Beruflich Dokumente
Kultur Dokumente
Received 11 March 2005; received in revised form 1 June 2005; accepted 2 June 2005
Abstract
The effect of the membrane thickness on the pervaporation separation of methanol and methyl tertiary butyl ether mixtures through
membranes was studied. Membranes of a wide range of thicknesses were prepared from two different polymers: cellulose acetate and
poly(2,6-dimethyl-1,4-phenylene oxide). For each membrane, the experiments were performed at the same feed pressure, feed temperature
and permeate pressure. The results showed that the permeate flux through both membrane types decreased markedly with increasing the
membrane thickness, while the separation factor remained nearly constant. This behavior was discussed in terms of a resistance-in-series
model.
© 2005 Published by Elsevier B.V.
thickness on the separation of water/acetic acid mixtures The main objective of the current study is to investi-
using polysulfone, poly(vinyl chloride) and polyacrylonitrile gate the membrane thickness influence on the pervaporation
membranes. It was observed that the selectivity was indepen- separation of methanol/methyl tertiary butyl ether mixtures.
dent of the membrane thickness above 15 m, but below this Dense membranes with a wide range of thicknesses were pre-
limiting thickness, the selectivity decreased with decreasing pared by using two different polymers: cellulose acetate and
membrane thickness. This dependence, which could not poly(2,6-dimethyl-1,4-phenylene oxide). The pervaporation
be explained by differences in the polymer morphology, behavior for the separation of methanol and methyl tertiary
or by flow coupling, was attributed to the formation of butyl ether from their mixtures was studied in terms of the
induced defects in the membrane during the pervaporation permeation rate and the separation factor. The analysis of the
process. influence of the membrane thickness on the pervaporation
Qunhui et al. [11] studied the influence of the membrane performance was carried out by means of a resistance-in-
thickness on the permselectivity of chitosan membranes, used series model.
for the separation of water/ethanol mixtures. For membranes
with thicknesses lower than 30 m, it was found that the
selectivity increased with the membrane thickness, whereas 2. Experimental
for membranes with thickness higher than 50 m, the mem-
branes exhibited constant selectivities. It was also found that 2.1. Materials
the flux was proportional to the reciprocal of the membrane
thickness. Cellulose acetate (CA) polymer of a molecular weight of
Recently, Kanti et al. [12] studied the effect of the mem- 37,000, with a 39.8% degree of acetylation, was purchased
brane thickness on the permselectivity for the dehydration from Aldrich Chemicals. Poly(2,6-dimethyl-1,4-phenylene
of a mixture of 95.4 wt.% ethanol and 4.6 wt.% water, using oxide) (PPO) powder of an intrinsic viscosity of 1.57 dL/g
blended chitosan/sodium alginate membranes. It was found and a density of 1.04 g/cm3 was supplied by General Electric.
that the flux decreased significantly with the increase in Two solvents were used in this study to prepare the casting
the membrane thickness from 25 to 190 m, whereas the solutions: acetone for CA and chloroform for PPO. To carry
selectivity increased to a lesser extent. The variation of the out the pervaporation experiments, methanol and methyl ter-
selectivity with the membrane thickness was related to the tiary butyl ether (MTBE) of analytical purity grade (97–99%)
existence of a dry layer in the membrane on the permeate side, were used without further purification.
which was responsible of the permselective properties of the
membrane. It was explained that the thickness of this dry 2.2. Membrane preparation
layer increased with the total membrane thickness, causing
a rise in the membrane mass transfer resistance. Therefore, Casting solutions were first prepared by dissolving
the selectivity increased when the membrane thickness was 3.3 wt.% of CA polymer in DMF. The membrane samples
increased. Sridhar et al. [13] observed the same behavior were prepared by pouring a predetermined amount of poly-
for chitosan membranes using mixtures of water and mer solution over a mirror-polished glass plate with a circular
acetamide. edge. The solution was then dried in three steps. First, the bulk
From the above-cited studies, it can be concluded that of the solvent was removed by slow evaporation inside a fume
an optimal membrane thickness is required in order to hood at an average humidity of 30% and at a temperature
obtain a constant selectivity, and below which the selectivity of 23 ◦ C until the membrane was formed. Subsequently, the
decreases with membrane thickness decreasing. Moreover, membrane was kept in an oven at 70 ◦ C during 8 h. Finally,
the flux through the membrane decreases with its thickness the formed membrane was left overnight in a vacuum oven
to a variable extent. at 70 ◦ C to remove the traces of the solvent.
On the other hand, different classes of models for perva- The PPO polymer solution was prepared by using 4 wt.%
poration can be found in the literature. Reviews on perva- in chloroform. Different volumes of PPO solution were
poration models were published by Feng and Huang [4] and spread smoothly over a leveled glass plate inside a stain-
Lipnizki and Trägårdh [14]. One of the models developed to less steel-made O-ring of about 10 cm inner diameter. The
study the mass transport in membranes is the resistance-in- casting ring was then covered with a filter paper to keep out
series approach, which has been used by several researchers of dust. After 24 h at a temperature of 25 ◦ C, the membranes
in pervaporation [15–18]. Basically, this approach considers were removed very cautiously by immersing the glass plate
that the mass transfer from the liquid feed to the permeate in a water bath. The membrane was then dried at 25 ◦ C for
vapor involves four successive steps: (i) a mass transfer from 24 h in a fume hood, and for 72 h in vacuum to remove the
the feed bulk to the feed–membrane interface boundary layer, last traces of solvent.
(ii) a sorption into the membrane, (iii) a mass transport in the The thickness of each membrane was measured by a
membrane matrix and (iv) a desorption to the permeate. Each Millitron micrometer (Mahr Feinpruf 1202 IC) over at least
step is modeled with different approaches, and various fun- 20 different spots, and the mean value was used in this
damental assumptions have been considered. study.
82 J.P.G. Villaluenga et al. / Separation and Purification Technology 47 (2005) 80–87
2.3. Pervaporation experiments some simplifying assumptions have been made: absence
of flow coupling effects, constancy of the diffusivity of the
Pervaporation experiments were performed by using components in the membrane, equilibrium at the membrane
the system described elsewhere [19,20]. It consists of a interfaces and steady-state conditions. Based on the results
separation cell, a circulation pump, two permeate traps, published in previous papers [19,20], the two first assump-
two vacuum pumps and a pressure transducer. The effective tions may seem not to be reasonable in the case of the
membrane pervaporation surface area was 28 cm2 . The feed pervaporation of methanol and MTBE mixtures when PPO
was circulated over the membrane sample. The feed pressure and CA membranes are used; however, the consistency of
was kept near 105 Pa. The permeate stream was evacuated by the results and the model predictions will be used in order to
one of the vacuum pumps, and the permeate was collected in justify the above assumptions.
one of the traps immersed in a filled liquid nitrogen flask. In The model considers that the transport across the system
all the experiments, the downstream pressure was maintained is produced by a gradient of the chemical potential of the feed
less than 133 Pa. After the completion of each experiment, mixture components. Thus, the flux, Ji , of component i can
the permeate collected inside the cold trap was warmed up to be written as
room temperature, and then weighed. The feed and permeate dµi
compositions were determined by measuring their refractive Ji = −Li (2)
dz
index with an Abbey-type refractometer Model 60/ED. The
pervaporation selectivity of the membranes was studied in where dµi /dz is the gradient of chemical potential of compo-
terms of the separation factor, α, which is defined as: nent i and Li is a phenomenological coefficient.
The mass transport of component i from the bulk feed to
wp,i /wp,j
α= (1) the feed membrane interface can be written as:
wb,i /wb,j
Ji = Lbl,i (µb,i − µbl,i ) (3)
where wb and wp are the weight fractions of the components
i and j in the bulk feed and permeate, respectively. Indexes where Lbl,i is the mass transfer coefficient in the boundary
i and j refer to the more permeable component and the less layer formed at the membrane feed side, µb,i is the chemical
permeable one, respectively. potential of component i at the bulk and µbl,i is the chemical
In each experimental run, it was observed that the con- potential of component i at the feed–membrane interface.
centration in the feed solution after the completion of the The transport through the membrane matrix can be
experiment was almost the same as that of the initial feed solu- expressed as:
tion. Therefore, the feed concentrations could be considered
(µmb,i − µmp,i )
constant throughout the experiment. In each experimental Ji = Lm,i (4)
run, at least three samples were collected to determine the l
total flux and the composition of the permeate. The alternative where Lm,i is the mass transfer coefficient of component i in
use of two cold traps allowed a continuous sampling in order the membrane, µmb,i and µmp,i are the chemical potentials of
to avoid interrupting the experiment. It must be mentioned i, in the membrane, at the feed–membrane interface and at
that both membranes exhibited initially high fluxes, which the permeate–membrane interface, respectively and l is the
then gradually reached steady-state values. This behavior is membrane thickness.
due to the conditioning process, which is a time-dependent The transport of component i can also be written as fol-
adaptation of the membrane transport properties because of lows:
the rapidly changed process conditions. This conditioning (µb,i − µp,i )
time, which can last from minutes to several hours, could be Ji = Lov,i (5)
l
explained in terms of the polymer relaxation. All data given in
the present paper correspond to the final steady-state values. where Lov,i is the overall mass transfer coefficient of compo-
In this study, the pervaporation experiments were con- nent i, and µb,i and µp,i are the chemical potentials at the bulk
ducted at a feed temperature of 25 ◦ C using; as feed, binary and at the permeate, respectively. If equilibrium conditions
mixtures of methanol/MTBE with a 21 wt.% of methanol, in are assumed at both membrane interfaces, the following rela-
the case of the CA membranes and 47 wt.% methanol, in the tionship between the transport coefficients can be obtained
case of the PPO membranes, were employed. from Eqs. (3) to (5):
1 1 1
= + (6)
Lov,i lLbl,i Lm,i
3. Theory
Following Raghunath and Hwang [15], it is of practical
As previously mentioned, the resistance-in-series interest to write Eq. (6) in terms of typical transport coef-
approach considers that the mass transfer of a mixture, ficients often employed in pervaporation. In Eq. (2), the
from the feed bulk to the permeate, takes place in four chemical potential difference may be related to the differ-
successive steps. In order to make the model more useful, ences in pressure, temperature, concentration and electrical
J.P.G. Villaluenga et al. / Separation and Purification Technology 47 (2005) 80–87 83
potential. In the case of pervaporation, where the driving force In various pervaporation studies [15,21], it was shown that
is generated by concentration and pressure gradients, the fol- second term of the right-hand side is negligible.
lowing equation is applied: In pervaporation, the overall flux is expressed in terms of
the fugacity difference between the bulk feed and the perme-
dµi = RT d ln(γi xi ) + vi dp (7) ate as follows [22]:
where xi is the mole fraction of i, γ i the activity coefficient,
fb,i − fp,i (psat γi xb,i − p2 xp,i )
vi the molar volume of component i and p is the pressure. In Ji = Qi = Qi i (16)
the case of a liquid, the integration of Eq. (7) gives l l
where Qi is the overall or apparent permeability of component
µi = µoi + RT ln(γi xi ) + vi (p − psat
i ) (8)
i, and fb,i and fp,i are the fugacities of component i at the bulk
where µoi is the chemical potential of pure i at a reference and at the permeate, respectively.
pressure, which is defined as the saturation vapor pressure, From Eqs. (15) and (16), under the assumptions discussed
psat
i . The following equation may be obtained from Eqs. (2)
above, it can be obtained that
and (8),
pi Qi
Lov,i = (17)
Li RT dxi dp RT
Ji = − − Li v i (9)
xi dz dz
where
If the solution–diffusion model [21] is considered, this
equation can be applied within the membrane limits, and the i γi x
(psat b,i − pp xp,i )
pi = (18)
γx
following expression is obtained: ln xi p,ib,i
Lm,i RT xmb,i
Ji = ln (10) Finally, Eq. (6) can be rewritten as follows:
l xmp,i
1 pi pi
where xmb,i and xmp,i are the mole fractions of i in the = + (19)
membrane, at the feed–membrane interface and at the Qi RTLbl,i l Di cm,i
membrane–permeate interface, respectively.
This equation can be expressed in a more practical form
If the diffusion of compounds in the membrane is Fickian
with a diffusion coefficient independent of the concentration, 1 1 1
it can be written = + (20)
Qi ki l D i S i
(xmb,i − xmp,i )
Ji = ρm Di (11) where
l
where Di is the diffusion coefficient of component i in the RTLbl,i
ki = (21)
membrane and ρm is the membrane density. The comparison pi
of Eqs. (10) and (11) gives cm,i
Si = (22)
cm,i Di pi
Lm,i = (12)
RT
where ki is the mass transfer coefficient in the boundary layer
where with respect to the fugacity difference and Si is the solu-
ρm (xmb,i − xmp,i ) bility coefficient of component i in the membrane. Eq. (20)
cm,i = (13) shows that the apparent permeability varies with the mem-
ln(xmb,i /xmp,i )
brane thickness when the boundary layer contributes to the
On the other hand, by using Eq. (8) the difference in the mass transport of compounds. In addition, by plotting the
chemical potential between the bulk feed and permeate may inverse permeability as a function of the inverse membrane
be expressed as follows: thickness, a straight line should be obtained. From the slope
of the line ki can be calculated, and from the intercept Di Si
γi xb,i
µb,i − µp,i = RT ln + vi (p1 − p2 ) (14) can be estimated. It is worth quoting that Di Si is the intrin-
xp,i sic permeability of component i in the membrane (Pm,i ). An
where xb,i and xp,i are the mole fractions of i at the bulk and interesting additional finding can be obtained from Eq. (20)
at the permeate, respectively, and p1 and p2 are, respectively, by considering that the overall mass transfer resistance of
the pressure at the feed and permeate. Using Eq. (14), Eq. (5) component i (Rov,i = l/Qi ) consists of the sum of the resistance
can be rewritten as follows: in the liquid boundary layer (Rbl,i = 1/ki ) and a membrane
resistance (Rm,i = l/Pm,i ). Thus, it can be noticed that the so-
Lov,i RT γi xb,i vi
Ji = ln + (p1 − p2 ) (15) defined overall mass resistance coefficient depends on the
l xp,i RT membrane thickness.
84 J.P.G. Villaluenga et al. / Separation and Purification Technology 47 (2005) 80–87
thinnest membrane (20 m) than for the thickest one (96 m).
In addition, as observed for PPO membranes, it was also
checked that the fluxes were proportional to the inverse of
the membrane thickness with correlation coefficients higher
than 0.98.
It can be observed in Figs. 1 and 2 that the overall perme-
ation flux through the PPO membranes is greater than that of
the CA membranes. Based on the solution–diffusion model,
the permeability of the membranes is determined by the sol-
ubility and diffusivity of permeants in the membranes. It was
shown in previous papers [19,20] that the liquid sorption of
PPO was larger than that of CA due to the higher affinity
of the PPO membranes towards the liquid mixture than that
of CA. This makes PPO membrane to swell more than CA
membrane. Because of the higher swelling, the diffusivity of
permeants in the PPO membrane was larger than in the CA
membrane. Consequently, the higher flux observed for the
Fig. 1. Overall and partial fluxes of methanol and MTBE as a function of
PPO membrane is due to the greater solubility and diffusiv-
the membrane thickness for PPO membranes.
ity of the permeants. On the other hand, in the present study, it
4. Results and discussion is also observed that the MTBE flux of CA membranes is two
orders of magnitude lower than that of methanol. This indi-
Fig. 1 shows the data on the overall flux, and the methanol cates that the selectivity of CA membranes is higher than that
and MTBE fluxes through PPO membranes, as a function of of PPO membranes, although both PPO and CA membranes
the membrane thickness. The composition of the feed solu- are methanol selective. In Fig. 3, the separation factors of both
tion was the same in all cases, i.e. a 47 wt.% methanol in a membrane types are presented as a function of the membrane
methanol/MTBE mixture. Both the overall flux and the partial thickness. There is no clear tendency between the separation
fluxes of methanol and MTBE decreased with the membrane factor and the membrane thickness within experimental error.
thickness. For example, the overall flux obtained when using It seems that the separation factor is about 2.1 for PPO mem-
the thinnest membrane (28 m) is approximately twice that branes and around 192 for CA membranes. It was found [20]
of the thickest membrane (126 m). It was also observed that that the higher separation factor of CA membranes was due
plots of fluxes versus the reciprocal of the membranes thick- to the combination of both high sorption and diffusion selec-
ness gave straight lines with correlation coefficients higher tivities. In contrast, the lower separation factor exhibited by
than 0.99. Fig. 2 presents the results of the overall, methanol the PPO membranes was due to a low sorption selectivity as
and MTBE fluxes, obtained using CA membranes of differ- it was reported elsewhere [19].
ent thicknesses. The feed was a mixture of methanol and As stated earlier, the data given in Figs. 1–3 were ana-
MTBE with 21 wt.% of methanol. Both the overall flux and lyzed by using the resistance-in-series approach developed
the component fluxes decreased with membrane thickness. in the preceding section. First, the values of Qi were calcu-
The overall flux, as an example, is about twice that of the lated from Eq. (16). Data on the mole fractions of methanol
Fig. 2. Overall and partial fluxes of methanol and MTBE as a function of Fig. 3. Separation factor in pervaporation of methanol/MTBE mixtures
the membrane thickness for CA membranes. through PPO and CA membranes.
J.P.G. Villaluenga et al. / Separation and Purification Technology 47 (2005) 80–87 85
Table 1
Constant values in Eq. (23) for methanol and MTBE
a1 a2 a3 a4
Methanol −8.54796 0.76982 −3.1085 1.54481
MTBE −7.82516 2.95493 −6.94079 12.17416
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