Received: 19 July 2021 Revised: 6 November 2021 Accepted: 30 December 2021

DOI: 10.1002/aic.17585

SEPARATIONS: MATERIALS, DEVICES AND PROCESSES

Reverse osmosis and pervaporation of organic liquids using

organosilica membranes: Performance analysis and predictions

Guanying Dong1 | Yatao Zhang1 | Takaaki Sato2 | Hiroki Nagasawa2 |

Masakoto Kanezashi2 | Toshinori Tsuru2

1
School of Chemical Engineering, Zhengzhou
University, Zhengzhou, China Abstract
2
Department of Chemical Engineering, This study systematically investigated and modeled the organic solvent reverse
Hiroshima University, Hiroshima, Japan
osmosis (OSRO) and pervaporation (PV) performances of bis(triethoxysiyl)acetylene
Correspondence (BTESA)-derived microporous organosilica membranes with different microstructures
Toshinori Tsuru, Department of Chemical
and permeation properties. BTESA membranes calcined at a low temperature of
Engineering, Hiroshima University, 1-4-1
Kagamiyama, Higashi-Hiroshima 739-8527, 100
C exhibited great promise for utility in the challenging OSRO separation of
Japan.
methanol/organic azeotropes such as methanol/toluene and methanol/methyl tert-
Email: tsuru@hiroshima-u.ac.jp
butyl ether and demonstrated ultrahigh values for both permeating flux and rejection
Funding information
together with good operation stability. In addition, a generalized solution-diffusion
New Energy and Industrial Technology
Development Organization model enabled a suitable description of the permeation behaviors of organic solvent
molecules through the BTESA membranes irrespective of the use of either OSRO or
PV modalities, which allowed us to predict the OSRO performance via PV, and vice
versa.

KEYWORDS
methanol, organic solvent reverse osmosis, organosilica membranes, pervaporation, solution-
diffusion model

1 | I N T RO DU CT I O N
The separation and purification of organic liquids are of primary
importance in biofuel, chemical, and pharmaceutical industries, but it
remains a challenging process. For instance, the organic solvent in the
waste generated in a typical pharmaceutical process usually approxi-
mates as much as 80% of the nonaqueous mass of materials used for
1
manufacturing active pharmaceutical ingredients (APIs). Currently,
industrial separation of organic liquids has relied predominantly on
costly and energy-intensive separation processes such as distillation,
evaporation, and extraction. The need to develop an economically via-
ble and highly efficient organic liquid separation technology is, there-
fore, of paramount significance and urgency for sustainable
production in the long run.
As an alternative technology, it is plausible that membrane-based
separation of organic liquids could reduce the energy expenditure of
the aforementioned traditional separation methods by as much as
90%, while also offering other competitive advantages such as a
robust process design and a much smaller plant footprint.2 These fac-
tors explain the enormous scope of recent efforts to develop
advanced membrane materials for use in the separation of organic liq-
uids. Organic solvent nanofiltration (OSN) has recently achieved very
favorable performance owing to the development of membrane mate-
rials such as ultrathin polyamide membranes (less than 10 nm in thick-
ness) and to the introduction of characteristics such as semi-flexible
microporosity.3,4 However, OSN membranes generally possess pore
sizes that range from 1 to 2 nm, and, as the name suggests, these
membranes primarily involve the hydrodynamic sieving of organic
molecules with molecular weights that range from 200 to 1000 Da
such as dyes and APIs. Therefore, the sufficiently effective separation
of organic liquids that have much lower molecular weights (<200 Da),
and/or similar molecular sizes (<1–3 Å), is relatively difficult to achieve
via OSN membranes.
In recent years, the development of high-performance mem-
branes and novel separation techniques that could differentiate liquid
hydrocarbon isomers and solutes with similar sizes dissolved in

AIChE J. 2022;68:e17585. wileyonlinelibrary.com/journal/aic © 2022 American Institute of Chemical Engineers. 1 of 13

https://doi.org/10.1002/aic.17585
2 of 13
organic liquids have been enduring research hotspots.5 Examples
include the recovery of para-xylene from xylene isomers, separation
of hydrocarbon mixtures with both linear and branched components,
and the separation of oxygenated molecules present in biorefinery
processing. These pursuits represent challenging, yet important, appli-
cations with huge economic interests.6 Using pervaporation (PV) and
the newly developed process of organic solvent reverse osmosis
(OSRO), the membrane-based separation of these organic liquids has
shown promise, and membranes with pore sizes of less than 1 nm and
a capacity for shape sieving (i.e., entropy selectivity) are particularly
desirable.
As a typical thermal-based separation process, PV refers to the
separation of organic liquids by partial vaporization through dense
membranes.7 To date, the most extensively explored membrane mate-
rials for PV are zeolite MFI, metal–organic frameworks (MOFs), and
functionalized polymers. These are used to create either homoge-
neous or heterogeneous membranes for the highly effective
separation of isomers, azeotropic/close-boiling-point mixtures, and
8,9
heat-sensitive mixtures. Recently developed organosilica-based
membranes already have extended the existing knowledge of the sep-
aration of methanol/organic azeotropes. These membranes have
incredibly high levels of methanol permeance and permselectivities
that are primarily the result of a combination of the preferential sorp-
tion of methanol and the excellent size/shape sieving of other large-
sized organic molecules.10 In contrast to PV, OSRO is known to
undergo an entirely liquid-phase separation process without the
involvement of either vaporization or condensation, which amounts
to dramatic energy savings compared with PV. Furthermore, a high
level of transmembrane pressure that exceeds the inherent osmotic
pressure is essential in OSRO to induce practical permeation, which
therefore requires OSRO membranes to have sufficient mechanical
strength with no obvious structural deformations. Nevertheless, mem-
brane materials capable of performing OSRO separations have
remained extremely scarce to this point, despite the fact that the con-
cept of OSRO was originally proposed by Sourirajan as early as
1970.11 Current state-of-the-art OSRO membranes have been devel-
oped in recent years from several classes of microporous materials
such as carbon molecular sieves (CMS), N-aryl-linked spirocyclic
polymers, and organosilica. Via elaborate control of the pyrolysis of
cross-linked polymeric poly(vinylidene fluoride) (PVDF), Lively et al.12
fabricated thin asymmetric CMS hollow-fiber membranes. These
membranes were able to enrich the para-xylene from an equimolar
para/ortho-xylene feed to 81 mol% in permeate while also retaining
their structural and mechanical integrity at applied pressures of more
than 10 MPa. In a recent study, Finn et al.13 took advantage of the
modestly flexible single-bond C N linkages to generate a spiro-
bifluorene aryl diamine series of thin-film composite membranes with
noninterconnected microporosity. They demonstrated the possibility
of using these composites in the OSRO separation of light crude oils
with molecular weights of approximately 170 Da. Meanwhile, our
group pioneered the OSRO separation of a series of organic azeo-
tropes using sol–gel-derived bis(triethoxysiyl)acetylene (BTESA)
organosilica membranes.14 In that study, a particularly impressive
DONG ET AL.
feature of the BTESA membrane was the ability to bear a maximum
transmembrane pressure that could reach as high as 18 MPa, which
highlighted the superior pressure resistance of BTESA membranes.
During the separation of methanol/toluene, BTESA membranes
yielded methanol flux that is at least one order of magnitude higher
than conventional methanol-selective membranes operated in the PV
modality with comparable separation factors.14 Also, great success
has been achieved by exploring other types of membrane materials
such as Torlon®, aliphatic polyketone supported polyamide, and
perfluoropolymer to produce OSRO-type separations of similar-sized
molecules.15–17
Permeation theory defines the solution-diffusion (SD) model as a
single unified approach, which includes both the RO and PV perme-
ation processes, and the overall driving force of a single permeant
under either mode is the gradient in its chemical potential across a
membrane.18 Previously, we reported a generalized SD model (gSD)
and used it to successfully analyze the separation properties of PV
and RO.19 The correlation between RO and PV has been substanti-
ated, and modeling has shown that the ceiling flux and selectivity that
membranes can achieve in RO are equal to those in PV. Moreover, it
is possible to predict the permeation performance of RO from those
of PV for a single component or for aqueous mixtures, and vice
versa.20 Experimental and theoretical comparisons of RO and PV per-
formance are quite important in discussions confirming the concept of
the SD model. However, to the best of our knowledge, no such dis-
cussion of a correlation between RO and PV performance for organic
systems has been reported thus far.
In the present work, we focused on OSRO and PV separations of
diverse types of organic azeotropes using BTESA-derived organosilica
membranes calcined at different temperatures. The effect of calcina-
tion temperature on the pore subnano-environment tailoring of
BTESA membranes as well as their OSRO performance was systemati-
cally investigated, and this had not been a focus of our previous
work.14,21 Besides, it is important to note that the results of this study
are the first to correlate the OSRO and PV performance of BTESA
membranes by simultaneously performing both OSRO- and PV-type
separations and analyzing the permeation performance via the use of
a gSD model.
2 | THEORY
To analyze and predict OSRO and PV performance, solvent transport
through BTESA membranes was described using equations derived
from a gSD model, the usefulness of which had been demonstrated in
our earlier work on PV10 and OSRO,21 which showed that the separa-
tion performance of the organosilica-based membranes for diverse
organic azeotropes could be well simulated. There had never been,
however, a comparison between OSRO and PV performance. The
gSD model assumes a uniform pressure across the membrane and that
solvent transport through the membrane is the result of the gradient
in the chemical potential, which is a concentration gradient that is
schematically illustrated in Figure 1. By assuming a chemical potential
DONG ET AL. 3 of 13

P J
In the PV case : ¼ , ð6Þ
l r1 x1 pv  p2

P J J
In the OSRO case : ¼ RT  RT ¼ ,
l υ lnðr 1 x1 Þ þ p1  ν lnðr 2 x2 Þ þ p2
Δp  Δπ
ð7Þ

where

Δp ¼ p1  p2 ,

 
RT r 1 x1
Δπ ¼  ln :
υ r 2 x2
F I G U R E 1 Schematic illustration of the pressure (p), chemical
potential (μ), and component concentration (c) for a profile of the
In Equations (1)–(7) and Figure 1, J, x, p pv , v, R, and T are the permeat-
generalized solution-diffusion model
ing flux (mol m2 s1), molar fraction (), pressure (Pa), saturation
vapor pressure (Pa), molar volume (m3 mol1), gas constant
equilibrium between the membrane surface and a solution, the PV flux (8.314 J mol1 K1), and absolute temperature (K), respectively. Here,
for each component with respect to the pressure and concentration is r is the activity coefficient () determined from the Wilson equations
defined by Equation (1). in Table S1. The subscripts 1 and 2 refer to the feed and permeate
sides, respectively, and the superscript m represents the membrane


p x2 v ðp  p1 Þ phase. In Equations (6) and (7), Δp and Δπ are the transmembrane
J ¼ K r1 x1  2 exp v , ð1Þ
pv RT
pressure (Pa) and osmotic pressure difference (Pa), respectively,
in OSRO.
where

DCm 3 | EX PE RI MENT AL
K¼ : ð2Þ
lr m

3.1 | BTESA sol synthesis, xerogel powders, and

Thus, the permeating flux ratios of component M over component membrane preparation
N are equal to the molar fractions of the components in the permeate
with a downstream pressure, p2 , of zero. First, BTESA monomer was synthesized using procedures described in
the literature,14 which is available in the supporting information
JM ½Kr1 x1 M (Section S2). BTESA membranes were fabricated on commercially
¼ : ð3Þ
JN ½Kr1 x1 N
available porous α-alumina tubes (Nikkato Co., Tokyo, Japan; porosity:
50%; average pore size: 1 μm; outer diameter: 10 mm; length: 10 cm)
In the case of OSRO, the permeating flux and flux ratio of component through multiple coating procedures. First, two different sizes of
M over component N can be written as follows: α-Al2O3 particles (average size: 0.2 and 1.9 μm) were loaded onto the
outer surface of the membrane support by hand coating to cover the


vðp2  p1 Þ large pores, coupled with silica-zirconia colloidal sol (SiO2-ZrO2) as a
J ¼ K r1 x1  r2 x2 exp , ð4Þ
RT
binder that was prepared from tetraethoxysilane and zirconium tet-
h i rabutoxide (Si/Zr = 1/1 in mol). Afterward, the supports were fired at
vðp2 p1 Þ
JM ðx2 ÞM K M r1 x1  r2 x2 exp RT 550
C for 20 min under air. Before coating the BTESA sol, a SiO2-
¼ ¼ h iM : ð5Þ
JN ðx2 ÞN K N r1 x1  r2 x2 exp vðp2 p1 Þ ZrO2 intermediate layer was formed with an average pore size of sev-
RT N
eral nm to prevent the penetration of the BTESA sol. Finally, BTESA
sol was coated as the top layer, followed by flash calcination in a
It should be noted that K is an activity-normalized membrane three-zone tubular furnace with a constant temperature of either
permeance (mol m2 s1) that is assumed to be constant, and it is com- 100 or 300
C under N2 for 1 h and then cooling to 50
C with a
1
2
prised of the diffusion coefficient D (m s ), total molar concentration cooling rate of 10
C min1.
Cm (mol m3), activity coefficient γ m (), and membrane thickness l (m), Meanwhile, BTESA xerogel powders were obtained by evaporat-
but K is defined in a different manner from the following intrinsic ing the solvent from the BTESA sol under air at 50
C with subsequent
2 1 1
permeance, P=l (mol m s Pa ), which is normalized by the driving calcination in the same manner as the top layer of the membranes.
force and is the most commonly used parameter in the literature. The resultant BTESA membranes and xerogel powders fired at
4 of 13
100 and 300
C are referred to here as BTESA-100-x and BTESA-
300-x. For example, BTESA-100-1 refers to the BTESA membrane cal-


cined at 100 C with the membrane number of 1.
3.2 | Characterization of BTESA-derived xerogel
powders and membranes
Characterization techniques for BTESA-derived xerogel powders and
membranes, including N2 and/or organic vapor adsorption/desorption
isotherms, Fourier-transform infrared spectroscopy (FTIR), Field emis-
sion scanning electron microscope (FESEM), and X-ray photoelectron
spectroscopy (XPS) are described in detail in the supporting informa-
tion (Section S2).
3.3 | Gas permeation, OSRO, and PV measurement
Prior to OSRO and PV separations, single-gas (He, H2, CO2, N2, CH4,
CF4, and SF6) permeation tests were conducted on a homemade setup
via the constant pressure method, as illustrated in Figure S1.
A combined apparatus was designed and developed for both
OSRO and PV separations, as shown in Figures 2 and S2, which elimi-
nated the potential influence caused by using different membrane
modules. The BTESA membrane was carefully installed in the module
(inner diameter: 4 cm; height: 10 cm; effective volume: 126.5 cm3)
before performance evaluation, and a stirrer was applied with vigor-
ous agitation at 800 rpm to avoid possible concentration polarization.
The OSRO separation was performed under continuous total rec-
irculation by employing a plunger pump (NP-FX[II]-20, NIHON
SEIMITSU KAGAKU CO. LTD, Tokyo, Japan) to recycle the retentate
back to the feed at a flow rate of 8 ml min1. The applied pressure
was slowly ramped via a back-pressure valve (Swagelok, KPB) in a
range of 0–20 MPa (gauge pressure). The permeate was collected
from the inner side of the membrane via a microtube pump (EYELA,
F I G U R E 2 Schematic diagram of the apparatus for both OSRO
and PV testing. OSRO, organic solvent reverse osmosis; PV,
pervaporation
DONG ET AL.
MP-2000) under a steady state, which was typically achieved within
2 h after commencing the experiment. During PV separation, the
back-pressure valve was released while the feed was continuously
recirculated. A vacuum pump was connected to maintain a constant
pressure of about 130 Pa on the permeate side, and permeate was
collected in a glass trap and cooled in a liquid nitrogen container. Of
note, a certain small amount of pure methanol was added to the feed
tank at intervals to maintain the feed at a constant concentration
throughout the PV test. A gas chromatograph (Shimadzu GC 2014)
equipped with a flame ionization detector was employed to analyze
the organic solvent compositions of the feed and permeate samples,
and the results are reported as the average of four parallel tests. The
separation performance of the BTESA membrane was assessed by the
permeating flux and rejection of organic/organic mixtures including
methanol/toluene (Tol), methanol/dimethyl carbonate (DMC), and
methanol/methyl tert-butyl ether (MTBE). The concentration of the
feed methanol ranged from 100 to 10 wt%. Furthermore, PV separa-
tions of methanol (MeOH) from ethanol (EtOH), iso-propanol, butanol,
methyl acetate, and butyl acetate (BA) were also performed using
BTESA membranes at 50
C to evaluate the pore-size distribution of
BTESA membranes calcined at 100 and 300
C.
The permeating flux, J (kg m2 h1), rejection, R (), and separa-
tion factor, β (), for OSRO and PV tests are defined by Equations (8)–
(10):
Q
J¼ , ð8Þ
A  Δt
 
x2
R¼ 1  100%, ð9Þ
x1
ð1  x2 Þ ð1  x1 Þ
β¼ = : ð10Þ
x2 x1
In Equation (8), Q, A, and Δt are the permeate weight (kg), effective
membrane area (m2), and permeation time (h), respectively. x1 and x2
in Equations (9) and (10) are the molar fractions of the “solute” in the
feed and permeate. Herein, methanol and other organic molecules are
denoted as “solvent” and “solute,” respectively.
4 | RESULTS AND DISCUSSION
4.1 | Characterization and gas separation
performance of BTESA membranes
BTESA membranes were prepared on the α-alumina supports through
a sol–gel method at different calcination temperatures. An asymmetric
structure with a uniform and continuous separation layer (i.e., BTESA
layer) was formed as thin as 200 nm, as shown in Figure S3.
To understand the differences in the microstructures of BTESA
membranes that is induced by the calcination temperatures, a series
of characterizations were performed accordingly on BTESA films and
xerogel powders. As shown in Figure 3A, all the FTIR spectra for
DONG ET AL.
F I G U R E 3 (A) FTIR spectra of BTESA films. (B) N2 sorption isotherm of BTESA powders. BTESA, bis(triethoxysiyl)acetylene; FTIR, Fourier
transform infrared spectroscopy
BTESA films feature almost the same absorption bands, whereby the
intensive absorption band centered at 1065 cm1 can be attributed to
the Si O Si domains, which suggests that siloxane constitutes the
main backbone of the BTESA layer. Moreover, the peak intensities of
Si OH and C≡C at 890 and 2200 cm1 decreased while that of Si C
at 800 cm1 increased as the calcination temperature for BTESA films


was increased from 100 to 300 C, suggesting that the high calcination
temperature may have accelerated the decomposition of C≡C bonds
and the generation of Si C and Si O Si bonds. It was noted that the
peak area assigned to Si O Si was clearly greater for BTESA-300
than that for BTESA-100, evidencing that the crosslinking proceeded
at a higher degree with a higher calcination temperature. Also, the
presence of hydroxyl groups probably formed from water vapor and
Si OH was confirmed by a broad adsorption band that ranged from
3100 to 3600 cm1, the intensity of which was more prominent for
the BTESA-100 film. Figure 3B shows the N2 adsorption at 77 K for
BTESA xerogel powders under relative pressure that ranged from
104 to 1.0, whereby both samples displayed typical Type I isotherms
that correspond to a microporous structure. The specific area and
micropore volume increased from 114 m2 g1 and 0.065 cm3 g1 for
BTESA-100 to 478 m2 g1 and 0.209 cm3 g1 for BTESA-300, which
suggests that a high level of calcination temperature for BTESA pow-
der is beneficial for the improvement of microporosity. This observa-
tion is in accordance with our previous report and can be reasonably
explained by the pyrolysis and rearrangement of the functional groups
such as C≡C, Si OH, and Si C and by a subsequent change in the
cross-linking degree of the silica network structure.22,23 To further
quantitatively analyze the surface composition of the BTESA mem-
branes, XPS analysis was conducted on the corresponding BTESA
powders. The data from the O 1s, C 1s, Si 2s, and Si 2p XPS spectra
shown in Figure S4 show that the silicon contents in both BTESA
powders are basically comparable, that is, from 21.8% to 24.6%. Nev-
ertheless, higher calcination temperatures generated an increase in
the oxygen content of from 52.8% to 62.5%, while the carbon content
varied from 25.4% to 12.9% (Table S2). Therefore, in contrast to
BTESA-100 powder, BTESA-300 powder is relatively more oxygen
rich, albeit carbon poor. Also, we observed that C 1s peaks were
5 of 13
shifted by around 0.4 eV to higher binding energy values as the calci-
nation temperature increased, which provides additional evidence for
a change in the chemical state of the carbon atoms and can be reason-
ably explained by the reduction and/or cleavage of the Si C≡C Si
bridges as well as by the enhanced formation of new Si C bonds.24
These XPS results suggest that the siloxane network of the BTESA
powder calcined at a higher temperature is more oxidized, although
fired under a N2 atmosphere. Again, we deduced that the organic moi-
eties in BTESA-300 networks could have been more decomposed and
accompanied by the generation of ample new Si O Si bonds, which
would have resulted in a higher degree of cross-linking and agreed
with the FTIR analysis.
Figure 4 summarizes the molecular size dependence of single-gas
permeance at 100
C for all of the used BTESA membranes together
with the PV permeance of BTESA-100-1 and BTESA-300-1 mem-
branes for methanol/organic mixtures at a feed methanol concentra-
tion of 10 wt% and 50
C (Figure S5). All BTESA membranes showed
decreased permeance with an increase in the molecular size of the
permeating molecules primarily based on the molecular sieving mech-
anism. Meanwhile, the reproducibility of the as-prepared BTESA
membranes has been confirmed. In addition to SF6, all the gas
permeance values for BTESA-300 membranes were higher than, or at
least comparable to, those for BTESA-100 membranes. As a result,
the BTESA-300 membranes exhibited more pronounced selectivities
for N2/SF6 and H2/SF6 at 500–2400 and 6000–25,000, respectively,
which far exceeded values for the BTESA-100 membranes (50–130
for N2/SF6 and 900–1900 for H2/SF6).
Similar to gas permeance, the PV permeance was decreased as
the molecular size of solvents increased, and the BTESA-300 mem-
brane showed a lower level of permeance, albeit with a sharper slope,
than that of the BTESA-100, which suggests a more significant level
of molecular sieving. Interestingly, the PV permeance of the BTESA-
300 membrane almost overlapped that of single-gas permeation. The
same was not true, however, for the BTESA-100 membrane, the PV
permeance of which deviated greatly from that of single-gas
permeance. A similar phenomenon occurred in our previous work on
the PV dehydration of alcohol aqueous solutions using the
6 of 13 DONG ET AL.

F I G U R E 4 Values for the

molecular size dependency of single-
gas permeance for (A) BTESA-100 and
(B) BTESA-300 membranes at 100
C
and for the PV separation of methanol/
organic mixtures (10 wt%/90 wt%) at
50
C. The molecular sizes of the gases
and organic solvents that were used
are summarized in Table S3. BTESA,
bis(triethoxysiyl)acetylene; PV,
pervaporation

bis(triethoxysilyl)ethane (BTESE)-derived membranes that were like-

wise calcined at 100 and 300
C. This was attributed to the adsorbed
water in the low-temperature calcined BTESE membranes,25 which,
via hydrogen bonding, interacted more strongly with the organic sol-
vents relative to their interactions with gas molecules. Thus, the
adsorbed water was likely to have been removed during PV, resulting
in an enlargement of the membrane pore size and greater levels of PV
permeance. Therefore, it seems clear that PV is the more appropriate
mechanism to describe the pore-size distribution regarding the
BTESA-100 membranes. On the other hand, the existence of
adsorbed water provides another explanation for the smaller specific
area and micropore volume of the BTESA-100 xerogel powder shown
in Figure 3B, which was degassed at 90
C before measurement
(Section S2). Although adsorbed water molecules had narrowed the
pore sizes of the BTESA-100 membranes, the SF6 permeance
remained greater than that for the BTESA-300 membranes. That fact
suggests a higher portion of large-sized micropores for BTESA-100
F I G U R E 5 Comparison of the OSRO results for BTESA-100-2
membranes that enabled SF6 to readily permeate. and BTESA-300-2 membranes using pure methanol and methanol/
organic mixtures (95 wt%/5 wt%) at 50
C and 8 MPa. BTESA,
bis(triethoxysiyl)acetylene; OSRO, organic solvent reverse osmosis
4.2 | OSRO performance of BTESA membranes for
different organic azeotropes
were calculated to be 43.5 and 35.9 kJ mol1 for BTESA-100 and
Figure 5 demonstrates the effect that the calcination temperature BTESA-300 xerogel powders, respectively. Those results demonstrate
exerted on the OSRO performance of the BTESA membranes. In the a stronger affinity to methanol molecules by the BTESA-100 xerogel
case of pure methanol, the BTESA-100 membrane recorded a higher powder. In addition, the pore-opening effect that resulted from the
level of flux than that of the BTESA-300 membrane, which is opposite removal of the adsorbed water during OSRO could remarkably accel-
the trend observed for single-gas permeation, despite the fact that erate the diffusion of methanol in BTESA-100 membranes, which is
the molecular size of a methanol molecule (3.8 Å) approximates that consistent with the PV permeance shown in Figure 4.
of a CH4 molecule (3.8 Å). This inconsistency can be rationally attrib- Subsequently, the same BTESA membranes were subjected to
uted to the difference in the surface chemistry and pore-size distribu- the OSRO separation of the dilute organic/organic mixtures that
tion of both types of BTESA membranes. On the basis of the SD included methanol/DMC, methanol/toluene (Tol), and methanol/
principle, BTESA-100 membranes featured a greater number of silanol MTBE, all of which are azeotropes, while complete membrane wash-
groups, which would result in an enhanced solution process for meth- ing was strictly performed by immersing the membrane into pure
anol. As evidenced by the isothermal adsorption of methanol shown methanol under magnetic stirring (800 rpm) for 24 h at 50
C between
in Figure S6 and in Table S4, the adsorption enthalpies for methanol each feed mixture measurement to recover the permeating flux.
DONG ET AL.
F I G U R E 6 (A) Time course of OSRO for methanol/MTBE (90 wt%/10 wt%) through the BTESA-100-2 membrane at 50
C and 8 MPa.
(B) Change in the OSRO performance of the BTESA-100-2 membrane for methanol/toluene (95 wt%/5 wt%) at 50
C and 8 MPa during 190 days
of aging in methanol. MTBE, methyl tert-butyl ether; OSRO, organic solvent reverse osmosis
Clearly, the order of the permeating fluxes was BTESA-100 > BTESA-
300 with approximately the same values for three different types of
solutes, and the corresponding rejections followed the order of meth-
anol/DMC < methanol/toluene ≈ methanol/MTBE. This selective per-
meation behavior can be well understood by the combination of
sorption and diffusion. In the separation of organic/organic mixtures
by hydrophobic membranes, weakly polar organic molecules typically
show a higher affinity to the membrane than the strongly polar ver-
sions.26 As Table S5 shows, the value of the polar component of
Hansen solubility parameters for DMC (8.6 MPa1/2) is significantly
higher than that for either toluene or MTBE (1.4 and 3.6 MPa1/2,
respectively), which could lead to a favorable sorption of DMC mole-
cules onto the hydrophilic BTESA membranes and an accelerated rate
of permeation. This speculation is further supported by the results of
the isothermal adsorption of different organic vapors onto the BTESA
xerogel powders, which exhibited a level of DMC adsorption that was
higher than that for either toluene or MTBE (Figure S7). Although the
molecular size of DMC is unavailable,27 the moderate rejection values
of 65%–85% for DMC suggest a molecular size that is somewhat
smaller than the average membrane pore size. However, both toluene
and MTBE molecules have molecular sizes (0.525 and 0.63 nm)28 that
approximate that of the SF6 (0.55 nm) and have planar and T-shape
structures, respectively, that create significant amounts of steric hin-
drance. As a result, both BTESA membranes achieved surprisingly high
levels of rejection (>98%) for toluene and MTBE. The favorable com-
bination of ultrahigh flux and rejection for BTESA-100 membranes
shows particular promise for practical use in the OSRO separation of
the methanol/toluene and methanol/MTBE azeotropes.
Despite high separation performance, the most crucial point asso-
ciated with membranes for practical application is long-term stability.
We, therefore, subjected the BTESA-100 membrane to continuous
OSRO measurement in a methanol/MTBE feed mixture for 100 h, as
shown in Figure 6A. During the overall test period, the BTESA-100
membrane exhibited very stable levels of permeating flux and rejec-
tion with a feed methanol concentration of 90–99.8 wt% in the per-


meate at 50 C and 8 MPa. After a complete methanol washing, the
stability of the same BTESA-100 membrane was subjected to an envi-
ronment of pure methanol for 190 days to evaluate the aging
7 of 13
behavior principally induced by chemisorption. The OSRO perfor-
mance for methanol/toluene was used as a primary benchmark by
recording the variations in permeating flux and rejection with respect
to the time of aging. As shown in Figure 6B, the permeating flux was
increased by nearly 85% relative to its original value during the initial
150 days and finally stabilized at about 5.4 kg m2 h1 with only a
slight drop in rejection of from 98.4 to 97.1%. This phenomenon is
highly desired, as the flux increase barely sacrificed rejection during
the aging in methanol, which is indicative of the great potential of the
BTESA-100 membrane for real applications. The reason for the
changes in the permeating flux and rejection for the BTESA-100
membrane was likely due to the hydrolytic cleavage of a small portion
of the Si O Si bonds within the organosilica network to form Si OH
groups induced by the inevitable water molecules in methanol.29,30
This reaction impacts not only the membrane micropore size and
affinity toward methanol but also steric hindrance for larger organic
molecules such as toluene and MTBE.
4.3 | Comparison of the OSRO and PV
performance of BTESA membranes
In this section, the OSRO and PV performances of BTESA membranes
are compared using methanol/DMC as a model feed liquid. As shown
in Figure 7, a testing sequence for PV-OSRO-PV was delicately per-
formed on the newly prepared BTESA-100 and BTESA-300 mem-
branes at 50
C. During the PV process with the feed DMC
concentration increased from 10 to 90 wt%, a decrease in total flux
and an increase in the separation factor were clearly observed for
both BTESA membranes. This phenomenon was encountered in our
previous work on the PV separation of methanol/DMC and was
attributed to a dramatic change in the driving forces (i.e., partial pres-
sure) for methanol and DMC molecules.10 It is noteworthy that the
pure methanol flux could be completely recovered to its original value,
suggesting that BTESA membranes were not susceptible to the nega-
tive impacts of pore plugging and/or membrane fouling during PV,
which was very important for the subsequent OSRO separations by
ensuring the accuracy of the OSRO measurements. This allowed us to
8 of 13 DONG ET AL.

F I G U R E 7 Time courses for the separations of different weight ratios of methanol/DMC (wt%/wt%) mixtures through (A) BTESA-100-3 and
(B) BTESA-300-3 membranes operated with a PV-OSRO-PV testing sequence at 50
C. BTESA, bis(triethoxysiyl)acetylene; DMC, dimethyl
carbonate; OSRO, organic solvent reverse osmosis; PV, pervaporation

F I G U R E 8 OSRO separation performance of (A) BTESA-100-3 and (B) BTESA-300-3 membranes using different weight ratios of methanol/
DMC (wt%/wt%) mixtures with transmembrane pressures ranging from 2 to 12 MPa at 50
C. BTESA, bis(triethoxysiyl)acetylene; DMC, dimethyl
carbonate; OSRO, organic solvent reverse osmosis

compare the OSRO and PV performance of the same BTESA mem-
brane on an approximately fair basis, and it highlighted the critical
advantages of the organosilica-based membranes over conventional
polymeric membranes that generally suffer from undesired organic
swelling and compaction. The results of OSRO separations appear in
Figure 8 and will be discussed later. However, when the same BTESA
membrane was measured for another PV separation of the pure
methanol following OSRO, values for residual methanol flux reached
approximately 76% and 72% of the original values for BTESA-100 and
BTESA-300 membranes, respectively, confirming that a fraction of the
microchannels through the BTESA membranes could have been
plugged by the DMC molecules during OSRO. Although the plugging
was generally much more prominent under high pressure and with
high solute concentrations in the feed,14 BTESA membranes
DONG ET AL.
F I G U R E 9 A direct comparison of PV and OSRO performances (closed and open symbols) of (A) BTESA-100-3 and (B) BTESA-300-3
membranes for different weight ratios of methanol/DMC (wt%/wt%) mixtures at 50
C and 4–12 MPa. BTESA, bis(triethoxysiyl)acetylene; DMC,
dimethyl carbonate; OSRO, organic solvent reverse osmosis; PV, pervaporation
continued to show high and reasonable levels of flux even following
OSRO under 12 MPa and 70 wt% feed DMC.
Figure 8 shows the OSRO results for the BTESA-100 and BTESA-
300 membranes during permeation experiments using methanol/
DMC in a wide range of pressures (2–12 MPa) and DMC concentra-


tions (0–70 wt%) at 50 C. Similar to OSN and aqueous RO, both the
flux and rejection were increased with an increase in the transmem-
brane pressure. Nevertheless, an increase in the DMC concentration
resulted in simultaneous decreases in flux and rejection. These trends
are commonly observed and can be reasonably ascribed to variations
in the osmotic pressure difference that is closely related to the applied
pressure and feed concentrations.21
Figure 9 shows a direct comparison of the PV and OSRO per-
formances of the BTESA membranes using methanol/DMC mix-
tures with respect to the total flux and separation factors. Clearly,
the OSRO flux and separation factors achieved by the BTESA
membranes when using methanol/DMC were substantially lower
than that achieved by PV under the same circumstances. For
instance, in the case of a feed mixture of 70 wt% of DMC at 50
C
and 12 MPa, the BTESA-100 membrane exhibited approximately
12- and 19-fold higher levels of PV flux (5.72 kg m2 h1) and sep-
aration factor (39.2), respectively, than values recorded by the
OSRO modality. This was due to the fact that the separation
potential of OSRO is markedly lower than that of PV, which is
accompanied by vaporization in the permeate stream. 31,32 Mean-
while, the separation factors for OSRO and PV recorded both
downward and upward trends in accordance with changes in the
concentration of the feed DMC, which suggested lower and higher
9 of 13
increases in the rate of methanol flux for OSRO and PV,
respectively.
4.4 | Theoretical analysis of the correlations
between OSRO and PV
Under the same feed conditions, which included temperature and sep-
aration targets, we hypothesized that Equations (1)–(5) would share
the same K values for a particular membrane irrespective of working
under either the OSRO or PV mode, because K is a parameter that is
related only to the intrinsic characteristics of membrane materials.
Based on the experimental results shown in Figure 9, the K values for
methanol and DMC calculated via the use of Equations (1)–(5) for
each condition (feed concentration and pressure) are summarized as a
function of the DMC concentration and transmembrane pressure. As
Figure 10 shows, the K values for methanol were about two orders of
magnitude larger than those for DMC, but the K values determined by
the use of either OSRO or PV were surprisingly overlapped, which
confirmed our previous hypothesis that the parameter K is indepen-
dent of the separation modes. This observation is completely different
from the intrinsic permeance calculated using Equations (6) and (7),
which was serval orders larger for PV than for RO, and indicated that
the gSD model is suitable for correlating and predicting RO and PV
performance. The details can be found in Figure S8. Also, it is appar-
ent that the K values under PV were relatively unaffected by changes
in the feed concentrations. On the other hand, an increase in the feed
DMC concentration resulted in slight decreases and increases in the
10 of 13 DONG ET AL.

K values for methanol and DMC, respectively, under OSRO, which
suggested a more complicated permeation behavior. Generally, the
interactions among the membrane–solvent–solute cannot be ignored
for RO membranes, particularly when using nonaqueous mixtures
with high molar volumes and high solute concentrations, which, how-
ever, is considered outside the gSD model.19,33 Methanol and DMC
molecules are thought to be involved in the intermolecular interac-
tions by forming hydrogen bonds under low-feed DMC concentra-
tions, which could generate a dragging effect for DMC transport.
With a further increase in the feed DMC concentration, the dipole–
dipole interactions between DMC molecules predominate and selec-
tively form cis–trans clusters through the carbonyl groups, which
hinder methanol permeation and plugs pores.34 Another possible
explanation could be competitive adsorption on the membrane pore
walls between methanol and DMC molecules.
In addition to the feed concentration, the effect of transmem-
brane pressure on the K values of BTESA membranes during OSRO is
further illustrated in Figure S9. Analogous to the effects of the feed

F I G U R E 1 0 The relationship between activity-normalized permeance, K, and the feed DMC concentration during the PV and OSRO
separations of methanol/DMC mixtures through (A) BTESA-100-3 and (B) BTESA-300-3 membranes at 50
C. BTESA, bis(triethoxysiyl)acetylene;
DMC, dimethyl carbonate; OSRO, organic solvent reverse osmosis; PV, pervaporation

F I G U R E 1 1 Using PV and OSRO separation of methanol/DMC mixtures at 50
C and at different transmembrane pressures to compare the
experimental flux and methanol concentration in the permeate (open and closed symbols) with the modeling prediction levels (solid curves) using
(A) BTESA-100-3 and (B) BTESA-300-3 membranes. BTESA, bis(triethoxysiyl)acetylene; DMC, dimethyl carbonate; OSRO, organic solvent reverse
osmosis; PV, pervaporation
DONG ET AL. 11 of 13

TABLE 1 Summary of the membrane averages for methanol, DMC, and MTBE permeance in PV at 50
C

Membranes Feed mixture (M/N) KM  102 (mol m2 s1) KN  104 (mol m2 s1) KM/ KN ()
BTESA-100-3 Methanol/DMC 7.2 ± 0.4 17.5 ± 0.5 41
BTESA-300-3 Methanol/DMC 5.8 ± 0.3 8.7 ± 0.5 67
BTESA-300-4 Methanol/MTBE 3.0 ± 0.3 0.048 ± 0.006 6250

Abbreviations: BTESA, bis(triethoxysiyl)acetylene; DMC, dimethyl carbonate; MTBE, methyl tert-butyl ether; PV, pervaporation.

DMC concentration in Figure 10, the K values for methanol and DMC
decreased and increased, respectively, with increases in the trans-
membrane pressure. It is apparent that the K values for methanol with
the BTESA-100 membrane varied within a much wider range relative
to that of the BTESA-300 membranes, which indicated that methanol
transport through the BTESA-100 membrane was more susceptible to
transmembrane pressure. These observations can be reasonably
explained by the presence of convective coupling and by the differ-
ences in the microstructures of the BTESA membranes. Convective
coupling between solvent and solute within RO membranes such as
cellulose acetate and polyamide membranes is believed to occur
mainly in the free voids. Therefore, increasing the transmembrane
pressure would significantly enhance the convective coupling by
increasing the size and/or the number of the free voids.35,36 Our
BTESA membranes feature micropores that are more rigid, and thus
the effect of the transmembrane pressure on the size and/or the num-
ber of the free voids may not be as prominent as that for polymer-
based RO membranes. Nevertheless, larger free voids always exist
within BTESA membranes due to the pore nonuniformity, whereby
convective coupling could occur between methanol and DMC mole-
cules. Also, the pore-plugging phenomenon recorded in Figure 7 is
strong evidence for the residue of larger sizes of DMC molecules in
the free voids, which is assisted by high levels of transmembrane pres-
sure. In particular, the BTESA-100 membrane had a lower degree of
cross-linking and a higher percentage of organic moieties than the F I G U R E 1 2 Comparison of the gSD modeling predictions (solid
curves) with the experimental results (open and closed symbols) for
BTESA-300 membrane, which should allow for a higher level of flexi-
total flux and methanol in the permeate. Experimental: a full range of
bility in the network. Accordingly, changes in the size and/or the num-
concentrations for methanol/MTBE mixtures separated by a BTESA-
ber of free voids in BTESA-100 membranes are likely to be more 300-4 membrane at 50
C under PV mode; OSRO separation of
significant under higher levels of transmembrane pressure. methanol/MTBE mixtures using the same BTESA-300-4 membrane at
Despite the differences in the sensitivity of K to the concentra- 50
C and 8 and 10 MPa. BTESA, bis(triethoxysiyl)acetylene; gSD,
tion and pressure of the feed under OSRO and PV modes, as shown generalized solution-diffusion; OSRO, organic solvent reverse
osmosis; PV, pervaporation
in Figure 10, it is likely that the OSRO and PV performance of a partic-
ular BTESA membrane for methanol/DMC can be well correlated by
the gSD model due to the similarities in the K values, which was the used for each component, the predicted curves for both BTESA-100
main focus of the present study. As far as we could ascertain, the pre- and BTESA-300 membranes agreed well with the values for the meth-
sent study is the first to use OSRO and PV data to synchronously clar- anol concentration in the permeate and with the values for PV flux in
ify a gSD model. Meanwhile, it should be noted that the membrane a full range of feed concentrations as well as with the OSRO flux mea-
permeance, K, is the only modeling parameter unknown in the gSD sured at 6, 8, and 10 MPa. A comparison of the experimental and
model that should be determined prior to the use of this model for predicted data in Figure S10, shows averaged absolute deviations of 7.2
simulating the PV and OSRO conditions. Figure 11 compares the and 2.2% for total flux and methanol concentration in the permeate,
experimental OSRO and PV results from different methanol/DMC respectively, which confirms the viability of the gSD modeling equations
feed mixtures with the results predicted by the gSD model using for predicting both simple PV and osmotically moderated permeation.
K values that represent the averages of PV results that are listed in This verifies the success of this strategy in predicting the OSRO perfor-
Figure 10 and summarized in Table 1. Although only one K value was mance of rigid microporous organosilica membranes by using the gSD
12 of 13
model in combination with fundamental PV data. Once again, this
clearly shows the effectiveness of the gSD model. Additional discussion
on the comparison of the K values for BTESA membranes achieved in
this study and our previous work21 is provided in Table S6.
Subsequently, the applicability of the gSD model was further
extended to the methanol/MTBE mixtures allowing for the effect of
solute types. Similarly, a fresh BTESA-300 membrane was measured
using a sequence of PV-OSRO-PV tests at 50
C, and the modeling
parameters, K, for methanol and MTBE under PV and OSRO condi-
tions were compared, as shown in Figure S11. Unsurprisingly, the
BTESA-300 membrane achieved an impressively high PV separation
factor for methanol/MTBE that reached as high as 10,000, which
was almost 2 orders of magnitude higher than that for methanol/
DMC due to the larger molecular size of MTBE, which indicates an
enhanced molecular sieving performance. When compared with
other previously reported membranes for PV separation of metha-
nol/DMC and methanol/MTBE, our BTESA membranes exhibited
decent performance (Figure S12 and Tables S7 and S8). It is note-
worthy, however, that the K values for MTBE determined by OSRO
were larger than those by PV, which again can be ascribed to the
coupling effect between methanol and MTBE molecules. However,
the general trends for permeating flux and variations in the concen-
tration of the permeate with feed conditions under either the OSRO
or PV mode can still be reasonably described using the theoretical
predictions and the K values for methanol/MTBE shown in Table 1,
despite the deviation observed in the case of OSRO (Figure 12). In
addition, the modeling curves recorded an extremely low OSRO flux
with a high-feed MTBE concentration. This was due to the increase
in the osmotic pressure difference that resulted from the level of
rejection for MTBE that was higher than that for DMC (Figure S13).
5 | C O N CL U S I O N S
This work involved the preparation of organosilica-derived BTESA
membranes calcined at different temperatures and subsequently
applied to both OSRO and PV separation of diverse methanol/
organic azeotropes to explore the correlation between OSRO and
PV performance. With the assistance of a series of characteriza-
tions and single-gas permeation tests, BTESA membranes calcin-
ated at 100 and 300
C showed significant differences in their
microstructures with different cross-linking degrees of their silica
networks. In particular, BTESA membranes calcinated at 100
C
showed great potential for the challenging OSRO separation of
methanol/toluene and methanol/MTBE azeotropes with both ultra-
high permeating flux and rejection, while retaining their stability
over the course of operation for 100 h and the suppressing the
aging of methanol for as long as 190 days. More importantly, this
study is the first to establish a clear correlation between the PV
and OSRO performances of BTESA-derived microporous mem-
branes, which revealed that the permeation behavior of organic sol-
vents under OSRO can be well predicted by the PV experimental
results as well as by the use of a gSD model, and vice versa.
DONG ET AL.
Although further investigation is required regarding the complex
convective coupling behavior in the BTESA membranes that is not
considered in the gSD model, this model shows great advantages of
mathematical simplicity and sufficiency in describing the permeat-
ing flux and rejection results for the studied PV and OSRO cases.
This study demonstrated a useful strategy to predict the OSRO per-
formance of organosilica membranes, which could help the mem-
brane researchers efficiently select the most appropriate
organosilica-based membrane materials for OSRO separations, and
also could aid in the development of more advanced versions of
OSRO membranes.
ACKNOWLEDG MENT
This work was financially supported by Grants-in-Aid for Scientific
Research (KAKEN) and the New Energy and Industrial Technology
Development Organization (NEDO).
AUTHOR CONTRIBU TIONS
Guanying Dong: Data curation (lead); formal analysis (lead); investiga-
tion (lead); methodology (lead); writing – original draft (lead). Yatao
Zhang: Supervision (equal); writing – review and editing (equal).
Takaaki Sato: Investigation (equal). Hiroki Nagasawa: Supervision
(equal); writing – review and editing (equal). Masakoto Kanezashi:
Supervision (equal); writing – review and editing (equal). Toshinori
Tsuru: Funding acquisition (equal); supervision (equal); writing –
review and editing (equal).
DATA AVAILABILITY STAT EMEN T
The data that support the findings of this study are available in the
supplementary material of this article.
OR CID
Guanying Dong https://orcid.org/0000-0002-9878-7037
Yatao Zhang https://orcid.org/0000-0002-6832-3127
Masakoto Kanezashi https://orcid.org/0000-0003-1435-9754
Toshinori Tsuru https://orcid.org/0000-0002-8561-4962
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SUPPORTING INF ORMATION
Additional supporting information may be found in the online version
of the article at the publisher's website.
How to cite this article: Dong G, Zhang Y, Sato T,
Nagasawa H, Kanezashi M, Tsuru T. Reverse osmosis and
pervaporation of organic liquids using organosilica
membranes: Performance analysis and predictions. AIChE J.
2022;68(4):e17585. doi:10.1002/aic.17585