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Sintered metal fibers@carbon molecular sieve

Cite this: RSC Adv., 2017, 7, 37604
membrane (SMFs@CMSM) composites for the
adsorptive removal of low concentration
isopropanol
Yan Shao, *a Huanhao Chen,*b Yibiao Li,a Shan Xiea and Bin Lia

Carbon molecular sieve membranes (CMSM) were fabricated on sintered metal fibers (SMFs) by a template
method using resorcinol–formaldehyde resin as precursor. The morphology and textural properties of the
as-synthesized SMFs@CMSM composite were characterized by FTIR, BET and SEM, respectively. The
adsorption performances of isopropanol in the structured fixed-bed adsorber based on the SMFs@CMSM
Received 6th May 2017
Accepted 19th July 2017
composites were evaluated. The adsorption dynamic results showed that the mass transfer in the
structured fixed-bed has been obviously enhanced via adding the SMFs@CMSM composites in the outlet.
DOI: 10.1039/c7ra04984f
The length of unused bed (LUB) theory and Bed Depth Service Time (BDST) model were also applied to
rsc.li/rsc-advances further analyze the bed utilization efficiency and adsorption dynamic data.

microbrous entrapped activated carbons.11 Among them,

1. Introduction porous sintered metal bers (SMFs)@inorganic membranes/
Many environmental and health problems are caused by the coatings composites have been widely designed, fabricated
emissions of volatile organic compounds (VOCs).1,2 Specically, and applied in the eld of adsorption and catalysis due to their
isopropanol as one of the most important air pollutants, has large surface area, unique porous network structures, excellent
a toxic effect on human health and causes acute or chronic mass/heat transfer efficiency as well as thermal/chemical
poisoning to humans by prolonged contact.3 Therefore, several stability.12–14 For example, Chen et al.13,14 designed and
methods have been applied to eliminate or recovery VOCs such as prepared gradient SMFs@ZSM-5 zeolite membrane, and also
absorption, thermal catalytic oxidations,4 pervaporation2 and studied its applications in the adsorptive removal and catalytic
photocatalytic oxidation.5 Particularly, adsorption based tech- oxidation of VOCs.
nology has been widely applied to remove VOCs due to its low cost CMSM as one kind of new carbon-based inorganic
and high-efficiency.3 The development of high-efficiency adsor- membrane have a slit-like pore structure, which provides
bents has been always considered as one of the key processes in a unique combination of micropore and ultramicropore
adsorption technology. Various porous materials including acti- networks.15,16 In addition, CMSM is more conducive to indus-
vated carbons,6 zeolites and resin,7 have been applied in the xed- trial applications due to low cost and simple manufacturing
bed adsorber. However, such xed-bed adsorbers loaded with processes comparing with other membrane materials (e.g.
pelleted adsorbents with large particle size possess several draw- zeolite molecular sieve membranes).17 Therefore, SMFs@CMSM
backs including relatively higher mass-transfer resistance and composites will be promising structured adsorbents/catalysts in
bed pressure drop. Therefore, it is necessary to develop novel the eld of adsorption and catalysis. CMSM are usually fabri-
structured adsorbent materials that can be applied in the xed- cated via pyrolysis of polymeric precursors, and various polymer
bed adsorber to enhance mass-transfer. precursors have been applied to determine the CMSM's prop-
Recently, structured porous materials with low mass/heat erties and control their pore structures such as poly-
transfer resistance, low bed pressure drop and high contact- etherimide,18 polyimide,19 polyfurfuryl alcohol,20 phenolic
ing efficiency have attracted more and more attention, resin.21 In particular, resorcinol–formaldehyde resin has been
including zeolite coating/sintered metal bers composites,8,9 recently demonstrated to be an excellent precursor material for
honeycomb material supported zeolite membranes,10 and the fabrication of CMSM due to its considerable xed-carbon
yield, high inherent purity and low cost.22 On the other hand,
ordered mesoporous CMSM with unique and tunable pore
a
School of Chemical and Environmental Engineering, Wuyi University, Jiangmen structures, high surface areas and mechanical stability can be
52920, PR China. E-mail: wyuchemsy@126.com; Tel: +86 07503299397 fabricated by using resorcinol–formaldehyde resin as precursor
b
Mork Family Department of Chemical Engineering and Materials Science, University which can be synthesized via so templates such as
of Southern California, Los Angeles, CA 90089, USA. E-mail: huanhaoc@usc.edu

37604 | RSC Adv., 2017, 7, 37604–37611 This journal is © The Royal Society of Chemistry 2017
Paper RSC Advances

amphiphilic surfactants (e.g. pluronic F-127 and P-123).23 There Table 1 Synthesis conditions for different samples
is currently no published experimental information regarding
Recipe no. R/F127 R/HCl R/F R/EtOH R/water
the design and fabrication of carbon molecular sieve
membranes (CMSM) on the surface of SMFs by using resor- S1 1 : 0.005 1 : 0.18 1.1 8.3 16
cinol–formaldehyde resin as precursor. S2 1 : 0.002 1 : 0.18 1.1 8.3 16
This paper aims to develop novel porous SMFs@CMSM S3 1 : 0.007 1 : 0.18 1.1 8.3 16
composites which can be applied in structured xed-bed for the S4 1 : 0.005 1 : 0.1 1.1 8.3 16
S5 1 : 0.005 1 : 0.3 1.1 8.3 16
low concentration isopropanol removal.

2. Experimental
added to the above solution and stirred for 30 min. Finally, HCl
2.1. Materials
was added as a catalyst to the solution. The molar ratios of the
Sintered metal bers (SMFs) plates (diameter: 20 mm; porosity: solutions were 0.002–0.007F127 : 8.3EtOH : 16water : 1.0R :
0.75
0.05) used as support were supplied by Xian fuerth lter 1.1F : 0.1–0.3HCl. Aer stirring for 6 h, the precursor solution
company (China). Resorcinol (R) was purchased from Guangz- separated into two-phases. The transparent upper phase was
hou Chemical Reagent Factory. Formaldehyde (F, 37 wt%) was ethanol–water rich, which was discarded. The yellow lower
obtained from Guangzhou Donghong Chemical Factory. Plur- phase was polymer-rich resorcinol formaldehyde resin precur-
onic F-127 (EO106PO70EO106) was supplied by Sigma-Aldrich Co. sors. The pretreated SMFs support was impregnated into it for
LLC. HCl was purchased from Dongguan Shuangde Chemical at least 10 min. Subsequently, the resulting support was pre-
Co. Ltd. Ethanol (EtOH) was provided by Tianjin Fuyu Fine heated in an oven at 90  C for 12 h.
Chemical Co. Ltd. Deionized water was used in all synthesis 2.2.3. Carbonization. The obtained brown polymer
process. All of the chemical reagents used in this study were membranes were carbonized under a nitrogen atmosphere with
analytical grade. the ow rate of 80 mL min1. Calcination was carried out at
400  C with a heating rate of 2  C min1 and held at this
2.2. Preparation of SMFs@CMSM composites temperature for 1 h. Then the temperature was increased to
600  C for 2 h with a heating rate of 2  C min1. Aerward, the
2.2.1. Pretreatment of support. The SMFs support was
membranes were allowed cooling down to room temperature.
calcined in air at 550  C for 5 h to form an oxide layer on the
The samples were designated as S1 to S5. The details of
stainless steel bers surface.
synthetic conditions and sample names were showed in Table 1.
2.2.2. Synthesis of resorcinol–formaldehyde resin precur-
sors and coating. The schematic diagram of the preparation of
SMFs@CMSM composites can be seen in Fig. 1. Pluronic F127 2.3. Characterization of SMFs@CMSM composites
was added in ethanol solution and stirred until F127 complete Fourier-transform infrared spectroscopy (FTIR) spectra proles
dissolution. Resorcinol (R) was dissolved in water. Then the two of the as-synthesized samples were recorded in the 500–4000
solutions were mixed and formaldehyde (F) was dropping cm1 range using a Vertex70 spectrometer (Bruker Optics,

Fig. 1 The schematic diagram of the preparation of SMFs@CMSM composites.

This journal is © The Royal Society of Chemistry 2017 RSC Adv., 2017, 7, 37604–37611 | 37605
RSC Advances Paper

Germany) at 4 cm1 resolution. The N2 adsorption–desorption 4. Results and discussion

isotherms were measured at 196  C using Micromeritics tris-
tar 3020 (Micromeritics Instrument Co., USA). All of the samples 4.1. Characterization analysis
were preheated at 150  C for 8 h. The BET surface area of 4.1.1. FTIR. Fig. 2 shows the FTIR spectra of the resorcinol–
SMFs@CMSM composites were calculated using the BET (Bru- formaldehyde resin polymer and carbon molecular sieve parti-
nauer–Emmett–Teller) method. The morphologies of cles prepared using the recipe S1 in Table 1. During the
SMFs@CMSM composites were also obtained by a FEI/Quanta synthesis process, the major reactions between resorcinol and
400 FEG scanning electron microscopy (SEM). formaldehyde include an addition reaction to form hydroxy-
methyl derivatives (–CH2OH), and then a condensation reaction
of the hydroxymethyl derivatives to form methylene (–CH2–)
2.4. Adsorption dynamics of isopropanol in structured xed- bridged compound.21 In addition, the other function of resor-
bed cinol is to develop self-assembly structure with F127 by forming
stable three-dimensional network structure, which is the rudi-
The structured xed bed was lled with granular activated
mental framework of ultimate ordered porous structure in
carbons (GACs) (average particle diameter ¼ 1.5 mm) with a bed
carbon molecular sieve.26
height of 2 cm in the inlet of xed bed, and SMFs@CMSM
As can be seen in the spectrum of original resorcinol–form-
composites (cut into 2 cm diameter) with a bed height of 1 cm in
aldehyde resin polymer in Fig. 2, the reection bands can be
the outlet of xed bed. Specically, the BET surface area of GACs
assigned as follows: the –OH bond (3600–3700 cm1), –C]C–
used in this work is 906 m2 g1.11 For comparison purpose, xed
double bond in aromatic rings (1610 cm1), aromatic C–H (1511
bed with bed height of 3 cm lled with individual GACs was also
cm1), aliphatic C–H (1459 cm1), the O–H in-plane deforma-
designed. The inlet concentrations (C0) of isopropanol were 2,
tion (1383 cm1), the conjunct contribution of the existence of
2.8, 3.6 mg L1 (mixed with air), respectively, while the volu-
C–O–C or ]C–O–C groups (1298 and 1090 cm1) structure in RF
metric ow rates studied in this work were 3, 4, 5 L min1,
resin and F127, and the ring CH wagging by two adjacent
respectively. The inlet and outlet concentrations of isopropanol
hydrogen in 1,4-substituted benzene (843 cm1).26–28 For the
were monitored using an off-line gas chromatography (Agilent
carbon molecular sieve particle spectrum, most the bands in the
7890A, USA) equipped with a ame ionization detector (FID)
spectrum disappeared except for aromatic structure. It can be
and a HP-5 capillary column with N2 as carried gas.
inferred that nonaromatic atoms gradually decompose from the
matrix in the form of H2, CO, and CO2, etc. In the meantime, the
residual structure would be combined and reorganized, leading
3. Mathematical models to the formation of more condensed aromatic structure such as
carbon sheet, turbostratic carbon.27
3.1. The length of unused bed (LUB)
4.1.2. N2 adsorption/desorption isotherm. Fig. 3 and 4
The LUB value represents the length of the mass transfer zone, show the N2 adsorption/desorption isotherms of SMFs@CMSM
which is important in design of adsorption xed bed. It was composites and the corresponding pore sizes distributions
estimated by analyzing breakthrough curve: calculated by the BJH method. The surface area, pore diameter
 tb  and pore volume of the SMFs@CMSM composites are also
LUB ¼ 1  L (1)
t*
where L is total bed height (cm), tb is the breakthrough time
corresponding to C ¼ Cb (where C/C0 ¼ 0.05) and t* is the time
(min) at which C/C0 ¼ 0.5.

3.2. Bed Depth Service Time (BDST) model

The bed depth service time model was rst proposed by Bohart
and Adams in 1920 in their study on the adsorption of chlorine
in charcoal.24 The BDST model can be expressed as a linear
relationship between the service time and the bed depth by
eqn (2):25
 
N0 Z 1 C0
t¼  ln 1 (2)
C0 v Ka C0 Ct

where C0 is the inlet concentration (mg L1), Ct is the outlet

concentration (mg L1) at time the service time t (min), Z is the
bed depth (cm), v is the linear ow rate (cm min1), K is the
adsorption rate constant (L mg1 min1), and N0 is the Fig. 2 FTIR spectra of resorcinol–formaldehyde resin polymer (a), and
adsorption capacity (mg L1). carbon molecular sieve 3 particle (b).

37606 | RSC Adv., 2017, 7, 37604–37611 This journal is © The Royal Society of Chemistry 2017
Paper RSC Advances

Fig. 3 N2 adsorption–desorption isotherms of the SMFs@CMSM composites.

Table 2 Pore characteristics of SMFs@CMSM composites

Average pore BJH adsorption BJH desorption

Recipe no. BET (m2 g1) diameter (nm) volume (cm3 g1) volume (cm3 g1)

S1 60.21 3.48 0.0484 0.0477

S2 5.72 7.85 0.0140 0.0168
S3 13.76 11.77 0.0253 0.0253
S4 64.51 5.17 0.0586 0.0692
S5 60.01 3.96 0.0477 0.0483

presented in Table 2. The N2 adsorption/desorption isotherms to the presence of mesopores. Specically, for materials with
indicate the existence of both micropores and mesopores in pores larger than ca. 5 nm, the width of the hysteresis loop is
SMFs@CMSM composites. It can be seen in Fig. 3 that all of the dependent on their pores quality such as uniformity. For
adsorption isotherms present type IV with obvious increasing of example, MCM-41 with less uniform pore structures usually
adsorbed amount at low relative pressure (P/P0 < 0.1), indicating possesses a relatively broad hysteresis loop.29 The existing of
the presence of micropores in these materials. There is a sharp hysteresis indicates the mesopores-rich of as-synthesized
capillary condensation step at intermediate P/P0 probably due membrane based adsorbents. For SMFs@CMSM composites,

Fig. 4 Pore size distributions of the SMFs@CMSM composites.

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RSC Advances Paper

Fig. 5 SEM micrographs of the SMFs@CMSM composites (a); cross section of the SMFs@CMSM composites: 5000 (b), 10 000 (c) and
20 000 times (d) magnification.

well-dened H2-type hysteresis loops are observed, which the amount of F127 can reduce the surface area and the pore
associated with capillary condensation and desorption sug- volume. It is appropriate to select R : F127 as 1 : 0.005. Very
gesting the formation of worm-like mesopores. The mesopores little change has been observed when the amount of catalyst
will enhance their adsorption capacity as well. The H2-type (HCl) changed according to the BET surface areas of S1, S4 and
hysteresis loop of S1 is smaller than the others owing to their S5. Hence, the factor of catalyst is less important than that of
relatively small mesopore size (3.48 nm, shown in Table 2). As template agent during the synthesis process. The possible
can be seen in Table 2, the BET surface areas of the reason is the strategy of polymer (resorcinol–formaldehyde
SMFs@CMSM composites relied on the amount of template resin) and surfactant (F127) forming an organic–organic inter-
agent (F127) and catalyst (HCl) added. Increasing or decreasing action and the charged polymer chain interacting with the tails

Fig. 6 Breakthrough curves for isopropanol adsorption in structured Fig. 7 Breakthrough curves for isopropanol adsorption in structured
fixed bed and 3 cm conventional GACs fixed bed (inlet concentration fixed bed and 3 cm conventional GACs fixed bed (inlet concentration
¼ 2–3.6 mg L1, flow rate ¼ 4 L min1). ¼ 2.8 mg L1, flow rate ¼ 3–5 L min1).

37608 | RSC Adv., 2017, 7, 37604–37611 This journal is © The Royal Society of Chemistry 2017
Paper RSC Advances

Table 3 Length of unused bed (LUB) for isopropanol adsorption in stainless steel bers. The thicknesses of the CMSM were about
fixed beds 847.8 nm and 985.3 nm, respectively.
Inlet concentration Flow rate
(mg L1) (L min1) Adsorption xed beds LUB (cm)
4.2. Adsorption dynamics
2 4 GAC xed bed 1.1003 4.2.1. Breakthrough curves. The effects of inlet concentra-
Structured xed beda 0.7891 tion and ow rate on the adsorption breakthrough curves of
2.8 4 GAC xed bed 1.0543
Structured xed beda 0.9071
isopropanol over the structured xed bed and 3 cm conven-
3.6 4 GAC xed bed 1.3262 tional GACs xed bed are shown in Fig. 6 and 7, respectively.
Structured xed beda 1.1727 Specically, structured xed bed is lled with 2 cm GAC in the
2.8 3 GAC xed bed 1.0089 inlet and 1 cm SMFs@CMSM composites (S1) in the outlet of
Structured xed beda 0.8029 xed bed. Fig. 6 shows the isopropanol breakthrough curves
2.8 5 GAC xed bed 1.0025
Structured xed beda 1.0022
measured using the inlet concentration of 2–3.6 mg L1 while
a xed ow rate at 2 L min1. Fig. 7 presents the breakthrough
a
Relative to 3 cm structured xed bed lled with 2 cm GAC in the inlet curves measured at different gas ow rate (3–5 L min1), but
of bed and 1 cm SMFs@CMSM composites in the outlet of 2 bed.
keep the inlet isopropanol concentration constant at 2.8 mg
L1. In Fig. 6 and 7, it is clearly shown that the breakthrough
time of isopropanol in two different xed beds decreased with
of the surfactant. Then a thermally decomposition of the
increasing initial concentration and ow rate, which may be
surfactant will form a periodic ordered nanocomposite.30
attributed to a quicker saturation of adsorbent in xed bed at
Specically, in this work, F127 is carbonized by high-
higher inlet concentration and ow rate. Therefore, it can be
temperature calcination under N2 ow to form a carbona-
concluded that the utilization efficiency of adsorbents was
ceous pore wall. Therefore, the amount of F127 affects signi-
decreased with the increasing of inlet concentration and ow
cantly the formation of pore structures in the carbon molecular
rate. As seen in Fig. 6 and 7, it also can be found that the
sieve membranes and their surface areas.
steepness of all breakthrough curves of isopropanol adsorption
In addition, comparing with our previous work, the BET
in structured xed bed are more upright than those in indi-
surface area of SMFs@CMSM composites prepared by the
vidual xed bed at varying concentrations and ow rates. The
template method with resorcinol–formaldehyde resin precur-
increasing steepness of breakthrough curves indicates that the
sors are proved to be twice larger than that of composites
mass transfer in the structured bed has been obviously
prepared using PFA/PEG/acetone precursor, the BET surface
enhanced via adding the SMFs@CMSM composites, which can
area of which is only around 30 m2 g1.31 Based on the results in
be attributed to the shorter internal diffusion path of thin
Table 2, S1 was selected to do the following test and experiment
carbon molecular sieve membrane. The shorter internal diffu-
due to the catalyst playing little effect on the BET surface area.
sion path obviously reduced solid mass transfer resistance. And
4.1.3. SEM. Fig. 5(a) shows the SEM image of
the lm mass transfer area has also been signicantly increased
SMFs@CMSM composites (S1), while Fig. 5(b)–(d) are the cross-
due to the three-dimensional structure of SMFs@CMSM
sectional SEM images of composites. It clearly shows in Fig. 5(a)
composites.13
that the continuous carbon molecular sieve membranes
4.2.2. Determination of LUB. The LUB values were also
covered on the surface of stainless steel bers. The as-
calculated by analyzing the experimental breakthrough curves
synthesized carbon membranes are relatively compact and
of isopropanol in both conventional xed bed and structured
smooth with a little slit. The cross-sectional SEM images indi-
xed bed according to eqn (1), and the results are listed in Table
cate the membranes were successfully covered on the surface of
3. The LUB value represents bed utilization efficiency.32,33 The

Table 4 Parameters of BDST model for isopropanol adsorption in different fixed beds at various flow 1 rates and inlet concentrations

Values of parameters

Inlet concentration (mg L1) Flow rate (L min1) Adsorption xed beds N0 (g L1) Ka (L mg1 min1) R2

2.0 4 GAC xed bed 296.82 0.02056 0.9932

Structured xed beda 305.77 0.03362 0.9931
2.8 4 GAC xed bed 500.85 0.01836 0.9903
Structured xed beda 476.57 0.02457 0.9880
3.6 4 GAC xed bed 423.81 0.01319 0.9932
Structured xed beda 396.90 0.01881 0.9937
2.8 3 GAC xed bed 410.74 0.02095 0.9904
Structured xed beda 385.60 0.02498 0.9884
2.8 5 GAC xed bed 538.39 0.01977 0.9948
Structured xed beda 504.67 0.02490 0.9956
a
Relative to 3 cm structured xed bed lled with 2 cm GAC in the inlet of bed and 1 cm SMFs@CMSM composites in the outlet of bed.

This journal is © The Royal Society of Chemistry 2017 RSC Adv., 2017, 7, 37604–37611 | 37609
RSC Advances Paper

larger value for LUB implies the lower bed utilization. As can be Guangdong (2014KQNCX158), Foundation of the Department
seen in Table 3, comparing with conventional GAC xed bed at of Education of Guangdong Province (2016KTSCX144), Quality
the same operating condition, the LUB values for structured Engineering project of Wuyi University (JG2014025) and Science
xed bed obviously decreased due to the loading of Foundation for Young Teachers of Wuyi University (2015td01).
SMFs@CMSM composites in the outlet. Therefore, it can be
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