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C Journal of
Carbon Research
Communication
Novel Tubular Carbon Membranes Prepared from
Natural Rattans
Xuezhong He
Department of Chemical Engineering, Norwegian University of Science and Technology, NO-7491 Trondheim,
Norway; xuezhong.he@ntnu.no; Tel.: +47-73-593-942
Received: 7 December 2018; Accepted: 29 January 2019; Published: 1 February 2019
Abstract: The novel tubular carbon membranes produced from natural materials are, for the first
time, reported. The novelty of this idea is to use natural rattans as precursors for making carbon
membranes to address the challenges of cellulose polymers. The rattan precursors were carbonized to
present evenly distributed channels inside the tubular carbon membranes. Each channel has an inner
diameter of 2 × 10−4 m with a dense-selective inner layer and a porous outer layer. Future work on
selection of suitable rattans, proper pre-treatment, carbon structure tailoring can be conducted to
open a new research field of carbon membranes/materials.
Keywords: rattan; tubular carbon membrane; carbonization; gas separation
1. Introduction
Membrane technology possesses many advantages such as small footprint, low capital and
operating cost, and being environmentally friendly to be an alternative technology for gas separation
compared to the conventional separation technologies (e.g., cryogenic distillation, chemical and
physical absorption). He et al. reviewed the polymeric and inorganic (carbon, ceramic, metallic, zeolites,
etc.) membranes for various gas separation processes [1], and membrane gas separation is expected
to play an important role in the selected environment and energy processes, such as CO2 capture,
natural gas sweetening, biogas upgrading, and hydrogen purification. The polymeric membranes
are dominating the current industrial gas separation, but the trade-off of permeability/selectivity
as well as the chemical and mechanical stabilities limits their applications in the adverse conditions
(e.g., high pressure and/or high temperature processes). Developing alternative carbon membranes
shows a nice potential.
Carbon membranes are ultra-microporous inorganic membranes made from the carbonization of
polymeric precursors such as polyimide, polyacrylonitile (PAN), poly(phthalazinone ether sulfone
ketone), poly(phenylene oxide) and cellulose derivatives [2]. In the last decade, great attention
was placed on the development of supported carbon membranes [3,4] and self-support carbon
membranes [5]. Ceramic-supported carbon membranes was reported for high temperature applications
(e.g., H2 /CO2 separation from syngas and carbon membrane reactors) [6]. However, preparation of a
thin, defect-free carbon-selective layer on the top of support, increase of the compatibility between
support and carbon layer and reduction of the production cost are still challenging [7]. Self-supported
flat-sheet and hollow fiber carbon membranes prepared from polyimide precursors for CO2 /CH4 and
olefin/paraffin separation have been reported in the literature [8,9], but the main challenge of the high
production cost due to the non-commercial polyimide polymers hinders the upscaling. The Membrane
Research (Memfo) team at the Norwegian University of Science and Technology (NTNU) developed
the cellulosic-based hollow fiber carbon membranes with relatively good separation performance for
CO2 /N2 , CO2 /CH4 separation [10–14]. However, there are still challenges related to: (1) hollow fiber
precursors drying; (2) module construction due to the fragile and brittle carbon fibers; and (3) low gas
C 2019, 5, 9; doi:10.3390/c5010009 www.mdpi.com/journal/carbon
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permeance
the withbrittle
fragile and a symmetric
carbonstructure.
fibers; andThus, seeking
3) low gas novel precursors
permeance with for preparation
a symmetric of asymmetric
structure. Thus,
carbon membranes with high performance, low cost, good mechanical strength
seeking novel precursors for preparation of asymmetric carbon membranes with high performance, and easy module
construction
low (e.g.,mechanical
cost, good tubular) is essentially
strength and required
easy to bring carbon
module membranes
construction (e.g., into futureisapplications
tubular) essentially
in gas separation
required to bring processes.
carbon membranes into future applications in gas separation processes.
The natural rattan materials have unique tubular structure as shown in Figure 1. For the rattan
plants, water is initially absorbed from the underground and transported through the large channels
from bottom to the top of trunk, and can also pass pass through thethe wall
wall to
to the
the branches
branches (further
(further to
to leafs),
leafs),
which indicates a porous structure along the channel channel wall of of rattan
rattan materials.
materials. The previous work
reported on onthe production
the productionof artificial bonesbones
of artificial from rattan
from woods
rattanbywoods
carbonization at high temperature
by carbonization at high
(e.g., 800–2000 ◦ C) [15]. Moreover, the rattan materials are mainly composed of cellulose, with small
temperature (e.g., 800–2000 °C) [15]. Moreover, the rattan materials are mainly composed of cellulose,
amounts
with smallofamounts
hemicellulose and lignin,
of hemicellulose andand the chemical
lignin, structurestructure
and the chemical of rattanofisrattan
quiteissimilar to the
quite similar
regenerated
to cellulosecellulose
the regenerated hollow fibers.
hollowTherefore, in principle,
fibers. Therefore, in self-supported tubular carbon
principle, self-supported membranes
tubular carbon
can be prepared
membranes by prepared
can be carbonization of rattan materials.
by carbonization of rattan materials.
Figure 1. Cross-section
Cross-sectionofofrattan
rattanmaterials:
materials:(a)(a)
rattans with
rattans withdifferent outer
different diameters
outer (2.75
diameters mmmm
(2.75 to 7.5
to
mm); (b) (b)
7.5 mm); tested rattan
tested (outer
rattan diameter,
(outer do =d3.25
diameter, × 10×m);
−3 − 3
10 (c)m);
SEM(c)image.
o = 3.25 SEM image.
2. Material
2. Material and
and Methods
Methods
−3 m were provided by the Institute of
The natural
The natural rattans
rattans with
with an
an outer
outer diameter
diameter of 3.25×× 10
of 3.25 10−3 m were provided by the Institute of
Process Engineering,
Process Engineering, Chinese
Chinese Academy
Academy ofof Sciences.
Sciences. Acetic
Acetic acid
acid was
was purchased
purchased from
from Sigma-Aldrich
Sigma-Aldrich
(Oslo, Norway). The raw rattan was pre-hydrolyzed using an acetic acid aqueous solution
(Oslo, Norway). The raw rattan was pre-hydrolyzed using an acetic acid aqueous solution (50 (50 vol.%)
vol.%)
at 90 ◦ C overnight to partly remove hemicellulose, and increase the cellulose content in the precursors.
at 90 °C overnight to partly remove hemicellulose, and increase the cellulose content in the
The pre-treated
precursors. The rattan was carbonized
pre-treated rattan wasincarbonized
the furnaceinupthe 550 ◦ C using
to furnace up tothe
550protocol
°C usingreported in the
the protocol
reported in the previous work [14]. Thermogravimetric analysis (TGA) from TA Instruments USA),
previous work [14]. Thermogravimetric analysis (TGA) from TA Instruments (New Castle, DE, (New
model Q500
Castle, DE, and scanning
USA), modelelectron
Q500 microscopy
and scanning(SEM) from Hitachi
electron High Technology
microscopy (SEM) from (TM3030
Hitachitabletop
High
microscope, (TM3030
Technology Lidingø, tabletop
Sweden)microscope,
were used to characterize
Lidingø, Sweden)the were
structure,
usedmorphology and
to characterize property
the of
structure,
rattans and carbon membranes.
morphology and property of rattans and carbon membranes.
3. Results and Discussion
3. Results and Discussion
The Thermogravimetric Analysis (TGA) study on one type of rattan material showed the similar
The Thermogravimetric Analysis (TGA) study on one type of rattan material showed the similar
weight loss compared to the deacetylated cellulose acetate (DCA) precursors reported in our previous
weight loss compared to the deacetylated cellulose acetate (DCA) precursors reported in our previous
work [14] (shown in Figure 2, raw rattan, acetic acid processed rattan (AA (acetic acid pretreated)
work [14] (shown in Figure 2, raw rattan, acetic acid processed rattan (AA (acetic acid pretreated)
rattan), and DCA materials). A relatively low decomposition temperature range (220–320 ◦ C) was
rattan), and DCA materials). A relatively low decomposition temperature range (220–320 °C) was
found due to the present of hemicellulose and lignin in rattan materials compared to the regenerated
cellulose (DCA) precursor (290–350 °C) which contained almost pure cellulose. Pre-hydrolysis ofC 2019, 5 FOR PEER REVIEW 3 of 5
wood using acetic acid at high temperature was reported to partly remove hemicellulose, and
increase Cthe
2019,cellulose
5, 9 content [16], which has also been documented from the TGA 3results of 5 (AA
rattan in Figure 2). Compared to the raw rattan materials, the decomposition temperature of the pre-
treated rattan shifted towards the DCA precursor. The carbonization experiments of pre-treated
found due to the present of hemicellulose and lignin in rattan materials compared to the regenerated
rattan precursors
cellulose (DCA) (i.e.,precursor
rattans(290–350
soaked◦ C) inwhich
a 50 contained
vol.% acetic
almost acid
purefor 2 h) were
cellulose. conducted
Pre-hydrolysis at the final
of wood
temperature
usingof 550acid
acetic °C,atand highthe SEM images
temperature of the cross-sections
was reported to partly removeof carbon membranes
hemicellulose, and increase aretheshown in
cellulose content [16], which has also been documented from the TGA
Figure 3. It was found that rattan precursors can be carbonized under the controlled carbonization results (AA rattan in Figure 2).
Compared to the raw rattan materials, the decomposition
condition and presented the evenly distributed channels inside the tubular carbon membranes temperature of the pre-treated rattan
shifted towards the DCA precursor. The carbonization experiments of pre-treated rattan precursors
(Figure 3a), and each channel (inner diameter, di = 2 × 10−4 m) showed an asymmetric structure with
(i.e., rattans soaked in a 50 vol.% acetic acid for 2 h) were conducted at the final temperature of 550 ◦ C,
a dense-selective
and the SEM inner
imageslayer and
of the a porous (from
cross-sections parenchyma
of carbon membranes cells)
are shownouter in layer
Figure(Figure
3. It was 3b).
found The outer
diameterthatof rattan
the prepared
precursorscarbon membrane
can be carbonized underwasthereduced
controlled tocarbonization
2.2 × 10 mcondition
−3 (shrinkage of around 30%).
and presented
The prepared carbon membranes showed a very porous structure, which indicates thechannel
the evenly distributed channels inside the tubular carbon membranes (Figure 3a), and each processability
(inner diameter, d = 2 × 10 −4 m) showed an asymmetric structure with a dense-selective inner layer
in the preparation of carbon membranes from natural rattan precursors. However, the carbon
i
and a porous (from parenchyma cells) outer layer (Figure 3b). The outer diameter of the prepared
membrane may have defects in the carbon matrix due to the high amount of residual lignin and
carbon membrane was reduced to 2.2 × 10−3 m (shrinkage of around 30%). The prepared carbon
hemicellulose
membranes existing
showedin the rattan
a very porousprecursors. By applying
structure, which indicatesathe proper pre-treatment
processability (to remove most
in the preparation
hemicellulose
of carbon and lignin), afrom
membranes suitable
naturalpost-treatment
rattan precursors. canHowever,
potentially the mitigate the riskmay
carbon membrane of the formation
have
defects inItthe
of microvoids. is carbon
worthmatrix notingduethat
to thethehighinfluences
amount of residual lignin and
of cellulose hemicellulose
content, existing inof rattan
pre-treatment
the rattan precursors. By applying a proper pre-treatment (to
precursors and carbonization procedure (especially final temperature, heating rate, etc.) remove most hemicellulose and lignin),
are expected
a suitable post-treatment can potentially mitigate the risk of the formation of microvoids. It is worth
to be crucial to prepare high selective carbon membranes. The understanding on how the pore
noting that the influences of cellulose content, pre-treatment of rattan precursors and carbonization
structureprocedure
can be tuned by the
(especially employment
final of the pre-treatment
temperature, heating for the
rate, etc.) are expected to precursor
be crucial toandprepareoptimization
high of
carbonization
selective procedure is also very
carbon membranes. The important.
understanding It on
should
how the be pore
noted that the
structure canfocus
be tunedof this work is to
by the
employment
report the preparation of theofpre-treatment for the precursor
carbon materials from anda newoptimization of carbonization
biorenewable precursor procedure is also and no
of rattans,
very important. It should be noted that the focus of this work is
systematic gas permeation testing and characterization are included. Thus, the extended researchto report the preparation of carbon
materials from a new biorenewable precursor of rattans, and no systematic gas permeation testing
work on selection of suitable rattans, proper pre-treatment, carbon structure tailoring should be
and characterization are included. Thus, the extended research work on selection of suitable rattans,
further investigated
proper pre-treatment,to open a new
carbon research
structure field
tailoring in the
should be development
further investigated of natural
to open arattan-based
new research carbon
membranesfield for
in thegas separation.
development of natural rattan-based carbon membranes for gas separation.
Figure 2.Figure 2. The results
The TGA TGA results of rattan(dark
of rattan (dark line),
line),AA
AArattan (blue(blue
rattan dasheddashed
line), andline),
DCA and
(pink DCA
dashed(pink
line). dashed
line).C 2019, 5, 9 4 of 5
C 2019, 5 FOR PEER REVIEW 4 of 5
3. SEM images of the tubular carbon membranes from the rattan
Figure 3. rattan precursor:
precursor: (a) the whole
−3−m);
tubular (doo == 2.2
2.2 ××1010 3 m);
(b)(b)
single channel
single (di(d
channel = i2×10
=2× 10−4 m).
−4 m).
4. Conclusions
4. Conclusions
The
The natural
natural rattan-based
rattan-based carbon
carbon membranes
membranes were
were successfully
successfully prepared
prepared byby carbonization
carbonization of of
tubular rattan at a final temperature of 550 ◦ C. The prepared carbon membranes showed a very porous
tubular rattan at a final temperature of 550 °C. The prepared carbon membranes showed a very
structure. Some defects
porous structure. Somemay existmay
defects in theexist
carbon matrix
in the due matrix
carbon to the presence of lignin
due to the and hemicellulose
presence of lignin and
which need to which
hemicellulose be avoided
need by
to applying
be avoided suitable pre-treatment
by applying suitablemethods. The novel
pre-treatment tubular
methods. Thecarbon
novel
membranes made from natural rattans will open a new research field for the development
tubular carbon membranes made from natural rattans will open a new research field for the of carbon
materials
development for gas separation,
of carbon but for
materials the gas
intensive research
separation, but activities should
the intensive be conducted
research activities to explore
should be
its potential.
conducted to explore its potential.
Contributions: X.H. performed the experiments,
Author Contributions: experiments, data
data analysis,
analysis, and
and writing
writing of
of the
the paper.
paper.
Funding: This research
Funding: This research received
received no
no external
external funding.
funding.
Acknowledgments: This work was conducted in the Department of Chemical Engineering at the Norwegian
University of Science
Acknowledgment: and
This Technology.
work The author
was conducted in the acknowledges
Department of Arne Lindbråthen
Chemical and at
Engineering Yunhan Chu for the
the Norwegian
discussion of the results.
University of Science and Technology. The author acknowledges Dr. Arne Lindbråthen and Dr. Yunhan Chu
Conflicts of Interest:
for the discussion Theresults.
of the author declare no conflict of interest.
Conflicts of Interest: The author declare no conflict of interest.
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