shown in Figure 10, the C7-P2.8-T250 TR membrane exhibited the highest selectivity for all gas
pairs. Specifically, H2 /CO2 selectivity differed nearly by a factor of two and was observed to be 4 and
2.68 for C7-P2.8-T250 and C7-P0-T250, respectively. These findings indicate that the incorporation of
PPO additive enhanced the permselectivity of the derived TR membrane for H2 /CO2 . These results
can be attributed to the dense membrane structure obtained by blending a thermally stable polymer,
in this case PPO, and are in accordance with previous studies [29,30]. According to the work of
Ozaki [31], the pore structure of a carbon membrane is strongly influenced by polymeric precursors,
and their thermal properties are vital in determining the derived carbon membrane performance.
During thermal treatment, a thermally liable polymer precursor tends to decompose into volatile gas.
This provides a diffusion path for gas, leading to an increase in permeance and a decrease in selectivity.
The opposite trend in terms of gas permeance and selectivity was observed for the thermally stable
Figure
polymer 9. SEM
in this images
study. (1) of
Hence, therubber-derived TR membranes
addition of a thermally stableaspolymer
a function of polyphenylene
(PPO, in this study) oxide
improved
(PPO) additive
the resultant content and selectivity
TR membrane’s corresponding atomicofforce
because the microscopy (AFM)
thermal stable images of
property (2).the
(a: C7-P0-T250;
PPO during the
b: C7-P0.7-T250;
heating procedure. c: C7-P2.8-T250).

Figure 10. Gas separation performances obtained from rubber-derived TR membranes as a function of
Figure 10. Gascontent.
PPO additive separation performances
(a: single obtained
gas permeance; b:from rubber-derived
selectivity of differentTR membranes
gas pairs). as a function
of PPO additive content. (a: single gas permeance; b: selectivity of different gas pairs).
3.5. Comparison of Rubber-Derived TR Membrane with Other Published Literature
3.5. Comparison of Rubber-Derived TR Membrane with Other Published Literature
Table 2 compares the gas separation performance of the TR membrane derived from reclaimed
rubberTable 2 compares
to that the gas separation
of TR membranes performance
derived from expensiveofprecursors
the TR membrane derived
[9,10,32–35]. The from reclaimed
rubber-derived
rubber
membraneto that
at of TR membranes
a lower derived from expensive
thermal rearrangement precursors
temperature [9,10,32–35].
(250 ◦ C) The rubber-derived
was comparable to other TR
membrane
membranesat a lower with
fabricated thermal rearrangement
expensive temperature
polymer precursors (250 °C)
at higher was comparable
heating temperaturestobecause
other TR
of
membranes
its acceptablefabricated with
selectivity, expensive
remarkable polymerpermeability,
hydrogen precursors atand
higher heating temperatures
competitive because of
and feasible commercial
its acceptable
properties. As theselectivity,
hydrogen remarkable hydrogen
capacity of the permeability,
demonstration and competitive
plant in Japan and the
is 50 Nm3 /h [36], feasible
plant
needs a membrane with high flux but a reasonable separation factor for hydrogen enrichment.
The C7-P2.8-T250 membrane synthesized during this work, with a hydrogen permeability of
1333 Barrer, exhibits a similar hydrogen permeance to membranes applied in a biogas plant [37].
that the gas transport capability of the rubber-derived membrane (C7-P2.8-T250) lies in the upper-
right quadrant of Figure 11 and crosses the upper limit for H2/CO2 applications, showing that it can
be recognized as an attractive candidate for H2/CO2 gas separation.
The practical feasibility for the membrane’s commercial application was preliminarily evaluated
from the perspective of price per unit membrane area (USD/m2). The price per unit membrane area
Polymers 2020, 12, 2540 12 of 15
(USD/m2) was determined by the cost of the raw material, including the polymer precursor, and the
used solvent and additive, etc. Table 3 summarizes the data and assumptions employed in this study.
The costthe
Hence, of as-prepared
required solvent per ton with
membrane rubberhighequals
flux USD 50,309.4/ton,
has potential which was calculated
for application from the
in the commercial
solvent
H 2 /CO 2 price multiplied
gas-separation by
field.the rubber
The binarysolubility
gas mixturein solvent.
test The
will becost of raw
performed materials
in our ranged
future workfromto
USD 51,864.40
better understand to USD 52,975.40/ton,
the separation whichof
capability was obtained by summing
rubber-derived membranes. the price of reclaimed rubber
[38] In and the costfor
addition, of membrane
required solvent and the
scientists, subtracting
Robeson the uppervalue of national
bound aid. The price
set the appealing targetper unit
to aim
membrane
for and is a area (USD/m
commonly 2) instandard
used this workwith
waswhich
calculated to be 2.1–3.2
to evaluate USD/m
the gas 2, which
separation was acquired
performance by
in the
multiplying
field the cost
of polymeric of raw materials
membranes. To compareand our
the work
required
withpolymer per unit
other studies membrane.
in the field of TRAccording
membranes, to
Richard
the W. Baker
optimum [39], if the result
gas separation adopted precursor
in this is commercial polymer,
work (C7-P2.8-T250) and other these membrane
published modules
studies were
vary in price
illustrated from 10 to
in Robeson 100 (USD/m
upper 2), which
bound plots for H is2 /CO
far more expensive
2 separation. Thethan our figures.
comparison It is clear
clearly that
indicates
the membrane
that prepared
the gas transport with reclaimed
capability rubber is competitive
of the rubber-derived membranein(C7-P2.8-T250)
the capital market.
lies in We believe this
the upper-right
technology
quadrant ofisFigure
worthy 11of
anddevelopment
crosses thein the future
upper limit andfor Hcould
2 /COcontribute to a significant
2 applications, showing that reduction
it can bein
tire waste. as an attractive candidate for H2 /CO2 gas separation.
recognized

1000

Robeson's 2008 upper bound

H2/CO2 permselectivity

100

C7-P2.8-T250
10

PANI/PBI [35] PBI [34]

1
HAB-6FDA [33]
6FDA-HAB5DAM5 [32]
0.1
0.01 0.1 1 10 100 1000 10000 100000
H2 permeability (Barrer)
Figure 11. Robeson
Figure plot for
11. Robeson H2/CO
plot 2 separation
for H comparing the rubber-derived TR membrane with other TR
2 /CO2 separation comparing the rubber-derived TR membrane with
membrane prepared
other TR by different
membrane preparedprecursors.
by different precursors.

The practical feasibility for the membrane’s commercial application was preliminarily evaluated
from the perspective of price per unit membrane area (USD/m2 ). The price per unit membrane area
(USD/m2 ) was determined by the cost of the raw material, including the polymer precursor, and the
used solvent and additive, etc. Table 3 summarizes the data and assumptions employed in this study.
The cost of required solvent per ton rubber equals USD 50,309.4/ton, which was calculated from
the solvent price multiplied by the rubber solubility in solvent. The cost of raw materials ranged
from USD 51,864.40 to USD 52,975.40/ton, which was obtained by summing the price of reclaimed
rubber [38] and the cost of required solvent and subtracting the value of national aid. The price per
unit membrane area (USD/m2 ) in this work was calculated to be 2.1–3.2 USD/m2 , which was acquired
by multiplying the cost of raw materials and the required polymer per unit membrane. According
to Richard W. Baker [39], if the adopted precursor is commercial polymer, these membrane modules
vary in price from 10 to 100 (USD/m2 ), which is far more expensive than our figures. It is clear that
the membrane prepared with reclaimed rubber is competitive in the capital market. We believe this
technology is worthy of development in the future and could contribute to a significant reduction in
tire waste.
Polymers 2020, 12, 2540 13 of 15

Table 2. Comparison of rubber-derived TR membrane with other reports with respect to hydrogen
permeability and H2 /CO2 selectivity.

Thermal Rearrangement Permeability (Barrer) * H2 /CO2

Polymer Reference
Protocols H2 CO2 Selectivity

6FDA-HAB5DAM5 450 ◦ C for 1 h 1318 1607 0.82 [32]

HAB-6FDA 450 ◦ C for 1 h 530 410 1.29 [33]
Aromatic Polyimides 450 ◦ C for 1 h 738 295 2.50 [9]
Poly(benzoxazole-co-imide) 400 ◦ C for 2 h 222.1 172.8 1.29 [10]
Polybenzimidazole (PBI) 450 ◦ C for 1 h 1779 1624 1.1 [34]
PANI/PBI 300 ◦ C for 3 h 3.69 0.242 15.2 [35]
C7-P2.8-T250 250 ◦ C for 2 h 1333 333.25 4.0 This work
*: Barrer = 1 × 10−10 cm3 (STP)cm·cm−2 s−1 cmHg; the C7-P2.8-T250 membrane thickness is 1.116 µm.

Table 3. Summary of material price data and assumptions in this work.

Item
The price of reclaimed rubber [38] USD 1555–2666/ton
The required polymer per unit membrane 4–6 × 10−5 ton/m2
The price of solvent (toluene) USD 0.52/100 mL
The rubber solubility in solvent 1.04 × 10−5 ton reclaimed/100 mL solvent
National aid USD 100/ton reclaimed rubber

4. Conclusions
Our main conclusions are as follows:

(a) The as-received reclaimed rubber was intensively investigated by TGA and FTIR analysis.
The results revealed that the rubber type of reclaimed rubber is styrene–butadiene rubber,
which accounted for more than half of the total components (57%).
(b) The presence of carbon black and other filler was also found, and their presence decreased the
thermal stability of rubber.
(c) We measured the degree of devulcanization and the results showed that reclaimed rubber
exhibited 45.5% devulcanization.
(d) According to the gas permeation tests, all rubber-derived TR membranes exhibited the Knudsen
diffusion mechanism. In particular, the C7-P2.8-T250 membrane, with an ideal H2 /CO2 selectivity
of four and hydrogen permeability of 1333 Barrer, demonstrated a superior gas transport capability,
mainly due to the conversion of the reclaimed rubber layer into a microporous membrane structure
and the incorporation of a thermal stable filler.

In conclusion, these conditions showed that reclaimed rubber has significant potential as a precursor
for fabricating TR membranes for the hydrogen enrichment industry. We have provided a viable approach
to adopt reclaimed rubber as a precursor for preparing TR membranes with high performance for
H2 /CO2 separation.

Author Contributions: Conceptualization, M.-Y.W. and H.-H.T.; validation, G.-L.Z.; investigation, G.-L.Z.;
data curation, Y.-T.L. and G.-L.Z.; writing—original draft preparation, Y.-T.L.; writing—review and editing,
M.-Y.W. and H.-H.T.; visualization, Y.-T.L.; supervision, M.-Y.W. and H.-H.T.; project administration, M.-Y.W. and
H.-H.T.; funding acquisition, M.-Y.W. and H.-H.T. All authors have read and agreed to the published version of
the manuscript.
Funding: This research was funded by Environmental Protection Administration Taiwan (EPAT), Project
No. EPA-104-X05.
Acknowledgments: The authors would like to thank the Environmental Protection Administration Taiwan (EPAT)
(No. EPA-104-X05) for the encouragement and financial support.
Conflicts of Interest: The authors declare that they have no known competing financial interests or personal
relationships that could have appeared to influence the work reported in this paper.
Polymers 2020, 12, 2540 14 of 15

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